CN113817388A

CN113817388A - Liquid containing conductive polymer, conductive film, conductive laminate, and method for producing same

Info

Publication number: CN113817388A
Application number: CN202010559049.6A
Authority: CN
Inventors: 市川宗树; 松林总
Original assignee: Shin Etsu Polymer Co Ltd
Current assignee: Shin Etsu Polymer Co Ltd; Shin Etsu Chemical Co Ltd
Priority date: 2020-06-18
Filing date: 2020-06-18
Publication date: 2021-12-21

Abstract

The liquid containing a conductive polymer contains a conductive complex and an organic solvent, the conductive complex contains a pi-conjugated conductive polymer and a polyanion, a part of anionic groups of the polyanion has a substituent (A) formed by a reaction with an epoxy group-containing compound and a substituent (B) formed by a reaction with an amine compound, and the organic solvent preferably contains 1 or more selected from ester solvents and hydrocarbon solvents.

Description

Liquid containing conductive polymer, conductive film, conductive laminate, and method for producing same

Technical Field

The present invention relates to a conductive polymer-containing liquid containing a pi-conjugated conductive polymer and a method for producing the same, a conductive film having a cured layer of the conductive polymer-containing liquid and a method for producing the same, and a conductive laminate having a glass layer on the cured layer and a method for producing the same.

Background

As a coating material for forming the conductive layer, an aqueous dispersion of a conductive polymer obtained by doping poly (3, 4-ethylenedioxythiophene) with polystyrenesulfonic acid can be used.

Typically, the film substrate coated with the conductive layer comprises a hydrophobic plastic film. Therefore, the aqueous conductive polymer dispersion as an aqueous coating material tends to have low adhesion to a film substrate. Further, since the drying time of the aqueous conductive polymer dispersion is long, the productivity of forming the conductive layer tends to be low.

Therefore, a conductive polymer organic solvent dispersion obtained by replacing water as a dispersion medium of the conductive polymer aqueous dispersion with an organic solvent can be used.

As an organic solvent dispersion liquid of a conductive polymer, there is known a conductive polymer dispersion liquid obtained by freeze-drying an aqueous dispersion liquid of a conductive polymer containing a conductive complex composed of a pi-conjugated conductive polymer and a polyanion to obtain a dried product, and then adding an organic solvent and an amine compound to the dried product (patent document 1).

However, when an addition-curable silicone is added to a conductive polymer organic solvent dispersion liquid in order to make a conductive layer exhibit releasability, the presence of an amine compound may inhibit the curing of the addition-curable silicone. Therefore, when an addition-curable silicone is added to a conductive polymer organic solvent dispersion liquid using an amine compound, there is a problem that the conductive release film is difficult to cure.

As a measure against the above problem, it is known that a conductive polymer organic solvent dispersion is obtained by adding a cyclic ether compound having at least one of an ethylene oxide group and a propylene oxide group to a conductive polymer aqueous dispersion containing a conductive composite composed of a pi-conjugated conductive polymer and a polyanion (patent document 2). In the method described in patent document 2, an anionic group not doped in a pi-conjugated conductive polymer is reacted with an ethylene oxide group or a propylene oxide group of a cyclic ether compound to make the polymer hydrophobic, whereby the conductive composite is made organic solvent-dispersible.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-032382

Patent document 2: international publication No. 2014/125827

Disclosure of Invention

Problems to be solved by the invention

However, in the method described in patent document 2, the dispersibility of the conductive composite in the silicone solution may be insufficient.

However, an ester solvent such as ethyl acetate is industrially important because it can be mixed with a plurality of organic solvents such as alcohols, ethers, aromatic compounds, hydrocarbons and the like at an arbitrary ratio, and is often quick-drying, low-odor, and low-toxicity. For example, the resin composition is often used as a material for printing ink, adhesive, coating paint, and the like.

On the other hand, as disclosed in patent documents 1 to 2, even a conductive composite obtained by hydrophobization in such a manner as to be dissolved in an organic solvent such as toluene is not dissolved in an ester-based solvent, and has a problem that separation is performed within several minutes even when dispersed by a high-pressure homogenizer. Therefore, there is a problem that it is difficult to add and use the conductive composite to the raw material containing the ester-based solvent.

The invention provides a liquid containing a conductive polymer, which has excellent dispersibility in an organic silicon solution and can stably disperse even in an ester solvent guide such as ethyl acetate, a conductive film having a cured layer of the liquid containing the conductive polymer, a method for manufacturing the conductive film, a conductive laminate having a glass layer on the cured layer, and a method for manufacturing the conductive laminate.

Means for solving the problems

[1] A liquid containing a conductive polymer, which contains a conductive complex and an organic solvent, wherein the conductive complex contains a pi-conjugated conductive polymer and a polyanion, and the polyanion is a reaction product of part of anionic groups of the polyanion, an epoxy group-containing compound, and an amine compound.

[2] The liquid containing a conductive polymer according to [1], wherein the organic solvent contains an ester group-containing compound.

[3] The liquid containing a conductive polymer according to [1] or [2], wherein the organic solvent contains 1 or more selected from ester group-containing compounds represented by the following formula 1,

formula 1: r²¹-C(＝O)-O-R²²

[ in the formula, R²¹Represents a hydrogen atom, a methyl group or an ethyl group, R²²Represents a linear or branched alkyl group having 1 to 6 carbon atoms]。

[4] The liquid containing a conductive polymer according to any one of [2] or [3], wherein the content of the ester group-containing compound is 40% by mass or more based on the total mass of the organic solvent.

[5] The liquid containing a conductive polymer according to any one of [1] to [4], wherein the organic solvent contains a hydrocarbon solvent.

[6] The liquid containing a conductive polymer according to [5], wherein the hydrocarbon solvent is at least one selected from heptane and toluene.

[7] The liquid containing a conductive polymer according to [5] or [6], wherein the content of the hydrocarbon solvent is 40% by mass or more based on the total mass of the organic solvent.

[8] The liquid containing a conductive polymer according to any one of [1] to [7], wherein the organic solvent contains methyl ethyl ketone.

[9] The liquid containing a conductive polymer according to any one of [1] to [8], wherein the pi-conjugated conductive polymer is poly (3, 4-ethylenedioxythiophene).

[10] The liquid containing a conductive polymer according to any one of [1] to [9], wherein the polyanion is polystyrene sulfonic acid.

[11] The liquid containing a conductive polymer according to any one of [1] to [10], wherein the epoxy group-containing compound has 4 or more carbon atoms.

[12] The liquid containing a conductive polymer according to any one of [1] to [11], wherein the amine compound has a substituent having 4 or more carbon atoms on a nitrogen atom.

[13] The liquid containing a conductive polymer according to any one of [1] to [12], further comprising a binder component.

[14] The liquid containing a conductive polymer according to [13], wherein the adhesive component is an organosilicon compound.

[15] The liquid containing a conductive polymer according to [14], wherein the organosilicon compound is an addition-curable organosilicon.

[16] The liquid containing a conductive polymer according to [13], wherein the adhesive component is an acrylic adhesive, a silicone adhesive or a urethane adhesive.

[17] The liquid containing a conductive polymer according to [16], wherein the adhesive component is an acrylic adhesive.

[18] A method for producing a liquid containing a conductive polymer, comprising: a precipitate recovery step of adding an epoxy group-containing compound and an amine compound to an aqueous conductive polymer dispersion containing a conductive complex in an aqueous dispersion medium, the conductive complex containing a pi-conjugated conductive polymer and a polyanion, and then recovering a precipitate; and an organic solvent addition step of adding an organic solvent to the precipitate to obtain a preparation solution.

[19] The method for producing a liquid containing a conductive polymer according to [18], further comprising a washing step of washing the precipitate with an organic solvent for washing between the precipitate collection step and the organic solvent addition step.

[20] The method for producing a liquid containing a conductive polymer according to [18] or [19], wherein the organic solvent contains an ester group-containing compound.

[21] The method for producing a liquid containing a conductive polymer according to any one of [18] to [20], wherein the organic solvent contains 1 or more selected from ester group-containing compounds represented by the following formula 1,

formula 1: r²¹-C(＝O)-O-R²²

[22] The method for producing a liquid containing a conductive polymer according to [20] or [21], wherein a content of the ester group-containing compound is 40% by mass or more based on a total mass of the organic solvent.

[23] The method for producing a liquid containing a conductive polymer according to any one of [18] to [22], wherein the organic solvent contains a hydrocarbon-based solvent.

[24] The method for producing a liquid containing a conductive polymer according to [23], wherein the hydrocarbon solvent is at least one selected from heptane and toluene.

[25] The method for producing a liquid containing a conductive polymer according to [23] or [24], wherein a content of the hydrocarbon solvent is 40% by mass or more based on a total mass of the organic solvent.

[26] The method for producing a liquid containing a conductive polymer according to any one of [18] to [25], wherein the organic solvent contains methyl ethyl ketone.

[27] The method for producing a liquid containing a conductive polymer according to any one of [18] to [26], further comprising a step of adding an adhesive component to the preparation liquid.

[28] The method for producing a liquid containing a conductive polymer according to [27], wherein the adhesive component is an acrylic adhesive, a silicone adhesive, a urethane adhesive, a curable silicone or an ultraviolet curable acrylic resin.

[29] A method for producing a conductive film, comprising: a step of applying the liquid containing a conductive polymer according to any one of [1] to [17] onto at least one surface of a film base material to form a coating film; and a step of forming a conductive layer by drying the coating film.

[30] A method for producing a conductive laminate, comprising: applying the liquid containing a conductive polymer comprising the acrylic pressure-sensitive adhesive, the silicone pressure-sensitive adhesive, or the urethane pressure-sensitive adhesive according to [16] onto at least one surface of a film substrate to form a coating film; a step of forming a conductive layer by drying the coating film; and a step of bonding a glass layer to the conductive layer.

[31] A conductive film comprising a conductive layer on at least one surface of a film base, wherein the conductive layer comprises a cured layer of the liquid containing a conductive polymer according to any one of [1] to [17 ].

[32] A conductive laminate comprising a conductive layer on at least one surface of a film base, wherein the conductive layer comprises a cured layer of the liquid containing a conductive polymer comprising the acrylic-based adhesive, the silicone-based adhesive, or the urethane-based adhesive according to [16], and the conductive layer has a glass layer on the surface thereof.

Effects of the invention

The liquid containing a conductive polymer of the present invention is a liquid in which a conductive complex is stably dispersed in an organic solvent, particularly a hydrocarbon solvent such as toluene or an ester solvent such as ethyl acetate. Thus, the composition is suitable for use as a coating material, use in which the composition is mixed with other raw materials including hydrocarbon solvents and ester solvents, and the like. When used as a paint, a conductive layer having excellent conductivity can be easily formed.

The liquid containing a conductive polymer of the present invention can easily form a conductive layer having excellent dispersibility in a silicone solution and excellent conductivity.

According to the method for producing a liquid containing a conductive polymer of the present invention, a liquid containing a conductive polymer having the above-described effects can be easily produced.

According to the method for producing a conductive film of the present invention, a conductive film having a conductive layer excellent in conductivity can be easily formed.

According to the method for producing a conductive laminate of the present invention, a conductive laminate having a conductive layer with excellent conductivity can be easily formed.

The present invention is believed to contribute to the "manufacturing responsibility, usage responsibility" of the SDGs target 12.

In the present specification and claims, the lower limit value and the upper limit value of a numerical range represented by "-" are included in the numerical range.

Detailed Description

Liquid containing conductive polymer

A first aspect of the present invention is a liquid containing a conductive polymer, which contains a conductive complex and an organic solvent, wherein the conductive complex contains a pi-conjugated conductive polymer and a polyanion.

In the liquid containing a conductive polymer of this embodiment, the conductive complex may be in a dispersed state or a dissolved state.

< pi conjugated conductive Polymer

The effect of the present invention is not particularly limited as long as the pi-conjugated conductive polymer is an organic polymer having a main chain composed of pi-conjugated, and examples thereof include polypyrrole conductive polymers, polythiophene conductive polymers, polyacetylene conductive polymers, polyphenylene vinylene conductive polymers, polyaniline conductive polymers, polyacene conductive polymers, polythiophene vinylene conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophene-based conductive polymers, 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-di (dodecyloxy) thiophene), 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-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene).

Examples of the polypyrrole-based conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-ethylpyrrole), poly (3-N-propylpyrrole), poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3, 4-dimethylpyrrole), poly (3, 4-dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), Poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole).

Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), and poly (3-anilinesulfonic acid).

Among the above-mentioned pi-conjugated conductive polymers, poly (3, 4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity, transparency and heat resistance.

The number of the pi-conjugated conductive polymers contained in the conductive composite may be 1, or 2 or more.

< polyanion >

A polyanion refers to a polymer having 2 or more monomer units having an anionic group in the molecule. The anionic group of the polyanion functions as a dopant in the pi-conjugated conductive polymer, and improves the conductivity of the pi-conjugated conductive polymer.

The anionic group of the polyanion is preferably a sulfo group or a carboxyl group.

Specific examples of such polyanions include polymers having a sulfo group such as polystyrenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyacrylate having a sulfo group, polymethacrylate having a sulfo group (for example, poly (4-sulfobutyl methacrylate), sulfoethyl polymethacrylate, polymethacryloxybenzenesulfonic acid), poly (2-acrylamide-2-methylpropanesulfonic acid), and polyisoprene sulfonic acid; polymers having a carboxyl group such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly (2-acrylamide-2-methylpropionic acid), and polyisoprene carboxylic acid. These may be homopolymers or 2 or more kinds of copolymers.

Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, from the viewpoint of further improving the conductivity.

The polyanion constituting the conductive composite may be 1 species or 2 or more species.

The mass average molecular weight of the polyanion is preferably 2 to 100 ten thousand, more preferably 10 to 50 ten thousand. The mass average molecular weight is a mass-based average molecular weight determined in terms of polystyrene by gel permeation chromatography.

The polyanion is doped in a pi-conjugated conductive polymer to form a conductive complex. However, in the polyanion, some of the anionic groups are not doped in the n-conjugated conductive polymer, and the remaining anionic groups that are not involved in the doping are present. Since the remaining anionic groups are hydrophilic groups, the conductive composite has high water dispersibility and low organic solvent dispersibility in a state before reaction with the epoxy group-containing compound and the amine compound, as described later.

When the number of all anionic groups of the polyanion is 100 mol%, the remaining anionic groups are preferably 30 mol% or more and 90 mol% or less, and more preferably 45 mol% or more and 75 mol% or less.

The polyanion of the present invention is a reactant of the remaining anionic groups (hereinafter referred to as "partial anionic groups") that the polyanion has not participated in doping with the epoxy group-containing compound and the amine compound. That is, the polyanion of the present invention has a substituent (a) formed by the reaction of the epoxy group-containing compound with a part of the anionic groups and a substituent (B) formed by the reaction of the amine compound with a part of the anionic groups.

(substituent A)

The detailed analysis of the conductive composite is not always easy, but the substituent (a) is assumed to be a group represented by the following formula (a1) or a group represented by the following formula (a 2).

[ chemical formula 1]

[ in the formula (A1), R¹、R²、R³And R⁴Each independently is a hydrogen atom or an optional substituent]。

[ chemical formula 2]

[ in the formula (A2), m is an integer of 2 or more, and R's are plural⁵A plurality of R⁶A plurality of R⁷And a plurality of R⁸Each independently is a hydrogen atom or an optional substituent, a plurality of R⁵A plurality of R, which may be the same or different⁶Can be combined withSame or different, a plurality of R⁷A plurality of R, which may be the same or different⁸May be the same or different]。

In the formulae (a1) and (a2), the left bond indicates that the substituent (a) is substituted with a proton of an anionic group. Examples of the substituted anionic group having a proton include "-SO₃H "thus has an anionic group bonded to an active proton of an oxygen atom.

In the formula (A1), R is¹、R²、R³And R⁴Examples of the optional substituent(s) include an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent(s), an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent(s), and the like. R¹And R³May be bonded to form a ring which may have a substituent. For example, R may be mentioned¹And R³For the above hydrocarbon group, R is removed¹A 2-valent hydrocarbon group obtained by removing R from any 1 hydrogen atom of the 1-valent hydrocarbon group of (1)³The 2-valent hydrocarbon group obtained by removing any 1 hydrogen atom from the 1-valent hydrocarbon group in (1), may form a ring by bonding carbon atoms of the hydrogen atoms to each other.

In the formula (A2), R is⁵、R⁶、R⁷And R⁸Examples of the optional substituent(s) include an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent(s), an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent(s), and the like. R⁵And R⁷May be bonded to form a ring which may have a substituent. Examples of the ring formation are the same as those described above.

In the present specification, "may have a substituent" is meant to include the case where a hydrogen atom (-H) is substituted with a 1-valent group and a methylene group (-CH)₂-) both of which are substituted with a 2-valent group.

Examples of the 1-valent group as a substituent include an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a trialkoxysilyl group (e.g., a trimethoxysilyl group), and the like.

Examples of the substituent include an oxygen atom (-O-), -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 not less than the lower limit, the hydrophobicity of the conductive composite is sufficiently improved. If m is equal to or less than the upper limit, the hydrophobicity can be prevented from becoming too high or the conductivity can be prevented from decreasing.

The epoxy group-containing compound is a compound (epoxy compound) having 1 or more epoxy groups in 1 molecule. The epoxy group-containing compound is preferably a compound having 1 epoxy group in 1 molecule in terms of preventing aggregation or gelation.

The epoxy group-containing compound that reacts with the conductive composite may be 1 kind or 2 or more kinds.

Examples of the monofunctional epoxy group-containing compound having 1 epoxy group in 1 molecule include ethylene oxide, propylene oxide, 2, 3-epoxybutane, isobutylene oxide, 1, 2-epoxybutane, 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-epoxyoctadecane, 1, 2-epoxyhexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1, 2-epoxyeicosane, 2- (chloromethyl) -1, 2-epoxypropane, glycidyl, epichlorohydrin, epoxy propane, and the like, Propylene oxide bromide, 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, tetracyanooxirane, 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-heptadecafluorobutane, 3, 4-epoxytetrahydrofuran, glycidyl stearate, 3-glycidoxypropyltrimethoxysilane, epoxysuccinic acid, glycidyl phenyl ether, isophorone oxide, alpha-pinene oxide, 2, 3-epoxynorbornene, benzyl glycidyl ether, diethoxy (3-glycidoxypropyl) methylsilane, 3- [2- (perfluorohexylene)Yl) ethoxy]-1, 2-propylene oxide, 1,1,1,3,5,5, 5-heptamethyl-3- (3-glycidoxypropyl) trisiloxane, 9, 10-epoxy-1, 5-cyclododecadiene, 4-tert-butyl-phenylformic acid glycidyl ester, 2-bis (4-glycidoxyphenyl) propane, 2-tert-butyl-2- [2- (4-chlorophenyl)]Ethyl oxetane, styrene oxide, glycidyl triphenylmethyl ether, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5 alpha, 6 alpha-epoxide, oxidation

Glycidyl p-toluenesulfonate, ethyl 3-methyl-3-phenylglycidoate, N-propyl-N- (2, 3-epoxypropyl) perfluoro-N-octanesulfonamide, (2S,3S) -1, 2-epoxy-3- (tert-butoxycarbonylamino) -4-phenylbutane, 3-nitrobenzenesulfonic acid (R) -glycidyl ester, 3-nitrobenzenesulfonic acid-glycidyl ester, parthenolide, N-glycidylphthalimide, endrin, dieldrin, 4-glycidyloxycarbazole, 7-dimethyloctanoic acid [ oxiranylmethyl]Esters, 1, 2-epoxy-4-vinylcyclohexane, higher alcohol glycidyl ethers having 10 to 16 carbon atoms, and the like.

The higher alcohol glycidyl ether is preferably 1 or more of higher alcohol glycidyl ethers having 10 to 16 carbon atoms, more preferably 1 or more of higher alcohol glycidyl ethers having 12 to 14 carbon atoms, still more preferably at least 1 of higher alcohol glycidyl ethers having C12 (12 carbon atoms) and higher alcohol glycidyl ethers having C13 (13 carbon atoms), and particularly preferably a mixed higher alcohol glycidyl ether having C12 and C13.

Examples of the polyfunctional epoxy group-containing compound having 2 or more epoxy groups in 1 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 ester, triglycidyl isocyanurate, neopentyl glycol diglycidyl ether, 1,2:3, 4-diepoxybutane, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane polyglycidyl ether, hydrogenated bisphenol a diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, and the like.

The molecular weight of the epoxy group-containing compound is preferably 50 or more and 2,000 or less from the viewpoint of improving dispersibility in an organic solvent. In addition, from the viewpoint of high dispersibility in a low-polarity hydrocarbon-based solvent or ester-based solvent, the number of carbon atoms of the epoxy group-containing compound is preferably 4 or more and 120 or less, more preferably 7 or more and 100 or less, further preferably 10 or more and 80 or less, and particularly preferably 15 or more and 50 or less.

(substituent B)

The detailed analysis of the conductive composite is not always easy, but the substituent (B) is assumed to be a group represented by the following formula (B).

-HN⁺R¹¹R¹²R¹³···(B)

[ in the formula (B), R¹¹～R¹³Each independently is a hydrogen atom or a hydrocarbon group which may have a substituent, wherein R¹¹～R¹³At least 1 of them is a hydrocarbon group which may have a substituent]。

In the substituent (B), the left bond indicates that the negative charge of the anionic group is bonded to the positive charge of the amine compound. Examples of the anionic group capable of being negatively charged include "-SO₃ ^-"thus, an anionic group having an active proton bonded to an oxygen atom is provided.

R in the formula (B)¹¹～R¹³Is a hydrogen atom or a hydrocarbon group which may have a substituent. R in the formula (B)¹¹～R¹³Are substituents derived from amine compounds described later.

Examples of the hydrocarbon group in the formula (B) include 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.

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 for 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 1 selected from the group consisting of primary amines, secondary amines, and tertiary amines. The amine compound to be reacted with the conductive complex may be 1 kind or 2 or more kinds.

Examples of the primary amine include aniline, toluidine, benzylamine, and ethanolamine.

Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, and dinaphthylamine.

Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine.

Among the amine compounds, a tertiary amine is preferable, and at least one of trioctylamine and tributylamine is more preferable, from the viewpoint of enabling the conductive polymer-containing liquid of the present embodiment to be easily produced.

From the viewpoint of improving dispersibility in an organic solvent, particularly in a low-polarity hydrocarbon-based solvent or ester-based solvent, the amine compound preferably has a substituent having 4 or more carbon atoms on a nitrogen atom, more preferably has a substituent having 6 or more carbon atoms, and still more preferably has a substituent having 8 or more carbon atoms on a nitrogen atom.

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, more preferably 20:80 to 80:20, and further preferably 25:75 to 75: 25. When the A/B ratio is in the above range, the balance between dispersibility and conductivity can be easily obtained. The mass of [ substituent (a) ] can be calculated from [ (mass of the reactant a obtained by reacting the epoxy-containing compound with the conductive composite body) - (mass of the conductive composite body before the reaction with the epoxy-containing compound) ]. The mass of [ anionic group to which substituent (B) is bonded ] can be calculated from [ (mass of reactant B obtained by reacting reactant a with the amine compound) - (mass of reactant a obtained by reacting the epoxy-containing compound with the conductive composite) ].

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, more preferably 10 parts by mass or more and 700 parts by mass or less, and still more preferably 100 parts by mass or more and 500 parts by mass or less, with respect to 100 parts by mass of the pi-conjugated conductive polymer. When the content of the polyanion is not less than the lower limit, the doping effect in the pi-conjugated conductive polymer tends to be strong, and the conductivity tends to be further increased. On the other hand, if the content of the polyanion is not more than the above upper limit, the amount of anionic groups not participating in doping is appropriately suppressed, and the compound containing an epoxy group and the amine compound can be easily converted into hydrophobic groups when they react with the anionic groups.

The content of the conductive composite with respect to the total mass of the liquid containing a conductive polymer is, for example, preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.2% by mass or more and 10% by mass or less, still more preferably 0.3% by mass or more and 10.0% by mass or less, and particularly preferably 1.0% by mass or more and 5.0% by mass or less.

< organic solvent >

Examples of the organic solvent contained in the liquid containing a conductive polymer of the present embodiment include ester solvents, hydrocarbon solvents, ketone solvents, alcohol solvents, nitrogen atom-containing compound solvents, and the like.

The number of the organic solvents contained in the liquid containing a conductive polymer of this embodiment may be 1, or 2 or more.

The ester solvent is an ester group-containing compound having an ester group (-C (═ O) -O-).

When the organic solvent contains an ester-based solvent (ester-based compound), it is preferable to contain 1 or more kinds of ester-based compounds represented by the following formula 1 from the viewpoint of improving dispersibility of the conductive composite in the conductive polymer-containing liquid of the present embodiment.

Formula 1: r²¹-C(＝O)-O-R²²

From the viewpoint of improving the dispersibility of the conductive composite of this embodiment, R is²¹Preferably methyl or ethyl, more preferably methyl. Furthermore, R²²The number of carbon atoms of (A) is preferably 2 to 5, more preferably 2 to 4.

Suitable specific examples of the ester group-containing compound include ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, and the like.

The content of the ester group-containing compound contained in the organic solvent is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and may be 100% by mass, based on the total mass of the organic solvent. When the content of the ester group-containing compound is within the above range, the dispersibility of the conductive composite can be improved.

When the liquid containing a conductive polymer of the present embodiment contains an ester-based solvent, the liquid may further contain 1 or more kinds of organic solvents other than the ester-based solvent.

Examples of the organic solvent other than the ester-based organic solvent include hydrocarbon solvents, ketone solvents, alcohol solvents, nitrogen atom-containing compound solvents, and the like.

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, and isopropylbenzene.

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 nitrogen atom-containing compound solvent include N-methylpyrrolidone, dimethylacetamide, and dimethylformamide.

If the liquid containing a conductive polymer of the present embodiment contains a hydrocarbon-based solvent, the liquid containing a conductive polymer has high wettability to the plastic film substrate, and a low-polarity adhesive component can be easily added, which is preferable.

When the liquid containing a conductive polymer of the present embodiment contains a hydrocarbon-based solvent, examples of the hydrocarbon-based solvent include an aliphatic hydrocarbon-based solvent and an aromatic hydrocarbon-based solvent. 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, and isopropylbenzene.

Among them, toluene is preferred from the viewpoint of general use. When an organic silicon compound is added as an adhesive component, at least one of heptane and toluene is preferable from the viewpoint of excellent solubility of the organic silicon compound.

If methyl ethyl ketone is contained in addition to the hydrocarbon-based solvent, the dispersibility of the conductive composite is further improved, which is preferable. For example, methyl ethyl ketone is preferably 20 parts by mass or more and 120 parts by mass or less, more preferably 30 parts by mass or more and 100 parts by mass or less, and still more preferably 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the hydrocarbon-based solvent.

The content of the hydrocarbon-based solvent is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and may be 100% by mass, based on the total mass of the organic solvent. When the content of the hydrocarbon solvent is within the above range, the dispersibility of the conductive composite can be improved.

When the liquid containing a conductive polymer of the present embodiment contains a hydrocarbon-based solvent, the liquid may further contain 1 or more kinds of organic solvents other than the hydrocarbon-based solvent.

Examples of the organic solvent other than the hydrocarbon solvent include the ketone solvent, alcohol solvent, ester solvent, and nitrogen atom-containing compound solvent.

< adhesive component >

The liquid containing a conductive polymer of this embodiment may contain a binder component. By using a liquid containing a conductive polymer containing a binder component, the strength of the formed conductive layer can be improved or releasability can be imparted.

The binder component is a resin or a precursor thereof other than the pi-conjugated conductive polymer and the polyanion, and is a thermoplastic resin or a curable monomer or oligomer that is cured when the conductive layer is formed. The thermoplastic resin directly becomes the adhesive resin, and the resin formed by curing the curable monomer or oligomer becomes the adhesive resin.

The adhesive component may be an adhesive agent described later.

The binder component contained in the liquid containing a conductive polymer of this embodiment may be 1 type or 2 or more types.

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

The curable monomer or oligomer may be a thermosetting monomer or oligomer, or may be a photocurable monomer or oligomer. Here, the oligomer is a polymer having a mass average molecular weight of less than 1 ten thousand.

Examples of the curable monomer include an acrylic monomer (acrylic compound), an epoxy monomer, and an organosiloxane. Examples of the curable oligomer include an acrylic oligomer (acrylic compound), an epoxy oligomer, and a silicone oligomer (curable silicone).

In the case of using an acrylic monomer or an acrylic oligomer as the adhesive component, it can be easily cured by heating or light irradiation.

When the curable monomer or oligomer is contained, it is preferable to further contain a curing catalyst. For example, in the case of a thermosetting monomer or oligomer, a thermal polymerization initiator that generates radicals by heating is preferably included, and in the case of a photocurable monomer or oligomer, a photopolymerization initiator that generates radicals by light irradiation is preferably included.

The content ratio of the adhesive component (excluding the organic silicon compound described later) contained in the liquid containing a conductive polymer of the present embodiment may be, for example, 10 parts by mass or more and 10000 parts by mass or less, preferably 100 parts by mass or more and 5000 parts by mass or less, more preferably 200 parts by mass or more and 3000 parts by mass or less, and further preferably 300 parts by mass or more and 1500 parts by mass or less with respect to 100 parts by mass of the conductive composite.

If the lower limit value of the above range is not less than the lower limit value, the film strength of the conductive layer formed by the liquid containing a conductive polymer of the present embodiment can be sufficiently improved.

If the amount is less than or equal to the upper limit of the above range, sufficient conductivity of the conductive layer formed by the liquid containing a conductive polymer of the present embodiment can be ensured.

(organic silicon Compound)

Since the liquid containing a conductive polymer of this embodiment uses an organic solvent as a dispersion medium, an organic silicon compound having low polarity can be added as an adhesive component and sufficiently dispersed. When the organic solvent contains a hydrocarbon solvent or an ester solvent, the dispersibility of the organosilicon compound is further improved, which is preferable.

Examples of the organosilicon compound include curable silicones. When the adhesive component is a curable silicone, the conductive layer can be provided with releasability by curing the curable silicone.

The curable silicone may be any one of an addition curable silicone and a condensation curable silicone. In this embodiment, it is preferable to use an addition curing silicone because inhibition of curing is less likely to occur.

Examples of the addition-curable silicone include a linear polymer having a siloxane bond, which includes polydimethylsiloxane having vinyl groups at both ends of the linear polymer, and hydrosilane. Such an addition-curable silicone is cured by forming a three-dimensional crosslinked structure through an addition reaction. To promote curing, a platinum-based curing catalyst may be used.

Specific examples of the addition curing silicone include KS-3703T, KS-847T, KM-3951, X-52-151, X-52-6068 and X-52-6069 (manufactured by shin-Etsu chemical Co., Ltd.).

The addition curing silicone may be suitably a silicone dissolved or dispersed in an organic solvent.

The content ratio of the organic silicon compound contained in the conductive polymer-containing liquid of the present embodiment is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 60 parts by mass or less, and further preferably 20 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the conductive composite.

When the lower limit value of the above range is not less than the above range, sufficient releasability can be imparted to the conductive layer formed from the liquid containing a conductive polymer of the present embodiment.

[ Binders ]

The liquid containing a conductive polymer of this embodiment may contain a binder. By using a liquid containing a conductive polymer containing a binder, a conductive layer having adhesiveness can be formed.

The liquid containing a conductive polymer of the present embodiment contains an organic solvent, and therefore can be easily mixed with a binder dispersed in advance in the organic solvent. In the case where the organic solvent contained in the conductive polymer-containing liquid of the present embodiment contains a hydrocarbon solvent or an ester solvent, the organic solvent can be easily mixed with a binder dispersed in advance in the hydrocarbon solvent or the ester solvent, and the conductive composite can be stably dispersed in the mixed liquid, which is preferable.

The degree of adhesiveness possessed by the adhesive of the present embodiment is not particularly limited, and may be such an adhesiveness that can be easily peeled off by hand after attachment, or such an adhesiveness that is difficult to peel off after attachment. Difficult-to-peel adhesion can be interchanged with adhesion. That is, the adhesiveness may be such that it can be semi-permanently bonded.

As the binder, a known binder can be used. From the viewpoint of maintaining conductivity and exhibiting good adhesion, an acrylic adhesive, a silicone adhesive, and a urethane adhesive are preferable. The polyurethane-based adhesive is preferably: the resin contains a (meth) acrylic acid structural unit, and a structure in which a hydroxyl group of the (meth) acrylic acid structural unit reacts with isocyanate to form a urethane bond (urethane linkage).

(acrylic adhesive)

The acrylic adhesive may be used to bond solid surfaces and surfaces of the same type or different types to each other to integrate them. The acrylic adhesive contains an acrylic resin (acrylic polymer).

Specific examples of the acrylic monomer forming the acrylic resin include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, ditrimethylolpropane tetraacrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A ethylene oxide-modified diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, glycerol propoxytriacrylate, 4-hydroxybutyl acrylate, 1, 6-hexanediol diacrylate, 1-hydroxy-3-phenoxypropyl acrylate, and mixtures thereof, Acrylic esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, tripropylene glycol diacrylate and the like; methacrylates such as tetraethylene glycol dimethacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, allyl methacrylate, 1, 3-butanediol dimethacrylate, benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 1, 6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate and the like; (meth) acrylamides such as diacetone acrylamide, N-dimethylacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, N-methylolacrylamide, acryloylmorpholine, N-methacrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, N-phenylacrylamide, acryloylpiperidine, 2-hydroxyethyl acrylamide, and the like. The acrylic resin may be formed from 1 or 2 or more kinds of acrylic monomers. The adhesiveness can also be adjusted by using 2 or more kinds of acrylic monomers in combination.

The acrylic resin may be a copolymer of an acrylic monomer and a vinyl monomer other than the acrylic monomer.

Examples of the vinyl monomer include styrene, α -methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, and maleic anhydride.

The content of the acrylic monomer unit in the copolymer is preferably 50 mol% or more and less than 100 mol%, and more preferably 70 mol% or more and 98 mol% or less.

If the content of the acrylic monomer unit is not less than the lower limit, the adhesiveness can be easily expressed.

The content of the vinyl monomer unit in the copolymer may be, for example, 2 mol% or more and 20 mol% or less.

The glass transition temperature of the acrylic resin is preferably 80 ℃ or lower, more preferably 50 ℃ or lower, and still more preferably 0 ℃ or lower. The acrylic resin having a glass transition temperature exceeding 80 ℃ has low adhesion. The glass transition temperature of the acrylic resin is-80 ℃ or higher, and it is difficult to obtain a material having a lower glass transition temperature than that of the acrylic resin. The glass transition temperature of the acrylic resin can be determined by differential scanning calorimetry or dynamic viscoelasticity measurement.

Examples of the acrylic monomer having a tendency to lower the glass transition temperature of the acrylic resin include ethyl acrylate, butyl acrylate (particularly n-butyl acrylate), and 2-ethylhexyl acrylate. In the acrylic resin, the larger the proportion of these monomer units, the lower the glass transition temperature.

The mass average molecular weight of the acrylic resin is preferably 1 to 200 ten thousand, more preferably 3 to 100 ten thousand. When the mass average molecular weight of the acrylic resin is not less than the lower limit, a sufficient cohesive force can be secured. If the content is not more than the above upper limit, the adhesiveness can be further improved.

In the case where the acrylic resin has an acrylic monomer unit having a reactive functional group, it can be cured by reacting with a curing agent. When the acrylic resin is cured, the cohesive force of the conductive layer containing the binder is increased, and the strength can be improved. Further, by increasing the cohesive force of the conductive layer, a removable conductive layer which can be repeatedly attached and detached can be formed.

Examples of the reactive functional group include a hydroxyl group, a carboxyl group, an amino group, an amide group, and an epoxy group. In the case of reacting with a polyfunctional isocyanate described later, the reactive functional group is preferably a hydroxyl group, a carboxyl group, or an amino group, and more preferably a hydroxyl group.

Examples of the acrylic monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate.

Examples of the acrylic monomer having a carboxyl group include acrylic acid, methacrylic acid, and itaconic acid.

Examples of the acrylic monomer having an amino group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the like.

Examples of the acrylic monomer having an amide group include acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide and the like.

Examples of the acrylic monomer having an epoxy group include glycidyl acrylate and glycidyl methacrylate.

In the case of using a polyfunctional isocyanate as a curing agent, among the above acrylic monomers having a reactive functional group, acrylic monomers having a hydroxyl group are preferable in view of curability and cost, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are more preferable.

The acrylic monomer having a reactive functional group that forms the acrylic resin may be 1 type or 2 or more types.

The content ratio of the binder contained in the conductive polymer-containing liquid of the present embodiment is preferably 1000 parts by mass or more and 100000 parts by mass or less, more preferably 2000 parts by mass or more and 50000 parts by mass or less, and further preferably 3000 parts by mass or more and 10000 parts by mass or less with respect to 100 parts by mass of the conductive composite.

When the lower limit value of the above range is not less than the above range, sufficient adhesiveness can be imparted to the conductive layer formed from the liquid containing a conductive polymer of the present embodiment.

(curing agent)

In the case where the adhesive property included in the liquid containing a conductive polymer of the present embodiment has a reactive functional group, the liquid containing a conductive polymer of the present embodiment preferably contains a curing agent.

Examples of the curing agent include isocyanate-based curing agents such as polyfunctional isocyanates having 2 or more isocyanate groups in 1 molecule, and epoxy-based curing agents such as epoxy compounds having 2 or more epoxy groups in 1 molecule. Among these curing agents, polyfunctional isocyanates are preferable from the viewpoint of reactivity. In particular, in the case where the adhesive has a hydroxyl group-containing acrylic monomer unit, the curing agent is preferably a polyfunctional isocyanate.

Examples of the polyfunctional isocyanate include aliphatic polyfunctional isocyanates, alicyclic polyfunctional isocyanates and aromatic polyfunctional isocyanates.

Specific examples of the polyfunctional isocyanate include 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate, 1, 6-hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, trans-cyclohexane-1, 4-diisocyanate, 4' -dicyclomethane diisocyanate, 3' -dimethyl-4, 4' -diphenylmethane diisocyanate, dianisidine diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, and the like, 1, 5-naphthalene diisocyanate, 1, 4-cyclohexane diisocyanate, lysine ester triisocyanate, tetramethylxylene diisocyanate, 1,6, 11-undecane triisocyanate, 1,3, 6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, etc.

The polyfunctional isocyanate may be a modified diisocyanate obtained by modifying a modified polyfunctional isocyanate obtained by modifying the diisocyanate so that the NCO/OH molar ratio becomes 2/1 or more.

The polyfunctional isocyanate may be a modified polyisocyanate. Examples of the modified polyisocyanate include a polyurethane polyisocyanate obtained by reacting the above-mentioned polyfunctional isocyanate with a polyol, a polyisocyanate containing an isocyanurate ring obtained by polymerizing the polyfunctional isocyanate, and a polyisocyanate containing a biuret bond obtained by reacting the polyfunctional isocyanate with water.

The kind of the curing agent contained in the liquid containing a conductive polymer of the present embodiment may be 1 kind, or 2 or more kinds.

The content ratio of the curing agent contained in the conductive polymer-containing liquid of the present embodiment is, for example, preferably 1 part by mass or more and 100 parts by mass or less, more preferably 3 parts by mass or more and 50 parts by mass or less, and further preferably 5 parts by mass or more and 30 parts by mass or less, with respect to 100 parts by mass of the binder.

When the amount is within the above range, sufficient adhesiveness can be provided to the conductive layer formed from the liquid containing a conductive polymer of the present embodiment.

(high conductivity agent)

The liquid containing a conductive polymer of this embodiment may contain a highly conductive agent.

Here, the above-mentioned pi-conjugated conductive polymer, polyanion, organic solvent, binder, and adhesive component are not classified as a high-conductivity agent. However, the epoxy group-containing compound and the amine compound may be the high conductivity agent described herein.

The highly conductive agent is preferably at least 1 compound selected from the group consisting of saccharides, nitrogen-containing aromatic cyclic compounds, compounds having 2 or more hydroxyl groups, compounds having 1 or more hydroxyl groups and 1 or more carboxyl groups, compounds having amide groups, compounds having imide groups, lactam compounds, and compounds having glycidyl groups.

The number of the high-conductivity agents contained in the liquid containing a conductive polymer of this embodiment may be 1, or 2 or more.

The content of the high-conductivity 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 further preferably 100 parts by mass or more and 2500 parts by mass or less, with respect to 100 parts by mass of the conductive composite.

If the content of the high-conductivity agent is not less than the lower limit, the effect of improving the conductivity by adding the high-conductivity agent is sufficiently exhibited, and if the content is not more than the upper limit, the decrease in conductivity due to the decrease in the concentration of the n-conjugated conductive polymer can be prevented.

(other additives)

The liquid containing a conductive polymer may contain other known additives.

The additive is not particularly limited as long as the effects of the present invention can be obtained, and examples thereof include a surfactant, an inorganic conductive agent, an antifoaming agent, a coupling agent, an antioxidant, and an ultraviolet absorber.

The surfactant includes nonionic, anionic and cationic surfactants, and is preferably nonionic from the viewpoint of storage stability. In addition, a polymer-based surfactant such as polyvinylpyrrolidone may be added.

Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ions 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.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and the like.

When the conductive polymer-containing liquid of the present embodiment contains the additive, the content thereof is appropriately determined depending on the type of the additive, and may be, for example, in a range of 0.001 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the conductive composite.

Method 1 for producing liquid containing conductive polymer

A second aspect of the present invention is a method for producing a liquid containing a conductive polymer, the method including: a precipitate recovery step of adding an epoxy group-containing compound and an amine compound to an aqueous conductive polymer dispersion containing a conductive complex containing a pi-conjugated conductive polymer and a polyanion in an aqueous dispersion medium, and then recovering a precipitate; and an organic solvent addition step of adding an organic solvent to the precipitate to obtain a preparation solution.

The liquid containing a conductive polymer of the first embodiment can be produced by the production method of the present embodiment.

The production method of the present embodiment may further include a cleaning step between the precipitation and recovery step and the organic solvent addition step. Further, an adhesive component addition step may be provided after the organic solvent addition step.

[ precipitation recovery Process ]

The precipitate recovery step is a step of adding an epoxy group-containing compound and an amine compound to the aqueous conductive polymer dispersion to precipitate the conductive complex to obtain a precipitate, and then recovering the precipitate by filtration or decantation.

When the epoxy group-containing compound is added to the aqueous conductive polymer dispersion, the epoxy group of the epoxy group-containing compound reacts with a part of the anionic groups of the polyanion. The substituent (a) is formed as a result, and the conductive composite becomes hydrophobic, so that stable dispersion in an aqueous dispersion becomes difficult, and precipitates to form precipitates.

When the epoxy group-containing compound is added, heating may be performed to accelerate the reaction. The heating temperature is preferably 40 ℃ to 100 ℃.

The amount of the epoxy group-containing compound added is preferably 10 parts by mass or more and 10000 parts by mass or less, more preferably 100 parts by mass or more and 5000 parts by mass or less, and still more preferably 500 parts by mass or more and 3000 parts by mass or less, with respect to 100 parts by mass of the conductive composite.

When the amount is not less than the lower limit of the above range, the hydrophobicity of the conductive composite becomes sufficiently high, and the dispersibility in an organic solvent, particularly a hydrocarbon-based solvent and an ester-based solvent, is improved.

When the content is not more than the upper limit of the above range, the decrease in conductivity due to the unreacted epoxy group-containing compound can be prevented.

The organic solvent may be added before, simultaneously with, or after the addition of the epoxy group-containing compound to the aqueous conductive polymer dispersion. The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent is an organic solvent which dissolves in 100g of water at a temperature of 20 ℃ in an amount of 1g or more. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents, and ester solvents. The number of the organic solvents to be added may be 1 or 2 or more.

When an amine compound is added to the aqueous conductive polymer dispersion, the amine compound reacts with a part of the anionic groups of the polyanion. The substituent (B) is formed in this way, and the conductive composite becomes hydrophobic, so that stable dispersion in an aqueous dispersion becomes difficult, and precipitates form precipitates.

The amount of the amine compound to be added 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 still more preferably 50 parts by mass or more and 1000 parts by mass or less, based on 100 parts by mass of the conductive composite.

In the precipitation recovery step, the order of adding the epoxy group-containing compound and the amine compound is not particularly limited. From the viewpoint of ease of handling of the synthesis intermediate (reaction intermediate), it is preferable to add an epoxy group-containing compound to the aqueous conductive polymer dispersion, react with a part of the anionic groups of the polyanion, and then add an amine compound to react with a part of the anionic groups of the polyanion.

The aqueous dispersion of a conductive polymer is a dispersion containing a conductive composite containing a pi-conjugated conductive polymer and a polyanion in an aqueous dispersion medium.

Here, the aqueous dispersion medium is water or a mixture of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents, and ester solvents. The number of the water-soluble organic solvents contained in the aqueous dispersion medium may be 1, or 2 or more.

The content of water with respect to the total mass of the aqueous dispersion medium is preferably more than 50 mass%, more preferably 60 mass% or more, further preferably 80 mass% or more, and may be 100 mass%.

The aqueous conductive polymer dispersion can be obtained by, for example, chemical oxidative polymerization of a monomer that forms a pi-conjugated conductive polymer in an aqueous solution of a polyanion. Further, commercially available products can be used as the aqueous conductive polymer dispersion.

In the chemical oxidative polymerization, a known catalyst can be used. For example, a catalyst and an oxidizing agent may 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 may restore the reduced catalyst to its original oxidation state.

The amount of water in the precipitate obtained in the precipitation and collection step is preferably as small as possible, and most preferably, it is completely free of water, but from the practical viewpoint, it may contain water in the range of 10 mass% or less.

Examples of the method for reducing the amount of water include a method of washing the precipitate with an organic solvent, a method of drying the precipitate, and the like.

[ cleaning Process ]

The cleaning step between the precipitate recovery step and the organic solvent addition step is a step of cleaning the precipitate with an organic solvent for cleaning. By this washing step, residual water, unreacted epoxy group-containing compound, unreacted amine compound, a reaction product of the epoxy group-containing compound and the amine compound, and a hydrolysate of the epoxy group-containing compound are removed.

As the organic solvent for cleaning, a solvent which can be cleaned without dissolving the precipitate can be suitably used. Therefore, the organic solvent for cleaning is preferably an alcohol solvent. The number of the organic solvents contained in the organic solvent for washing may be 1, or 2 or more.

The washing method is not particularly limited, and for example, the precipitate may be washed by pouring a washing organic solvent from above the precipitate, or the precipitate may be washed by stirring the precipitate in a washing organic solvent.

[ organic solvent addition step ]

The organic solvent addition step is a step of adding an organic solvent to the precipitate to obtain a preparation solution.

As the organic solvent, an organic solvent contained in the liquid containing a conductive polymer of the first embodiment can be used. Among them, 1 or more selected from ester-based solvents (ester-containing compounds) and hydrocarbon-based solvents are preferable, and 1 or more selected from the ester-containing compounds represented by the above formula 1, heptane and toluene is more preferable. When heptane or toluene is contained in the organic solvent, methyl ethyl ketone is preferably further contained. By using such an appropriate organic solvent, the dispersibility of the precipitate in the preparation solution can be further improved.

The content of each solvent contained in the organic solvent is preferably within the preferred range exemplified in the first embodiment. When the organic solvent contains an ester solvent, the organic solvent may contain an organic solvent other than the ester solvent. When the organic solvent contains a hydrocarbon solvent, the organic solvent may contain an organic solvent other than the hydrocarbon solvent.

After the organic solvent is added to the precipitate, the dispersion treatment can be performed by stirring the preparation solution. The method of stirring is not particularly limited, and stirring with a weak shearing force such as a stirrer may be employed, or stirring may be performed using a dispersing machine (homogenizer or the like) with a high shearing force.

In the case where the production method of the present embodiment does not include the following [ adhesive component addition step ], the preparation liquid obtained in the organic solvent addition step is a liquid containing a conductive polymer.

[ adhesive component addition Process ]

The adhesive component adding step is a step of adding the adhesive component to the preparation solution. In this step, an arbitrary organic solvent may be added simultaneously with the above adhesive component.

Preferably, the adhesive component is added to the preparation solution, and then the mixture is stirred to improve the dispersibility of the adhesive component.

The curing agent may be added simultaneously with or after the addition of the binder.

When the adhesive component is an addition curing silicone, it is preferable to add a platinum curing catalyst simultaneously with or after the addition of the adhesive component.

[ addition of high-conductivity agent and additive ]

When the liquid containing the conductive polymer contains a high-conductivity agent, an additive, or the like, the high-conductivity agent, the additive, or the like may be added in any 1 or more of the organic solvent addition step and the adhesive component addition step.

Method 2 for producing liquid containing conductive polymer

The conductive polymer-containing liquid according to the first aspect of the present invention can be produced by the following production method including an epoxy compound addition step, a solvent substitution step, and an amine compound addition step.

[ procedure for adding epoxy Compound ]

First, an epoxy group-containing compound is added to an aqueous conductive polymer dispersion, and the conductive composite is reacted with the epoxy group-containing compound to precipitate the conductive composite, thereby obtaining a precipitate. This step can be performed in the same manner as the addition of the epoxy group-containing compound in the above-described production method 1.

[ solvent replacement Process ]

When the reaction solution in which the precipitate is precipitated is allowed to stand or centrifuged, the precipitate can be precipitated at the bottom of the reaction solution. Next, the supernatant liquid containing the aqueous dispersion medium is removed from the reaction solution by decantation or the like, and an organic solvent is added thereto. This operation of solvent replacement is preferably repeated a plurality of times. By this solvent replacement, a mixed solution containing the precipitate and the organic solvent is obtained.

The organic solvent used in this step is preferably the organic solvent used in the organic solvent addition step of production method 1, and more preferably contains 1 or more organic solvents selected from hydrocarbon solvents and ester solvents. Organic solvents other than hydrocarbon solvents and ester solvents may also be included.

[ Process for adding amine Compound ]

Next, an amine compound is added to the mixed solution, and the conductive complex contained in the precipitate is reacted with the amine compound, whereby the conductive complex can be dispersed in the organic solvent, in particular, in 1 or more kinds selected from the group consisting of a hydrocarbon solvent and an ester solvent. The present reaction can be carried out in the same manner as the addition of the amine compound in the above-described production method 1. As a result, the liquid containing the conductive polymer of interest in which the conductive composite is dispersed in the organic solvent constituting the mixture can be obtained. From the viewpoint of further improving the dispersibility of the conductive composite in the liquid containing a conductive polymer, it is preferable to further disperse the conductive composite by a high-pressure homogenizer or the like.

The liquid containing a conductive polymer obtained by the above-mentioned production method 2 may be added with a binder component, a high-conductivity agent, an additive, and the like.

Method 3 for producing liquid containing conductive Polymer

The liquid containing a conductive polymer according to the first aspect of the present invention can be produced by the following production method including a drying step and a preparation liquid preparation step.

[ drying Process ]

The drying step is a step of drying an aqueous conductive polymer dispersion containing a conductive composite containing a pi-conjugated conductive polymer and a polyanion in an aqueous dispersion medium to obtain a dried product of the conductive composite.

As the drying method in the drying step, known methods such as freeze drying, vacuum drying, spray drying, air drying, hot air drying, and heat drying can be applied.

In the freeze drying, the aqueous dispersion medium in the aqueous conductive polymer dispersion is frozen and vacuum-dried.

The temperature during freeze drying is preferably-60 to 60 ℃, more preferably-40 to 40 ℃. If the freeze-drying temperature is not lower than the lower limit, the temperature can be easily adjusted, and if the freeze-drying temperature is not higher than the upper limit, the aqueous conductive polymer dispersion can be easily freeze-dried.

In the vacuum drying, the aqueous dispersion medium may be heated to, for example, 40 ℃ or higher after reaching the freeze-drying temperature to sufficiently volatilize the aqueous dispersion medium.

In the spray drying, the aqueous conductive polymer dispersion is sprayed into a vacuum vessel to evaporate the aqueous dispersion medium and dry the dispersion.

The temperature during spray drying is preferably-20 to 40 ℃, more preferably 0 to 30 ℃. If the spray drying temperature is not lower than the lower limit, the aqueous conductive polymer dispersion can be easily dried, and if the spray drying temperature is not higher than the upper limit, thermal degradation of the conductive composite can be prevented.

The amount of water in the dried product obtained in the drying step is preferably as small as possible, and most preferably, it is completely free of water, but from the viewpoint of practical use, it may be contained in a range of 10 mass% or less.

In order to reduce the amount of water, for example, the drying time may be prolonged, the drying temperature may be increased, and the degree of vacuum may be increased.

[ preparation Process of preparation solution ]

The preparation step of the preparation solution is a step of adding an epoxy group-containing compound, an amine compound and an organic solvent to the dried product to react and obtain the preparation solution.

As described above, the organic solvent preferably contains 1 or more kinds selected from ester solvents and hydrocarbon solvents. Organic solvents other than ester solvents and hydrocarbon solvents may also be included.

In this step, the substituent (a) can be formed by adding an epoxy group-containing compound to the dried product to react a part of the anionic groups of the polyanion with the epoxy group-containing compound. When the epoxy group-containing compound is added, heating may be performed to accelerate the reaction. The heating temperature is preferably 40 ℃ to 100 ℃.

In this step, the amine compound is added to the dried product, and part of the anionic groups of the polyanion is reacted with the amine compound to form the substituent (B).

The order of adding the epoxy group-containing compound and the amine compound in the preparation step of the preparation solution is not particularly limited. From the viewpoint of ease of handling of the synthetic intermediate, it is preferable that an epoxy group-containing compound is added to the dried product to react with a part of the anionic groups of the polyanion, and then an amine compound is added to react with a part of the anionic groups of the polyanion.

The above-mentioned cleaning step may be provided between the drying step and the preparation liquid preparation step described in the above-mentioned production method 3. The preparation method may further include the adhesive component addition step after the preparation liquid preparation step.

In addition, in any 1 or more of the preparation liquid preparation step and the adhesive component addition step, a high-conductivity agent, an additive, and the like may be added.

(Effect)

In the liquid containing a conductive polymer of the present invention, since the polyanion constituting the conductive composite has the substituent (a) and the substituent (B), the dispersibility of the conductive composite in an organic solvent, particularly in an ester-based solvent such as ethyl acetate and a hydrocarbon-based solvent such as toluene is improved. As a result, a conductive layer having excellent conductivity can be formed using the liquid containing a conductive polymer of the present invention. Further, since the conductive composite has excellent dispersibility, the storage stability of the liquid containing the conductive polymer is also improved.

In addition, when another material (such as an adhesive component) including a hydrocarbon-based solvent and an ester-based solvent is mixed in the liquid containing a conductive polymer of the present invention, the conductive composite is not separated and can be easily mixed.

In the liquid containing a conductive polymer of the present invention, the polyanion constituting the conductive composite has the substituent (B), but the polyanion has the substituent (a) at the same time, so that the proportion of the substituent (B) is reduced as compared with the conventional conductive composite hydrophobized with only an amine compound. Therefore, when the liquid containing a conductive polymer of the present invention contains an addition-curable silicone, inhibition of curing of the addition-curable silicone can be suppressed. This can impart excellent releasability to the conductive layer.

Conductive film and method for producing same

A third aspect of the present invention is a method for producing a conductive film, including: a step of applying a liquid containing a conductive polymer according to a first embodiment to at least one surface of a film base material to form a coating film; and a step of forming a conductive layer by drying the coating film.

A fourth aspect of the present invention is a conductive film having a conductive layer on at least one surface of a film base, the conductive layer containing a cured layer of the liquid containing a conductive polymer according to the first aspect. The conductive film of the present embodiment can be produced by the production method of the third embodiment.

(conductive film)

The conductive layer of the conductive film of the present embodiment contains a conductive complex, and the conductive complex contains a pi-conjugated conductive polymer and a polyanion. Hydrogen atoms of part of the anionic groups of the polyanion contained in the conductive layer are substituted with the above-described substituent (a) and substituent (B).

When the liquid containing a conductive polymer applied to the film base contains a binder component, the conductive layer contains the binder component or a cured product obtained by curing the binder component.

The average thickness of the conductive layer is preferably 10nm to 20000nm, more preferably 20nm to 10000nm, and still more preferably 30nm to 5000 nm. When the average thickness of the conductive layer is not less than the lower limit, excellent conductivity is exhibited, and when the average thickness is not more than the upper limit, the conductive layer is difficult to be peeled off from the film base.

The average thickness of the conductive layer is a value obtained by measuring the thickness of any 10 sites and averaging the measured values.

Examples of the film substrate used in the production method of the present embodiment include a plastic film and paper.

Examples of the resin for the film base 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, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate, and cellulose acetate propionate. Among these film base resins, polyethylene terephthalate and triacetylcellulose are preferable from the viewpoint of low cost and excellent mechanical strength.

The resin for the film base may be amorphous or crystalline.

Further, the film substrate may be unstretched or stretched.

In order to further improve the adhesion of the conductive layer formed of a liquid containing a conductive polymer, the film base material may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or flame treatment.

The average thickness of the film base material 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 base material is not less than the lower limit, the film is less likely to break, and if the average thickness is not more than the upper limit, sufficient flexibility as a film can be secured.

The thickness of the film base material is a value obtained by measuring the thickness of any 10 sites and averaging the measured values.

(coating Process)

As a method for applying the liquid containing the conductive polymer in the above-mentioned coating step, there can be applied coating methods using coaters such as a gravure coater, a roll coater, a curtain coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a Fountain coater, a ruled coater, an air Knife coater, a Blade coater, a casting coater, a screen coater, etc., spraying methods using a sprayer such as an air sprayer, an airless sprayer, a Rotor damping (Rotor damping), dipping methods such as dipping, etc.

Among the above methods, a bar coater is sometimes used from the viewpoint of enabling easy coating. In a commercially available bar coater, the number of each type of mark is larger, and the thicker the coating can be.

The amount of the conductive polymer-containing liquid applied to the film substrate is not particularly limited, but is preferably 0.1g/m in terms of solid content²Above and 10.0g/m²The following ranges.

(drying Process)

Examples of the method of drying 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 used. When the heat drying is applied, the heating temperature may be appropriately set according to the dispersion medium used, and may be set to, for example, 50 ℃ to 150 ℃. Here, the heating temperature is a set temperature of the drying device.

When the conductive polymer-containing liquid contains an active energy ray-curable adhesive component, the drying step may be followed by an active energy ray irradiation step of irradiating the dried conductive polymer coating film with an active energy ray. If the active energy ray irradiation step is included, the formation rate of the conductive layer can be increased, and the productivity of the conductive film can be improved.

When the active energy ray irradiation step is provided, examples of the active energy ray used include ultraviolet rays, electron beams, visible light, and the like. Examples of the light source for ultraviolet rays include light sources such as an ultra-high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp.

The illuminance in the ultraviolet irradiation is preferably 100mW/cm²The above. If the illumination intensity is less than 100mW/cm²The active energy ray-curable adhesive component may not be sufficiently cured. Further, the integrated light amount is preferably 50mJ/cm²The above. If the integrated light quantity is less than 50mJ/cm²Then, the crosslinking may not be sufficient. The illuminance and the integrated light amount in the present specification are values measured using UVR-T1 (Industrial UV Detector, light receiver; UD-T36, measurement wavelength region; peak sensitivity wavelength of 300nm to 390 nm; about 355nm) manufactured by TOPCON.

Conductive laminate and method for producing same

A fifth aspect of the present invention is a method for manufacturing a conductive laminate, including: a step of applying a liquid containing a conductive polymer including the binder of the first embodiment to at least one surface of a film base material to form a coating film; a step of forming a conductive layer by drying the coating film; and a step of bonding a glass layer to the conductive layer.

A sixth aspect of the present invention is a conductive laminate having a conductive layer on at least one surface of a film base, wherein the conductive layer includes a cured layer of the conductive polymer-containing liquid containing the binder of the first aspect, and a glass layer is provided on a surface of the conductive layer. The conductive film of the present embodiment can be produced by the production method of the fifth embodiment.

In the fifth aspect, the method for obtaining a conductive film having a conductive layer on at least one surface of a film base material can be performed in the same manner as the method for producing a conductive film of the third aspect. Since the conductive layer contains a binder, the surface of the conductive layer exhibits adhesiveness. By attaching a desired glass plate to an arbitrary region of the surface, the intended conductive laminate can be obtained.

The average thickness of the glass plate is, for example, 500 μm or more and 5mm or less.

The thickness of the glass plate is measured at arbitrary 10 positions in the cross section of the conductive laminate of the present embodiment by a known method, and the measured values are averaged.

Examples of the glass plate include a glass plate made of borosilicate glass, aluminosilicate glass, or alkali-free glass.

When the conductive laminate is used for optical applications, the glass plate and the film base are preferably transparent. Specifically, the total light transmittance of each of the glass plate and the film base material is preferably 65% or more, more preferably 70% or more, and further preferably 80% or more. The total light transmittance is a value measured according to JIS K7136.

Examples

Production example 1 production of polystyrenesulfonic acid

206g of sodium styrenesulfonate was dissolved in 1000ml of ion-exchanged water, and 1.14g of an ammonium persulfate oxidizer solution previously dissolved in 10ml of water was added dropwise over 20 minutes while stirring at 80 ℃ and the solution was stirred for 12 hours.

To the resulting sodium styrenesulfonate-containing solution was added 1000ml of sulfuric acid diluted to 10 mass%, and about 1000ml of the solvent containing the polystyrenesulfonic acid solution was removed by ultrafiltration. Subsequently, 2000ml of ion exchange water was added to the residual liquid, and about 2000ml of the solvent was removed by ultrafiltration, and polystyrene sulfonic acid was washed with water. This washing operation was repeated 3 times.

The water in the resulting solution was removed under reduced pressure to obtain polystyrene sulfonic acid as a colorless solid.

Preparation example 2 Synthesis of conductive Polymer Dispersion containing Pi-conjugated conductive Polymer and polyanion

14.2g of 3, 4-ethylenedioxythiophene was mixed with a solution obtained by dissolving 36.7g of polystyrenesulfonic acid in 2000ml of ion-exchanged water at 20 ℃.

The mixed solution thus obtained was kept at 20 ℃ and stirred while slowly adding 29.64g of ammonium persulfate and 8.0g of iron sulfate dissolved in 200ml of ion-exchanged water as an oxidation catalyst solution, and the mixture was stirred for 3 hours to effect a reaction.

2000ml of ion-exchanged water was added to the obtained reaction solution, and about 2000ml of the solvent was removed by ultrafiltration. This operation was repeated 3 times.

Then, 200ml of sulfuric acid diluted to 10 mass% and 2000ml of ion-exchanged water were added to the obtained solution, and about 2000ml of the solvent was removed by ultrafiltration. 2000ml of ion-exchanged water was added to the residual liquid, and about 2000ml of the solvent was removed by ultrafiltration. This operation was repeated 3 times.

Subsequently, 2000ml of ion-exchanged water was added to the obtained solution, and about 2000ml of the solvent was removed by ultrafiltration. This operation was repeated 5 times to obtain an aqueous dispersion of polystyrenesulfonic acid-doped poly (3, 4-ethylenedioxythiophene) (PEDOT-PSS) at a concentration of 1.2% by mass.

(example 1)

To 100g of the aqueous dispersion of PEDOT-PSS obtained in preparation example 2, 200g of methanol and 25g of an epoxy compound (EpightM-1230, C12, C13 mixed higher alcohol glycidyl ether, Co., Ltd.) were added, and the mixture was stirred at 60 ℃ for 4 hours. At this time, the epoxy compound reacts with and bonds to a part of the remaining sulfonic acid groups of PEDOT-PSS that are not bonded to PEDOT of PSS. Next, 100g of isopropyl alcohol and 1.0g of trioctylamine were added. At this time, the amine compound is bonded to the remaining sulfonic acid groups of PEDOT-PSS which are not bonded to PEDOT of PSS. As a result, the PEDOT-PSS has a reduced water dispersibility, and a conductive complex comprising PEDOT-PSS modified by the reaction of an epoxy compound and an amine compound precipitates. The precipitate was collected by filtration to obtain 1.8g of a conductive composite.

Next, 798.2g of ethyl acetate was added to the above-mentioned conductive composite, and the mixture was dispersed by using a high-pressure homogenizer to obtain a liquid containing a conductive polymer.

The obtained liquid containing the conductive polymer was coated on a PET film (lumiror T60, manufactured by ori corporation) using a #4 bar coater, and dried at 100 ℃ for 1 minute. The results of measuring the surface resistance values of the obtained conductive films are shown in table 1.

(example 2)

A conductive film was produced in the same manner as in example 1 except that in example 1, butyl acetate was used instead of ethyl acetate, and the surface resistance value thereof was measured. The results are shown in Table 1.

(example 3)

A conductive film was produced in the same manner as in example 1 except that in example 1, isopropyl acetate was replaced with ethyl acetate, and the surface resistance value thereof was measured. The results are shown in Table 1.

(example 4)

A conductive film was produced in the same manner as in example 1 except that isobutyl acetate was used instead of ethyl acetate in example 1, and the surface resistance value thereof was measured. The results are shown in Table 1.

(example 5)

To 100g of the aqueous dispersion of PEDOT-PSS obtained in preparation example 2, 200g of methanol and 25g of butyl glycidyl ether were added, and the mixture was stirred at 60 ℃ for 4 hours. At this time, the epoxy compound reacts with and bonds to a part of the remaining sulfonic acid groups of PEDOT-PSS that are not bonded to PEDOT of PSS. Next, 100g of isopropyl alcohol and 1.0g of trioctylamine were added. At this time, the amine compound is bonded to the remaining sulfonic acid groups of PEDOT-PSS which are not bonded to PEDOT of PSS. As a result, the PEDOT-PSS has a reduced water dispersibility, and a conductive complex comprising PEDOT-PSS modified by the reaction of an epoxy compound and an amine compound precipitates. The precipitate was collected by filtration to obtain 1.7g of a conductive composite.

Next, 798.3g of ethyl acetate was added to the above-mentioned conductive composite, and the mixture was dispersed by using a high-pressure homogenizer to obtain a liquid containing a conductive polymer.

(example 6)

To 100g of the aqueous dispersion of PEDOT-PSS obtained in preparation example 2, 200g of methanol and 25g of an epoxy compound (Eplight M-1230, C12, C13 mixed with a higher alcohol glycidyl ether, Co., Ltd.) were added, and the mixture was stirred at 60 ℃ for 4 hours. At this time, the epoxy compound reacts with and bonds to a part of the remaining sulfonic acid groups of PEDOT-PSS that are not bonded to PEDOT of PSS. Next, 100g of isopropyl alcohol and 1.0g of tributylamine were added. At this time, the amine compound is bonded to the remaining sulfonic acid groups of PEDOT-PSS which are not bonded to PEDOT of PSS. As a result, the PEDOT-PSS has a reduced water dispersibility, and a conductive complex comprising PEDOT-PSS modified by the reaction of an epoxy compound and an amine compound precipitates. The precipitate was collected by filtration to obtain 1.7g of a conductive composite.

(example 7)

To 100g of the aqueous dispersion of PEDOT-PSS obtained in preparation example 2, 200g of methanol and 25g of an epoxy compound (Eplight M-1230, C12, C13 mixed with a higher alcohol glycidyl ether, Co., Ltd.) were added, and the mixture was stirred at 60 ℃ for 4 hours. At this time, the epoxy compound reacts with and bonds to a part of the remaining sulfonic acid groups of PEDOT-PSS that are not bonded to PEDOT of PSS, and the reaction product precipitates in the solution. Then, 150g of the upper layer (supernatant) of the solution was removed. Further, 300g of ethyl acetate was added, 300g of the solution upper layer (supernatant) was removed, and 649g of ethyl acetate and 1.0g of trioctylamine were added. At this time, the amine compound is bonded to the remaining sulfonic acid groups of PEDOT-PSS contained in the above-mentioned precipitate, which are not bonded to PEDOT of PSS. As a result, the precipitate is dissolved and dispersed in the solution.

Next, the mixture was further dispersed by a high-pressure homogenizer to obtain a liquid containing a conductive polymer.

Comparative example 1

To 100g of the aqueous dispersion of PEDOT-PSS obtained in preparation example 2, 200g of methanol and 25g of an epoxy compound (Eplight M-1230, C12, C13 mixed with a higher alcohol glycidyl ether, Co., Ltd.) were added, and the mixture was stirred at 60 ℃ for 4 hours. At this time, the epoxy compound reacts with and bonds to a part of the remaining sulfonic acid groups of PEDOT-PSS that are not bonded to PEDOT of PSS. Next, 100g of isopropyl alcohol was added. As a result, the PEDOT-PSS has a reduced water dispersibility, and the conductive complex containing the PEDOT-PSS modified by the reaction of the epoxy compound precipitates. The precipitate was collected by filtration to obtain 1.5g of a conductive composite.

Next, 798.5g of ethyl acetate was added with the above-mentioned conductive composite, and the mixture was dispersed by using a high-pressure homogenizer, but the study was stopped because all the conductive composite settled and separated within several minutes.

Comparative example 2

To 100g of the aqueous dispersion of PEDOT-PSS obtained in preparation example 2 were added 200g of methanol, 100g of isopropanol, and 1g of trioctylamine. As a result, PEDOT-PSS is reduced in water dispersibility, and a conductive complex comprising PEDOT-PSS and an amine compound bonded thereto is precipitated. The precipitate was collected by filtration to obtain 1.6g of a conductive composite.

Next, 798.4g of ethyl acetate was added with the above-mentioned conductive composite, and the mixture was dispersed by using a high-pressure homogenizer, but the study was stopped because all the conductive composite settled and separated within several minutes.

[ measurement of surface resistance value ]

The surface resistance of the conductive layer was measured with a resistivity meter (Hiresta, manufactured by mitsubishi chemical Analytech) under a voltage of 10V applied to the conductive film produced in each example. In the table, "2.0E + 06" means "2.0X 10⁶", the others are also the same.

[ Table 1]

< discussion 1 >)

In the liquids containing conductive polymers of examples 1 to 7, since the conductive composite is modified with an epoxy group-containing compound (epoxy compound) and an amine compound, the dispersibility in an ester-based solvent such as ethyl acetate is excellent. As a result of applying the liquid containing the conductive polymer to the film base, a conductive layer having excellent conductivity can be formed.

The conductive composite of comparative example 1 was not modified with the amine compound but only with the epoxy compound, and thus could not be dispersed in the ester solvent.

The conductive composite of comparative example 2 was not modified with an epoxy compound but modified with only an amine compound, and thus could not be dispersed in an ester-based solvent.

(example 8)

To 40g of the conductive polymer-containing liquid of example 1, 60g of SK Dyne1499M (manufactured by Soken chemical Co., Ltd., acrylic binder, 35% by mass of solid content, mixed solution of ethyl acetate and butyl acetate) and 1.6g of a curing agent L-45 (manufactured by Soken chemical Co., Ltd., toluene diisocyanate-trimethylolpropane adduct, 45% by mass of solid content, mixed solution of toluene and ethyl acetate) were mixed to obtain a coating material. The above coating was applied to a PET film (lumiror T60, toronto) using a #16 bar coater, and after drying at 100 ℃ for 1 minute, the surface resistance value of the formed conductive layer was measured. Subsequently, a PET film was pressure-bonded to a part of the conductive layer, and an alkali-free glass (thickness: 0.7mm) was pressure-bonded to the other part of the conductive layer, and the resultant was aged at room temperature for 48 minutes.

Subsequently, the PET film obtained by pressure bonding was cut into a long shape having a width of 10mm, and a 180 ° peel test was performed to measure the peel force. Further, the alkali-free glass was wiped with a nonwoven fabric, and the charged voltage was measured. The measurement results are shown in table 2.

(example 9)

A test sample was prepared and measured in the same manner as in example 8 except that in example 8, SK Dyne1499M was changed to SK Dyne1498B (a mixed solution of an acrylic binder, 35% by mass of solid content, ethyl acetate and methyl ethyl ketone, manufactured by seiko chemical corporation). The measurement results are shown in table 2.

Comparative example 3

A test sample was prepared and measured in the same manner as in example 8, except that the conductive polymer-containing liquid in example 8 was changed to ethyl acetate. The measurement results are shown in table 2.

Comparative example 4

A test sample was prepared and measured in the same manner as in example 9, except that the conductive polymer-containing liquid in example 9 was changed to ethyl acetate. The measurement results are shown in table 2.

[ measurement of peeling force ]

The coating films formed on the test samples of the respective examples were measured for peel force by the following method, and the releasability was evaluated.

According to JIS Z0237, the PET film (width: 10mm) pressure-bonded to the surface of the conductive layer was peeled off at an angle of 180 degrees (peeling speed: 0.3 m/min) using a tensile tester, and the peeling force (unit: N) was measured. The smaller the peeling force, the higher the releasability of the coating film.

[ with Voltage ]

The antistatic property was evaluated by measuring the static charging pressure on the surface of the alkali-free glass attached to the coating film of each test sample by the following method.

According to JIS C61340-2-2: 2006, the surface potential of the alkali-free glass charged by the nonwoven fabric wiping as described above was measured using a digital low potential measuring instrument (KSD-3000, manufactured by spring Motor Co.). The surface potential was taken as the charged voltage in the alkali-free glass plate. The lower the charged voltage, the more excellent the antistatic property.

[ Table 2]

< investigation 2 >

In the liquids containing conductive polymers of examples 8 to 9, a binder was added to the liquid containing conductive polymer of example 1. The conductive complex is sufficiently dispersed in the ester solvent in the liquid containing the conductive polymer before the binder is added. Therefore, the conductive composite is stably dispersed without settling even in the liquid (paint) containing the conductive polymer to which the binder containing the ester-based solvent is added. As a result, a conductive layer exhibiting excellent conductivity, adhesiveness, and antistatic property can be formed by applying the coating material on the film base.

In comparative examples 3 to 4, the coating film formed did not exhibit conductivity because the coating material contained no conductive composite.

(example 10)

To 60g of the conductive polymer-containing liquid obtained in example 1 were added 1.5g of KS-3703T (addition-curable silicone, 30% by mass solid content, toluene solution, manufactured by shin-Etsu chemical Co., Ltd.), 25.5g of toluene and 0.3g of CAT-PL-50T (platinum catalyst, manufactured by shin-Etsu chemical Co., Ltd.) to obtain a coating material. The coating material was applied to a PET film using a #8 bar coater, and dried at 150 ℃ for 1 minute to obtain a conductive film. The results of measuring the surface resistance value and the peeling force of the obtained conductive film are shown in table 3.

Comparative example 5

A test sample was prepared and measured in the same manner as in example 10, except that the conductive polymer-containing liquid in example 10 was changed to ethyl acetate. The measurement results are shown in table 3.

[ measurement of peeling force ]

The coating films formed on the films of the respective examples were measured for peel force by the following method, and the releasability was evaluated.

A polyester adhesive tape (No. 31B, manufactured by Nindon electric Co., Ltd.) having a width of 25mm was placed on the surface of the coating film of each film, and a load of 1976Pa was placed on the adhesive tape and pressure treatment was carried out at 25 ℃ for 20 hours. Next, the adhesive tape bonded to the above-mentioned coating film was peeled off at an angle of 180 ℃ by using a tensile tester in accordance with JIS Z0237 (peeling speed: 0.3 m/min), and the peeling force (unit: N) was measured. The smaller the peeling force, the higher the releasability of the coating film.

[ Table 3]

< investigation 3 >

In the liquid containing a conductive polymer in example 10, an organic silicon compound was added to the liquid containing a conductive polymer in example 1. In the liquid containing the conductive polymer before the organic silicon compound is added, the conductive complex is sufficiently dispersed in the ester solvent. Therefore, the conductive composite is stably dispersed without settling in the liquid (paint) containing the conductive polymer to which the organic silicon compound is added together with toluene as a nonpolar solvent. As a result, a conductive layer exhibiting excellent conductivity and releasability can be formed by applying the coating material to the film base.

In comparative example 5, the coating film formed did not exhibit conductivity because the coating material contained no conductive composite.

(example 11)

To 50g of the liquid containing a conductive polymer obtained in example 1, 10g of Art Resin UN-904M (urethane acrylate, manufactured by Utility Co., Ltd., solid content: 80% by mass, methyl ethyl ketone solution), 30g of pentaerythritol triacrylate, 10g of diacetone alcohol, and 1.6g of Irgacure 184 (manufactured by BASF Corp., photopolymerization initiator) were added to obtain a coating material. The above coating was applied to a PET film by using a #8 bar coater, dried at 100 ℃ for 1 minute, and irradiated with ultraviolet light of 400mJ to obtain a conductive film. The results of measuring the surface resistance values of the obtained conductive films are shown in table 4.

Comparative example 6

A test sample was prepared and measured in the same manner as in example 11, except that the conductive polymer-containing liquid in example 11 was changed to ethyl acetate. The measurement results are shown in table 4.

[ Table 4]

< discussion 4 >

In the liquid containing a conductive polymer in example 11, a photocurable acrylic compound was added to the liquid containing a conductive polymer in example 1. In the liquid containing the conductive polymer before the acrylic compound is added, the conductive complex is sufficiently dispersed in the ester solvent. Therefore, in the liquid (paint) containing a conductive polymer to which an acrylic compound is added together with methyl ethyl ketone as a polar solvent, the conductive composite is stably dispersed without being precipitated. As a result, the coating material is applied to the film base material, and a conductive layer exhibiting excellent conductivity and hardness (hard coat property) can be formed.

In comparative example 6, since the coating material contained no conductive composite, the formed coating film showed no conductivity.

(production example 3)

100g of the aqueous PEDOT-PSS dispersion obtained in preparation example 2 was added to a mixture of 91.7g of methanol and 183.3g of isopropyl alcohol, and the mixture was stirred at 80 ℃ for 5 minutes. Then, 22.5g of an epoxy group-containing compound (Eplight M-1230, C12, C13 mixed higher alcohol glycidyl ether, Co., Ltd.) and a mixture of 8.3g of methanol and 16.7g of isopropanol were added thereto, and the mixture was stirred at 80 ℃ for 8 hours. Thereafter, the temperature was returned to normal temperature, and 10g of tri-n-octylamine was added thereto and stirred for 10 minutes. Thereby, a precipitate of the conductive composite having the substituent (a) derived from the epoxy group-containing compound and the substituent (B) derived from the amine compound is obtained. The precipitate was collected by filtration, 100g of isopropyl alcohol was added thereto, and the mixture was stirred for 30 minutes, and then collected by filtration again, thereby washing was performed. This operation was repeated 1 time. Then, 100g of heptane was poured and washed to obtain 1.6g of a conductive composite.

Production example 4

100g of the aqueous PEDOT-PSS dispersion obtained in preparation example 2 was added to a mixture of 91.7g of methanol and 183.3g of isopropyl alcohol, and the mixture was stirred at 80 ℃ for 5 minutes. Then, 2.5g of 1, 2-epoxy-4-vinylcyclohexane and 22.5g of an epoxy group-containing compound (Eplight M-1230, manufactured by Kyoeisha Co., Ltd., mixed higher alcohol glycidyl ether of C12, C13) were added thereto, and a mixture of 8.3g of methanol and 16.7g of isopropyl alcohol was added thereto and the mixture was stirred at 80 ℃ for 8 hours. Thereafter, the temperature was returned to normal temperature, and 10g of tri-n-octylamine was added thereto and stirred for 10 minutes. Thereby, a precipitate of the conductive composite having the substituent (a) derived from the epoxy group-containing compound and the substituent (B) derived from the amine compound is obtained. The precipitate was collected by filtration, 100g of isopropyl alcohol was added thereto, and the mixture was stirred for 30 minutes, and then collected by filtration again, thereby washing was performed. This operation was repeated 1 time. Then, 100g of heptane was poured and washed to obtain 1.8g of a conductive composite.

Production example 5

1.5g of addition curing type silicone (KS-3703T, manufactured by shin-Etsu chemical Co., Ltd., solid content concentration 30 mass%, toluene solution) was mixed with 34.5g of toluene, 7.75g of methyl ethyl ketone, 42.75g of heptane, and 0.03g of platinum catalyst (CAT-PL-50T, manufactured by shin-Etsu chemical Co., Ltd.), to obtain a silicone solution (solid content concentration 0.53%).

(production example 6)

1.5g of addition curing type silicone (KS-3703T, manufactured by shin-Etsu chemical Co., Ltd., solid content concentration 30 mass%, toluene solution) was mixed with 34.5g of toluene, 7.65g of methyl ethyl ketone, 41.85g of heptane, and 0.03g of platinum catalyst (CAT-PL-50T, manufactured by shin-Etsu chemical Co., Ltd.), to obtain a silicone solution (solid content concentration 0.53%).

Production example 7

1.5g of addition curing type silicone (KS-3703T, a solid content concentration of 30% by mass, a toluene solution, manufactured by shin Etsu chemical Co., Ltd.) was mixed with 33.21g of toluene, 7.71g of methyl ethyl ketone, 43.28g of heptane, and 0.03g of platinum catalyst (CAT-PL-50T, manufactured by shin Etsu chemical Co., Ltd.) to obtain a silicone solution (solid content concentration of 0.53%).

Production example 8

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

(example 12)

To 0.6g of the conductive composite obtained in production example 3, 30g of methyl ethyl ketone and 70g of heptane were added, and dispersion treatment was performed using a high-pressure homogenizer to obtain a liquid containing a conductive polymer.

The obtained liquid containing a conductive polymer was applied to a polyethylene terephthalate film (manufactured by Toray corporation, LumirrorT60) by using a No.8 bar coater, and dried at 150 ℃ for 2 minutes to form a non-releasable conductive layer, thereby obtaining a conductive film.

In addition, 17.1g of the silicone solution obtained in production example 6 was mixed with 0.9g of the obtained liquid containing a conductive polymer to obtain a liquid containing a conductive polymer containing silicone.

The obtained liquid containing a conductive polymer was applied to a polyethylene terephthalate film (manufactured by Toray corporation, Lumiror T60) by using a No.8 bar coater, and dried at 150 ℃ for 2 minutes to form a conductive layer having releasability, thereby obtaining a conductive release film.

(example 13)

To 0.6g of the conductive composite obtained in production example 4, 30g of methyl ethyl ketone and 70g of heptane were added, and dispersion treatment was performed using a high-pressure homogenizer to obtain a liquid containing a conductive polymer.

The obtained liquid containing a conductive polymer was applied to a polyethylene terephthalate film (manufactured by Toray corporation, Lumiror T60) by using a No.8 bar coater, and dried at 150 ℃ for 2 minutes to form a non-releasable conductive layer, thereby obtaining a conductive film.

The obtained liquid containing the conductive polymer was applied to a polyethylene terephthalate film (manufactured by Toray corporation, Lumiror T60) by using a No.8 bar coater, and dried at 150 ℃ for 2 minutes to form a conductive layer having releasability, thereby obtaining a conductive release film.

(example 14)

To 1.8g of the conductive composite obtained in production example 4, 90g of methyl ethyl ketone, 90g of toluene, and 120g of heptane were added, and dispersion treatment was performed using a high-pressure homogenizer to obtain a liquid containing a conductive polymer.

In addition, 17.14g of the silicone solution obtained in production example 7 was mixed with 0.86g of the obtained conductive polymer-containing liquid to obtain a silicone-containing conductive polymer-containing liquid.

Comparative example 7

To 1.6g of the obtained conductive composite, 185g of methyl ethyl ketone and 185g of heptane were added and dispersion treatment was performed by a high-pressure homogenizer to obtain a liquid containing a conductive polymer, in the same manner as in production example 4, except that tri-n-octylamine was not added. The liquid containing the conductive polymer obtained was added to the silicone solution obtained in production example 6, but the conductive polymer was not dispersed but coagulated.

Comparative example 8

123.8ml of water was added to 1.25g of 3, 4-ethylenedioxythiophene and 62.5g of an aqueous solution of polystyrenesulfonic acid (solid content concentration: 10%), and the mixture was stirred at 30 ℃ for 10 minutes. Subsequently, 0.075g of iron sulfate dissolved in 12.4ml of water in advance and 2.75g of ammonium persulfate dissolved in 22.4ml of water were added thereto, and the mixture was stirred at 30 ℃ for 6 hours, thereby obtaining a reaction solution containing PEDOT-PSS.

To the obtained reaction solution containing PEDOT-PSS, 75ml of water was added, followed by stirring at 30 ℃ for 1 hour, then 10g of tri-n-octylamine dissolved in 150g of isopropyl alcohol was added, and stirring was carried out at room temperature for 16 hours, thereby obtaining a precipitate of an electrically conductive complex having a substituent (B) derived from an amine compound.

The precipitate was collected by filtration, 250g of acetone was added thereto, and after stirring for 3 hours, the precipitate was collected by filtration again, thereby washing was performed. This operation was repeated 2 times, whereby 4.4g of the conductive composite was obtained. To 0.74g of the obtained conductive composite, 70g of methyl ethyl ketone and 70g of heptane were added, and dispersion treatment was performed by a high-pressure homogenizer to obtain 130g of a liquid containing a conductive polymer.

The liquid containing the conductive polymer obtained was added to the silicone solution obtained in production example 5, but the conductive polymer was not dispersed but coagulated.

< evaluation >

[ measurement of surface resistance value ]

The surface resistance values of the conductive layers of examples 12 to 14 and comparative examples 7 to 8 were measured using a resistivity meter (Hiresta, manufactured by mitsubishi chemical Analytech) under an applied voltage of 10V. The measurement results are shown in table 5. In Table 5, "NT" means not tested. In table 5, "a/B ratio (mass ratio)" means the mass ratio of the substituent (a) to the substituent (B).

[ dispersibility ]

The state of the conductive polymer-containing liquid containing silicone after adding the silicone solution to the conductive polymer-containing liquids of examples 12 to 14 and comparative examples 7 to 8 was visually observed and evaluated according to the following evaluation criteria. The evaluation results are shown in table 5.

Good: no precipitation was confirmed.

X: precipitation was confirmed.

[ measurement of peeling force ]

The conductive layer peeling force of the conductive release films of examples 12 to 14 and comparative examples 7 to 8 was measured by the following method to evaluate the releasability. The specific measurement method was the same as that of example 10. The measurement results are shown in Table 5. The smaller the peeling force, the higher the releasability of the conductive layer.

[ Table 5]

< discussion 5 >

The liquids containing conductive polymers of examples 12 to 14 were able to form conductive films having high conductivity. In addition, the liquids containing conductive polymers of examples 12 to 14 exhibited excellent dispersibility in the silicone solution. In addition, the liquids containing the conductive polymers of examples 12 to 14 containing silicone can form conductive release films having excellent conductivity.

The liquids containing conductive polymers of comparative examples 7 and 8 had poor dispersibility in silicone solutions.

Claims

1. A liquid containing a conductive polymer, characterized in that,

the liquid containing a conductive polymer contains a conductive complex and an organic solvent,

the conductive complex comprises a pi-conjugated conductive polymer and a polyanion,

the polyanion is a reactant of a portion of the anionic groups of the polyanion with an epoxy-containing compound and an amine compound.

2. The liquid containing a conductive polymer according to claim 1, wherein,

the organic solvent comprises an ester group-containing compound.

3. The liquid containing a conductive polymer according to claim 2, wherein,

the organic solvent contains 1 or more selected from ester group-containing compounds represented by the following formula 1,

formula 1: r²¹-C(＝O)-O-R²²

In the formula, R²¹Represents a hydrogen atom, a methyl group or an ethyl group, R²²Represents a linear or branched alkyl group having 1 to 6 carbon atoms.

4. The liquid containing a conductive polymer according to claim 2 or 3, wherein,

the content of the ester group-containing compound is 40% by mass or more relative to the total mass of the organic solvent.

5. The liquid containing a conductive polymer according to claim 1, wherein,

the organic solvent contains a hydrocarbon solvent.

6. The liquid containing a conductive polymer according to claim 5, wherein,

the hydrocarbon solvent is at least one selected from heptane and toluene.

7. The liquid containing a conductive polymer according to claim 5 or 6, wherein,

the content of the hydrocarbon solvent is 40 mass% or more with respect to the total mass of the organic solvent.

8. The liquid containing a conductive polymer according to claim 5 or 6, wherein,

the organic solvent contains methyl ethyl ketone.

9. The liquid containing a conductive polymer according to claim 1, wherein,

the pi-conjugated conductive polymer is poly (3, 4-ethylenedioxythiophene).

10. The liquid containing a conductive polymer according to claim 1 or 9, wherein,

the polyanion is polystyrene sulfonic acid.

11. The liquid containing a conductive polymer according to claim 1, wherein,

the epoxy group-containing compound has 4 or more carbon atoms.

12. The liquid containing a conductive polymer according to claim 1 or 11, wherein,

the amine compound has a substituent having 4 or more carbon atoms on a nitrogen atom.

13. The liquid containing a conductive polymer according to any one of claims 1 to 3,

the liquid containing a conductive polymer further contains a binder component.

14. The liquid containing a conductive polymer according to claim 13, wherein,

the adhesive component is an organosilicon compound.

15. The liquid containing a conductive polymer according to claim 14, wherein,

the organic silicon compound is addition curing type organic silicon.

16. The liquid containing a conductive polymer according to claim 13, wherein,

the adhesive component is an acrylic adhesive, a silicone adhesive or a polyurethane adhesive.

17. The liquid containing a conductive polymer according to claim 16, wherein,

the adhesive component is an acrylic adhesive.

18. A method for producing a liquid containing a conductive polymer, comprising:

a precipitate recovery step of adding an epoxy group-containing compound and an amine compound to an aqueous conductive polymer dispersion containing a conductive complex containing a pi-conjugated conductive polymer and a polyanion in an aqueous dispersion medium, and then recovering a precipitate; and

and an organic solvent addition step of adding an organic solvent to the precipitate to obtain a preparation solution.

19. The method for producing a liquid containing a conductive polymer according to claim 18, wherein,

the method further comprises a cleaning step of cleaning the precipitate with a cleaning organic solvent between the precipitate recovery step and the organic solvent addition step.

20. The method for producing a liquid containing a conductive polymer according to claim 18, wherein,

the organic solvent comprises an ester group-containing compound.

21. The method for producing a liquid containing a conductive polymer according to claim 20, wherein,

formula 1: r²¹-C(＝O)-O-R²²

22. The method for producing a liquid containing a conductive polymer according to claim 20 or 21, wherein,

the content of the ester group-containing compound is 40% by mass or more based on the total mass of the organic solvent.

23. The method for producing a liquid containing a conductive polymer according to claim 18, wherein,

the organic solvent contains a hydrocarbon solvent.

24. The method for producing a liquid containing a conductive polymer according to claim 23,

the hydrocarbon solvent is at least one selected from heptane and toluene.

25. The method for producing a liquid containing a conductive polymer according to claim 23 or 24, wherein,

26. The method for producing a liquid containing a conductive polymer according to claim 23 or 24, wherein,

the organic solvent contains methyl ethyl ketone.

27. The method for producing a liquid containing a conductive polymer according to any one of claims 18 to 21,

the method for producing a liquid containing a conductive polymer further comprises a step of adding a binder component to the preparation liquid.

28. The method for producing a liquid containing a conductive polymer according to claim 27, wherein,

the adhesive component is an acrylic adhesive, a silicone adhesive, a polyurethane adhesive, a curable silicone or an ultraviolet curable acrylic resin.

29. A method for manufacturing a conductive film, comprising:

a step of applying the liquid containing a conductive polymer according to any one of claims 1 to 17 on at least one surface of a film base material to form a coating film; and a step of forming a conductive layer by drying the coating film.

30. A method for manufacturing a conductive laminate, comprising: applying the liquid containing a conductive polymer according to claim 16, which contains the acrylic adhesive, the silicone adhesive, or the urethane adhesive, on at least one surface of a film substrate to form a coating film; a step of forming a conductive layer by drying the coating film; and a step of bonding a glass layer to the conductive layer.

31. A conductive film characterized in that,

having a conductive layer on at least one side face of a film substrate,

the conductive layer contains a cured layer of the liquid containing a conductive polymer according to any one of claims 1 to 17.

32. A conductive laminate characterized in that,

a conductive layer is provided on at least one side surface of the film substrate, a glass layer is provided on the surface of the conductive layer,

the conductive layer contains a cured layer of the liquid containing a conductive polymer according to claim 16, which contains the acrylic adhesive, the silicone adhesive, or the polyurethane adhesive.