JP2022112741A - Conductive polymer-containing liquid and method for producing the same, and conductive laminate and method for producing the same - Google Patents

Abstract

To provide a conductive polymer-containing liquid that can form a conductive layer having high resistance to atmospheric exposure and a method for producing the same, and a conductive laminate including a conductive layer composed of a cured product of the conductive polymer-containing liquid and a method for producing the same.SOLUTION: A conductive polymer-containing liquid contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, and a dispersion medium. The polyanion is a copolymer of an anionic compound having an anion group and a vinyl group and an isocyanuric acid derivative represented by a specific chemical formula.SELECTED DRAWING: None

Description

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

A π-conjugated conductive polymer forms a conductive composite by doping with a polyanion having an anion group, and has dispersibility in water. Manufacture of a conductive film having a conductive layer by applying a conductive polymer-containing liquid (also referred to as a conductive polymer dispersion) containing a conductive composite to a film substrate or the like. can be done.
However, a conductive layer containing a conductive composite has a problem that its conductivity decreases over time due to exposure to the atmosphere. As a method of reducing this problem, a method of incorporating an antioxidant into the conductive layer has been disclosed (Patent Document 1).

Japanese Patent No. 5509462

There is a demand for a new conductive polymer-containing liquid to replace the invention disclosed in Patent Document 1.

The present invention provides a conductive polymer-containing liquid capable of forming a conductive layer excellent in resistance to atmospheric exposure, a method for producing the same, and a conductive layer comprising a cured product of the conductive polymer-containing liquid. A laminate and method for manufacturing the same are provided.

[1] A conductive polymer-containing liquid containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, and a dispersion medium, wherein the polyanion is an anionic compound having an anionic group and a vinyl group. and an isocyanuric acid derivative represented by the following formula (1).
[2] The conductive polymer-containing liquid according to [1], wherein part of the anion groups constituting the polyanion are modified by reaction with an amine compound or a quaternary ammonium compound.
[3] The conductive polymer-containing liquid according to [1], wherein part of the anionic groups constituting the polyanion are modified by reaction with an epoxy compound.
[4] The conductive polymer-containing liquid according to [1], wherein part of the anionic groups constituting the polyanion are modified by reaction with an epoxy compound and an amine compound or a quaternary ammonium compound.
[5] The π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene), or the compound having an anion group and a vinyl group is styrenesulfonic acid [1] The conductive polymer-containing liquid according to any one of [4].
[6] A conductive complex containing the π-conjugated conductive polymer and the polyanion by polymerizing a monomer forming the π-conjugated conductive polymer in a reaction solution containing a polyanion and a dispersion medium. and a conductive composite forming step of obtaining a conductive polymer-containing liquid containing the dispersion medium, wherein the polyanion is an anion having an anion group and a vinyl group. A method for producing a conductive polymer-containing liquid, which is a copolymer of a conductive compound and an isocyanuric acid derivative represented by the following formula (1).
[7] Preparation for obtaining the copolymer in advance by polymerizing the anionic compound and the isocyanuric acid derivative in a reaction solution containing the anionic compound, the isocyanuric acid derivative, an oxidizing agent, and a dispersion medium In the preparation step, the isocyanuric acid derivative to be supplied to the reaction solution is represented by the following formula (1), wherein R ¹ is a vinyl group-containing substituent and R ² is an epoxy group-containing substituent. , R ³ is a hydrogen atom or an arbitrary substituent, and in the reaction solution, during the polymerization, the epoxy group is ring-opened to form a hydroxyl group by the action of the oxidizing agent, [6 ].
[8] One or more selected from an epoxy compound, an amine compound and a quaternary ammonium compound is added to the conductive polymer-containing liquid obtained in the conductive composite forming step, and the conductive composite and [6] or [7], further comprising a modification step of obtaining a conductive polymer-containing liquid by reacting to precipitate a reaction product, recovering the precipitated reaction product, and adding a solvent to obtain a conductive polymer-containing liquid. A method for producing a conductive polymer-containing liquid.
[9] A conductive polymer comprising a substrate and a conductive layer formed on at least a part of the surface of the substrate, wherein the conductive layer is the conductive polymer according to any one of [1] to [5]. A conductive laminate, which is a cured product of the contained liquid.
[10] Conductive, comprising applying the conductive polymer-containing liquid according to any one of [1] to [5] to at least a part of the surface of a substrate to form a conductive layer. A method for manufacturing a laminate.

［式中、Ｒ^１，Ｒ^２，Ｒ^３は、それぞれ独立に水素原子又は任意の置換基であり、Ｒ^１，Ｒ^２，Ｒ^３のうち少なくとも１つがビニル基を有する置換基である。］

[In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom or an arbitrary substituent, and at least one of R ¹ , R ² and R ³ is a substituent having a vinyl group. ]

According to the conductive polymer-containing liquid of the present invention, it is possible to form a conductive layer having excellent resistance to atmospheric exposure.
According to the method for producing a conductive polymer-containing liquid of the present invention, the above-described conductive polymer-containing liquid can be easily produced.
The conductive film, which is an example of the conductive laminate of the present invention, is suitable for various uses because it has a conductive layer with excellent resistance to atmospheric exposure.
In the method for producing the conductive laminate of the present invention, the conductive polymer-containing liquid can be applied by a general-purpose coating method such as a bar coater, and the conductive layer can be easily formed.

The present invention is considered to contribute to SDGs Goal 12 “Responsible consumption and production”.

In the present specification and claims, the lower limit and upper limit of the numerical range indicated by "-" shall be included in the numerical range.

≪Liquid containing conductive polymer≫
A first aspect of the present invention is a conductive polymer-containing liquid containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, and a dispersion medium. The polyanion is a copolymer of an anionic compound having an anionic group and a vinyl group and an isocyanuric acid derivative represented by the following formula (1).
In the conductive polymer-containing liquid of this aspect, the conductive composite may be in a dispersed state or in a dissolved state.

In the conductive composite, the content of the polyanion (copolymer) with respect to 100 parts by mass of the π-conjugated conductive polymer is preferably 1 part by mass or more and 5000 parts by mass or less, more preferably 10 parts by mass or more and 1000 parts by mass or less. It is preferably 100 parts by mass or more and 500 parts by mass or less.
When it is at least the lower limit of the above range, the doping effect of the polyanion on the π-conjugated conductive polymer becomes stronger, the dispersibility of the conductive composite improves, the particle size of the conductive composite decreases, and the conductivity becomes higher.
If it is at most the upper limit of the range, it is possible to suppress the decrease in conductivity due to the decrease in the content of the π-conjugated conductive polymer.

The anion group of the polyanion of the conductive composite may be modified by reaction with one or more selected from epoxy compounds, amine compounds, and quaternary ammonium compounds, as described later. Details of this modification will be described later.

The content of the conductive composite with respect to the total mass of the conductive polymer-containing liquid of this embodiment is, for example, preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.2% by mass or more and 5% by mass or less. It is preferably 0.3% by mass or more and 2% by mass or less.
Within the above preferred range, the dispersibility of the conductive composite in the conductive polymer-containing liquid can be further enhanced.

<π-conjugated conductive polymer>
The π-conjugated conductive polymer is not particularly limited as long as it is an organic polymer whose main chain is composed of a π-conjugated system, as long as it has the effect of the present invention. conductive polymer, polyacetylene-based conductive polymer, polyphenylene-based conductive polymer, polyphenylene vinylene-based conductive polymer, polyaniline-based conductive polymer, polyacene-based conductive polymer, polythiophene vinylene-based conductive polymer, and These copolymers etc. are mentioned. Polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable from the viewpoint of stability in air, and polythiophene-based conductive polymers are more preferable from the viewpoint of transparency.

Polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), and poly(3-hexylthiophene). , poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly (3-chlorothiophene), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene) , poly(3-hydroxythiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene) , poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3 ,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene) , poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-didodecyloxythiophene), poly( 3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3- methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxy butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butyl pyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3 -carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole) , poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), poly(3-hexyloxypyrrole), poly(3-methyl-4-hexyloxypyrrole).
Polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid).
Among the above π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred from the viewpoint of conductivity, transparency and heat resistance.
The π-conjugated conductive polymer contained in the conductive composite may be of one type or two or more types.

<Polyanion>
Generally, a polyanion is a polymer having two or more monomer units having an anionic group in its molecule. The anion group of this polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer. The anion group is preferably a sulfo group or a carboxy group.

The polyanion of this embodiment is a copolymer of an anionic compound having an anionic group and a vinyl group and an isocyanuric acid derivative represented by the following formula (1). Here, the anionic compound is a compound different from the isocyanuric acid derivative.
The copolymer contained in the conductive composite of this aspect may be of one type or two or more types.

Since the copolymer has a plurality of anionic groups derived from an anionic compound, it can be bonded as a dopant to a π-conjugated conductive polymer like conventional polyanions. By doping the .pi.-conjugated conductive polymer with the copolymer, the conductivity of the .pi.-conjugated conductive polymer is improved and contributes to the reduction of the particle size, which will be described later.

The copolymer may be contained in the conductive polymer-containing liquid as an additive without being doped into the π-conjugated conductive polymer. In order for the conductive polymer (for example, PEDOT) to exhibit dispersibility in an aqueous dispersion medium, the π-conjugated conductive polymer is preferably doped with the copolymer.

The mass-average molecular weight Mw of the copolymer is determined from the viewpoint of the effect of doping the π-conjugated conductive polymer, the effect of improving the dispersibility of the conductive composite, the effect of increasing the resistance to atmospheric exposure of the conductive composite, etc. , is preferably 50,000 to 2,000,000, more preferably 10,000 to 1,000,000, and even more preferably 100,000 to 500,000.
Here, the mass average molecular weight is a mass-based average molecular weight measured by gel permeation chromatography (GPC method) using pullulan having a known mass average molecular weight as a standard substance.

In the copolymer, the ratio of the number of moles A of the monomer units derived from the anionic compound to the number of moles B of the monomer units derived from the isocyanuric acid derivative (number of moles A/number of moles B) is 2 or more. It is preferably 100 or less, more preferably 5 or more and 60 or less, and even more preferably 8 or more and 30 or less.
Within the above range, the conductive layer formed using the conductive polymer-containing liquid of the present embodiment has an excellent balance between improvement in conductivity and resistance to atmospheric exposure.

(anionic compound)
As an anionic compound that is a monomer of the copolymer, one or more conventional polyanion monomers can be applied. 1 type may be sufficient as the said anionic compound, and 2 or more types may be sufficient as it.
Specific examples of conventional polyanions include polystyrenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyacrylic acid esters having a sulfo group, polymethacrylic acid esters having a sulfo group (e.g., poly(4-sulfobutyl methacrylate, Polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polymers having a sulfo group such as polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, poly Polymers having a carboxy group such as allylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), and polyisoprenecarboxylic acid can be mentioned.
Among the monomers constituting these conventional polyanions, monomers having a sulfo group are preferable, and styrenesulfonic acid is more preferable, because the conductivity of the conductive composite of the present embodiment can be further increased.

(isocyanuric acid derivative)
The compound represented by the following formula (1) (hereinafter sometimes referred to as isocyanuric acid derivative (1)), which is a monomer of the copolymer, may be one kind or two or more kinds.

［式中、Ｒ^１，Ｒ^２，Ｒ^３は、それぞれ独立に水素原子又は任意の置換基であり、Ｒ^１，Ｒ^２，Ｒ^３のうち少なくとも１つがビニル基を有する置換基である。］

[In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom or an arbitrary substituent, and at least one of R ¹ , R ² and R ³ is a substituent having a vinyl group. ]

As the substituent having a vinyl group, a substituent represented by (*-R ³¹ -CH ₂ =CH ₂ ) is preferable. Here, * represents a nitrogen atom in formula (1), and R ³¹ represents a linear or branched alkylene group having 1 to 6 carbon atoms. One or more methylene groups of the alkylene group are (-O-), (-C(=O)-), (-C(=O)-O-), except when the oxygen atoms are adjacent to each other Alternatively, it may be substituted with (--OC(=O)--).

Examples of the optional substituents include alkyl groups having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), alkenyl groups having 2 to 6 carbon atoms (eg, propenyl group, butynyl group, etc.), alkoxy groups having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryl groups (eg, phenyl group, etc.), and the like. One or more hydrogen atoms bonded to any of these substituents may be substituted with a substituent (eg, hydroxyl group, epoxy group, carboxyl group, amino group, etc.).

The optional substituent is preferably a substituent having a hydroxyl group. This hydroxyl group-containing substituent was originally an epoxy group-containing substituent, and may have been ring-opened by an oxidizing agent during the polymerization of the copolymer to become a hydroxyl group. Since the monomer unit derived from the isocyanuric acid derivative (1) of the copolymer has a hydroxyl group, the dispersibility of the copolymer in water and alcohol solvents is improved, and the conductivity of the formed conductive layer is increased. .

As the substituent having an epoxy group, a substituent represented by (*-R ³² -R ³³ ) is preferable. Here, * represents a nitrogen atom in formula (1), R ³² represents a linear or branched alkylene group having 1 to 6 carbon atoms, and -R ³³ represents an epoxy group. One or more methylene groups of the alkylene group are (-O-), (-C(=O)-), (-C(=O)-O-), except when the oxygen atoms are adjacent to each other Alternatively, it may be substituted with (--OC(=O)--).

Specific examples of isocyanuric acid derivatives (1) include those represented by formulas (1-1) and (1-2).

When the polyanion (the copolymer) of the present embodiment forms a conductive complex by doping the π-conjugated conductive polymer, in the polyanion, a part of the anion group is the π-conjugated conductive polymer dope and have excess anionic groups that do not participate in doping. Since this surplus anionic group is a hydrophilic group, the conductive composite has high water dispersibility and low organic solvent dispersibility before modification as described later.
Assuming that the total number of anionic groups in the polyanion of this embodiment is 100 mol %, the excess anionic groups are preferably 30 mol % or more and 90 mol % or less, more preferably 45 mol % or more and 75 mol % or less.

Excess anionic groups not involved in the doping of the polyanion of the present embodiment (hereinafter also referred to as "partial anionic groups") are reacted with one or more selected from epoxy compounds, amine compounds and quaternary ammonium compounds. may be modified by

It is believed that the following substituent (A) is formed when some of the anionic groups of the polyanion react with the epoxy compound.
When some anionic groups of the polyanion react with the amine compound, it is believed that the following substituent (B) is formed.
When some of the anionic groups of the polyanion react with the quaternary ammonium compound, it is believed that the following substituents (C) are formed.

(Substituent A)
The substituent (A) is presumed to be a group represented by the following formula (A1) or a group represented by the following formula (A2).

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

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

In the formulas (A1) and (A2), the leftmost bond represents that the substituent (A) is substituted with the proton of the anion group. An anionic group having a proton to be substituted includes, for example, an anionic group having an active proton bonded to an oxygen atom such as “—SO ₃ H”.

In formula (A1), the optional substituents for R ¹ , R ² , R ³ and R ⁴ include an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent. Examples include an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be present. R ¹ and R ³ may combine to form a ring which may have a substituent. For example, R ¹ and R ³ are the above-mentioned hydrocarbon groups, a divalent hydrocarbon group excluding any one hydrogen atom of the monovalent hydrocarbon group of R ¹ , and a monovalent hydrocarbon group of R ³ A case where a divalent hydrocarbon group from which any one hydrogen atom is removed from the hydrogen group is combined with the carbon atoms from which the hydrogen atom is removed to form a ring is exemplified.
In formula (A2), the optional substituents for R ⁵ , R ⁶ , R ⁷ and R ⁸ include an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent. Examples include an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be present. R ⁵ and R ⁷ may combine to form a ring which may have a substituent. Examples of ring formation are the same as above.
As used herein, the term “optionally having a substituent” refers to cases in which a hydrogen atom (—H) is substituted with a monovalent group, and cases in which a methylene group (—CH ₂ —) is substituted with a divalent group. Including both when to replace.
Monovalent groups as substituents include alkyl groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), and trialkoxysilyl groups. (trimethoxysilyl group, etc.), and the like.
The divalent group as a substituent includes an oxygen atom (-O-), -C(=O)-, -C(=O)-O- and the like.
m is an integer of 2 or more, preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 25. Hydrophobicity of the conductive composite becomes sufficiently high that m is at least the above lower limit. When m is equal to or less than the upper limit, it is possible to prevent the hydrophobicity from becoming too high and the conductivity from decreasing.

An epoxy compound is a compound having one or more epoxy groups in one molecule (epoxy group-containing compound). From the viewpoint of preventing aggregation or gelation, the epoxy compound is preferably a compound having one epoxy group in one molecule.
One type or two or more types of epoxy compounds that react with the conductive composite may be used.

Monofunctional epoxy compounds having one epoxy group in one molecule include, for example, ethylene oxide, propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, 1 ,2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monoxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2- epoxy octadecane, 1,2-epoxyhexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2-(chloromethyl)-1,2-epoxypropane, glycidol, epichlorohydrin, Epibromohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2-(chloromethyl)-1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2- epoxy-1H,1H,2H,2H,3H,3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-methyl-1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H,1H,2H,2H,3H, 3H-heptadecafluorobutane, 3,4-epoxytetrahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzyl glycidyl ether, diethoxy(3-glycidyloxypropyl)methylsilane, 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl- 3-(3-glycidyloxypropyl)trisiloxane, 9,10-epoxy-1,5-cyclododecadiene, glycidyl 4-tert-butylbenzoate, 2,2-bis(4-glycidyloxyphenyl)propane, 2 -tert-butyl-2-[2-(4-chlorophenyl )] ethyloxirane, styrene oxide, glycidyl trityl ether, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α,6α-epoxide, stilbene oxide, glycidyl p-toluenesulfonate , ethyl 3-methyl-3-phenylglycidate, N-propyl-N-(2,3-epoxypropyl) perfluoro-n-octylsulfonamide, (2S,3S)-1,2-epoxy-3-( tert-butoxycarbonylamino)-4-phenylbutane, 3-nitrobenzenesulfonate (R)-glycidyl, 3-nitrobenzenesulfonate-glycidyl, parthenolide, N-glycidylphthalimide, endrin, deildrin, 4-glycidyloxycarbazole, 7, 7-dimethyloctanoic acid [oxiranylmethyl], 1,2-epoxy-4-vinylcyclohexane, higher alcohol glycidyl ether having 10 to 16 carbon atoms, and the like.

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

Examples of polyfunctional epoxy compounds having two or more epoxy groups in one molecule include 1,6-hexanediol diglycidyl ether, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, and 4-butanediol. diglycidyl ether, 1,2:3,4-diepoxybutane, diglycidyl 1,2-cyclohexanedicarboxylate, 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, glycerin diglycidyl ether, Trimethylolpropane triglycidyl ether, trimethylolpropane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol poly glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, and the like.

The epoxy compound preferably has a molecular weight of 50 or more and 2,000 or less because it is highly dispersible in an organic solvent. In addition, the epoxy compound preferably has 4 to 120 carbon atoms, more preferably 7 to 100 carbon atoms, and more preferably has 10 carbon atoms, because of its high dispersibility in low-polar hydrocarbon solvents and ester solvents. 80 or less is more preferable, and 15 or more and 50 or less is particularly preferable.

(Substituent B)
The substituent (B) is presumed to be a group represented by the following formula (B).

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

In the substituent (B), the leftmost bond represents that the negative charge of the anion group and the positive charge of the amine compound are bonded. Examples of negatively charged anionic groups include anionic groups in which active protons are bonded to oxygen atoms, such as “—SO ₃ ⁻ ”.

R ¹¹ to R ¹³ in the chemical formula (B) are hydrogen atoms or optionally substituted hydrocarbon groups. R ¹¹ to R ¹³ in chemical formula (B) are substituents derived from an amine compound to be described later.
The hydrocarbon group in the chemical formula (B) is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon having 6 to 20 carbon atoms. groups.
Examples of aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups.
A phenyl group, a hydroxyl group, etc. are mentioned as a substituent of an aliphatic hydrocarbon group.
A phenyl group, a naphthyl group, etc. are mentioned as an aromatic-hydrocarbon group.
Substituents for the aromatic hydrocarbon group include alkyl groups having 1 to 5 carbon atoms, hydroxyl groups and the like.

The amine compound is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. The number of amine compounds that react with the conductive composite may be one, or two or more.
Examples of primary amines include aniline, toluidine, benzylamine, ethanolamine and the like.
Secondary amines include, for example, diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Tertiary amines include, for example, triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine.
Among the amine compounds, tertiary amines are preferred, and at least one of trioctylamine and tributylamine is more preferred, since they can increase the electrical conductivity of the conductive composite of this embodiment.

Dispersibility in organic solvents, especially in low-polar hydrocarbon solvents and ester solvents increases, so the amine compound may have a substituent with 4 or more carbon atoms on the nitrogen atom. It preferably has 6 or more substituents, and more preferably has a substituent with 8 or more carbon atoms on the nitrogen atom. The upper limit of the carbon number of the substituent on the nitrogen atom is not particularly limited, and in consideration of solubility and reactivity in solvents, for example, 50 or less is preferable, 40 or less is more preferable, and 30 or less is even more preferable. .

When the conductive composite has a substituent (A) and a substituent (B), the mass ratio represented by [substituent (A)]:[substituent (B)] (hereinafter, A / B ratio is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 25:75 to 75:25. When the A/B ratio is within the above range, it becomes easier to balance dispersibility and conductivity. The mass of the [substituent (A)] is [(the mass of the reactant A obtained by reacting the epoxy compound with the conductive composite) - (the mass of the conductive composite before reacting with the epoxy compound. )]. Further, the mass of [substituent (B)] can be calculated from [(mass of reactant B obtained by reacting reactant A with an amine compound) - (mass of reactant A)]. can.

(Substituent C)
The substituent (C) is presumed to be a group represented by the following formula (C).

-N ⁺ R ¹¹ R ¹² R ¹³ R ¹⁴ (C)
[In Formula (C), R ¹¹ to R ¹⁴ are each independently a hydrocarbon group which may have a substituent. ]

In the substituent (C), the leftmost bond represents that the negative charge of the anion group and the positive charge of the quaternary ammonium cation are bonded. Examples of negatively charged anionic groups include anionic groups in which active protons are bonded to oxygen atoms, such as “—SO ₃ ⁻ ”.

R ¹¹ to R ¹⁴ in chemical formula (C) are hydrocarbon groups which may have a substituent. R ¹¹ to R ¹⁴ in chemical formula (C) are substituents derived from a quaternary ammonium compound.
The hydrocarbon group in the chemical formula (C) is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. groups.
Examples of aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups.
A phenyl group, a hydroxyl group, etc. are mentioned as a substituent of an aliphatic hydrocarbon group.
A phenyl group, a naphthyl group, etc. are mentioned as an aromatic-hydrocarbon group.
Substituents for the aromatic hydrocarbon group include alkyl groups having 1 to 5 carbon atoms, hydroxyl groups and the like.

Since the dispersibility in organic solvents increases, the quaternary ammonium compound preferably has a substituent with 4 or more carbon atoms on the nitrogen atom, and more preferably has a substituent with 6 or more carbon atoms. It is more preferable to have a substituent with 8 or more carbon atoms on the atom. The upper limit of the carbon number of the substituent on the nitrogen atom is not particularly limited, and in consideration of solubility and reactivity in solvents, for example, 50 or less is preferable, 40 or less is more preferable, and 30 or less is even more preferable. .
The total number of carbon atoms of R ¹¹ to R ¹⁴ in the quaternary ammonium compound is preferably 8-44, more preferably 12-40, even more preferably 16-36.
The number of carbon atoms of each substituent on the nitrogen atom may be the same or different.

Specific examples of quaternary ammonium compounds include tetra-n-octylammonium salts, tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, tetraphenylammonium salts, tetrabenzylammonium salts, tetranaphthyl Quaternary ammonium salts such as ammonium salts are included. Counter anions of ammonium cations include, for example, halogen ions such as bromide ions and chloride ions, and hydroxy ions.

When the conductive composite has a substituent (A) and a substituent (C), the mass ratio represented by [substituent (A)]:[substituent (C)] (hereinafter also referred to as the A / C ratio is preferably from 10:90 to 90:10, more preferably from 20:80 to 80:20, and even more preferably from 25:75 to 75:25. When the A/C ratio is within the above range, it becomes easier to balance dispersibility and conductivity. The mass of the [substituent (A)] is [(the mass of the reactant A obtained by reacting the epoxy compound with the conductive composite) - (the mass of the conductive composite before reacting with the epoxy compound. )]. Further, the mass of [substituent (C)] is calculated from [(mass of reactant C obtained by reacting reactant A with a quaternary ammonium compound) - (mass of reactant A)]. can do.

<Dispersion medium>
The dispersion medium contained in the conductive polymer-containing liquid of this embodiment is a liquid agent that disperses or dissolves the above-described conductive composite. In the present specification, the term "dispersion" may be used without distinguishing between dispersing and dissolving, and the term "dispersion medium" may be used without distinguishing between a dispersion medium and a solvent. Therefore, the dispersion medium may be called a solvent.

The dispersion medium contains at least one of water and an organic solvent.
The conductive composite contained in the conductive polymer-containing liquid of this embodiment tends to exhibit water dispersibility due to the surplus anionic groups of the polyanion. This surplus anionic group may be hydrophobized by modifying the substituents (A) to (C) as described above. When it is hydrophobized, it is preferable to use an organic solvent as a dispersion medium. When not hydrophobized, it is preferable to use an aqueous dispersion medium as the dispersion medium.

(Aqueous dispersion medium)
The aqueous dispersion medium is water or a mixture of water and a water-soluble organic solvent. Here, the water-soluble organic solvent is an organic solvent having a solubility of 1 g or more in 100 g of water at 20°C. One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination.
The content of water with respect to the total mass of the aqueous dispersion medium is 50% by mass or more, preferably 60% by mass or more, more preferably 80% by mass or more, and may be 100% by mass.

(Organic solvent)
The organic solvent in this embodiment may be a water-soluble organic solvent, a water-insoluble organic solvent, or a mixed solvent of a water-soluble organic solvent and a water-insoluble organic solvent. Here, the water-insoluble organic solvent is an organic solvent that dissolves less than 1 g in 100 g of water at 20°C.

Examples of water-soluble organic solvents include alcohol-based solvents, ether-based solvents, ketone-based solvents, nitrogen atom-containing solvents, and ester-based solvents.
Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, Ethylene glycol, propylene glycol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether and the like can be mentioned.
Examples of ether solvents include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, diethylene glycol diethyl ether and the like.
Ketone solvents include, for example, 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 nitrogen atom-containing solvents include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.
One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination.
As the water-soluble organic solvent, an alcohol-based solvent, a ketone-based solvent, or an ester-based solvent is preferable because the conductive polymer-containing liquid can be applied to the base material well.

Examples of water-insoluble organic solvents include hydrocarbon-based solvents. Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents.
Examples of aliphatic hydrocarbon solvents include hexane, cyclohexane, pentane, heptane, octane, nonane, decane, dodecane and the like.
Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
One of the water-insoluble organic solvents may be used alone, or two or more thereof may be used in combination.

When the polyanion has any one of the substituents (A) to (C) and is hydrophobized, the content of the organic solvent with respect to the total mass of the dispersion medium of the conductive polymer-containing liquid is 50% by mass. More than 70% by mass or more and 100% by mass or less is more preferable, and 90% by mass or more and 99.9% by mass or less is even more preferable. When the content of the organic solvent is within the above range, the hydrophobized conductive composite can be easily dispersed, and the conductive layer can be easily formed.

(Ester-based solvent)
The ester solvent is an ester group-containing compound having an ester group (--C(=O)--O--).
When the conductive polymer-containing liquid of this embodiment contains an ester solvent, it preferably contains one or more ester group-containing compounds represented by the following formula 1z from the viewpoint of enhancing the dispersibility of the conductive composite.
Formula 1z: R ²¹ -C(=O)-OR ²²
[In the formula, R ²¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ²² represents a linear or branched alkyl group having 1 to 6 carbon atoms. ]

From the viewpoint of enhancing the dispersibility of the conductive composite of this embodiment, R ²¹ is preferably a methyl group or an ethyl group, more preferably a methyl group. The number of carbon atoms in R ²² is preferably 2-5, more preferably 2-4.

Preferred specific examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate and the like.

The content of the ester solvent contained in the conductive polymer-containing liquid of this embodiment is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more, relative to the total mass of the dispersion medium. It is 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. When the content of the ester solvent is within the above range, the dispersibility of the conductive composite can be enhanced.

When the conductive polymer-containing liquid of this embodiment contains an ester solvent, it may further contain one or more organic solvents other than the ester solvent.

When the conductive polymer-containing liquid of this aspect contains an ester-based solvent, from the viewpoint of enhancing the dispersibility of the conductive composite, the polyanion contains the substituent (A) and the substituent (B), or It is preferable to have the substituent (A) and the substituent (C).

When the conductive polymer-containing liquid of this embodiment contains a polyanion having an acid group, the pH tends to be acidic. Specifically, the pH is likely to be 3 or less, and the pH is likely to be 2 or less.

When the dispersion medium of the conductive polymer-containing liquid of this embodiment is an aqueous dispersion medium, the particle size of the conductive composite in the aqueous dispersion medium at 25° C. is is preferably 300 nm or less, more preferably 10 nm or more and 250 nm or less, still more preferably 20 nm or more and 220 nm or less, and particularly preferably 30 nm or more and 200 nm or less. Within these preferred ranges, the dispersion stability of the conductive composite is further improved.
The particle size is obtained as a value obtained by measuring the cumulant average particle size by a dynamic light scattering method.

When the dispersion medium of the conductive polymer-containing liquid of this embodiment is an organic dispersion medium containing more than 50% by mass of an organic solvent, the particle size of the conductive composite in the organic dispersion medium at 25° C. is the same as that of the conductive polymer When the concentration of the conductive composite relative to the total mass of the containing liquid is adjusted to 0.01 to 0.1% by mass, it is preferably 300 nm or less, more preferably 10 nm or more and 250 nm or less, even more preferably 20 nm or more and 220 nm or less, and 30 nm or more. 200 nm or less is particularly preferred. Within these preferred ranges, the dispersion stability of the conductive composite is further improved.
The particle size is obtained as a value obtained by measuring the cumulant average particle size by a dynamic light scattering method.

<Binder component>
The conductive polymer-containing liquid of this aspect may contain one or more binder components. The binder component is a resin other than the π-conjugated conductive polymer and the polyanion or a precursor thereof, and is a thermoplastic resin or a curable monomer or oligomer that cures when the conductive layer is formed. The thermoplastic resin becomes the binder resin as it is, and the resin formed by curing the curable monomer or oligomer becomes the binder resin.

Specific examples of binder resins derived from binder components include epoxy resins, acrylic resins (acrylic compounds), polyester resins, polyurethane resins, polyimide resins, polyether resins, melamine resins, and silicones.
When the dispersion medium of the conductive polymer-containing liquid of this embodiment is an aqueous dispersion medium, the binder resin to be contained is preferably a water-dispersible emulsion resin or a water-soluble resin, more preferably a water-dispersible emulsion resin.

Specific examples of water-dispersible emulsion resins include acrylic resins (acrylic compounds), polyester resins, polyurethane resins, polyimide resins, melamine resins, etc., which are emulsified with an emulsifier. Among them, a polyester emulsion is preferable because the strength of a coating film obtained by coating a base material with a conductive polymer-containing liquid is increased. In particular, when coating on a polyester film substrate, a polyester emulsion is preferable because the adhesion of the coating film to the film substrate increases.

Specific examples of water-soluble resins include acrylic resins (acrylic compounds), polyester resins, polyurethane resins, polyimide resins, and melamine resins having an acid group such as a carboxy group or a sulfo group or a salt thereof. Here, the water-soluble resin preferably dissolves in 100 g of distilled water at 25° C. in an amount of 1 g or more, preferably 5 g or more, more preferably 10 g or more.

Acid groups such as carboxy groups and sulfo groups possessed by the water-dispersible resin may form salts with cations such as sodium ions and potassium ions.

The curable monomers or oligomers may be thermosetting monomers or oligomers or photocurable monomers or oligomers. Here, an oligomer is a polymer having a mass average molecular weight of less than 10,000.
Examples of curable monomers include acrylic monomers (acrylic compounds), epoxy monomers, and organosiloxanes. Examples of curable oligomers include acrylic oligomers (acrylic compounds), epoxy oligomers, and silicone oligomers (curable silicone).
When an acrylic monomer or acrylic oligomer is used as the binder component, it can be easily cured by heating or light irradiation.

When curable monomers or oligomers are included, it is preferable to further include a curing catalyst. For example, if it contains a thermosetting monomer or oligomer, it preferably contains a thermal polymerization initiator that generates radicals by heating, and if it contains a photocurable monomer or oligomer, it generates radicals by light irradiation. It preferably contains a photopolymerization initiator that causes the

The content ratio of the binder component (excluding the silicone compound described later) contained in the conductive polymer-containing liquid of the present embodiment is, for example, 1 part by mass or more and 10000 parts by mass with respect to 1 part by mass of the conductive composite. 10 parts by mass or more and 5000 parts by mass or less is more preferable, and 100 parts by mass or more and 1000 parts by mass or less is even more preferable.
When it is at least the lower limit of the above range, the properties of the binder component contained in the conductive layer formed from the conductive polymer-containing liquid of the present embodiment can be sufficiently exhibited.
When it is equal to or less than the upper limit of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be ensured.

(silicone compound)
When the conductive polymer-containing liquid of this embodiment contains an organic solvent, preferably a water-insoluble organic solvent, as a dispersion medium, a low-polarity silicone compound is added as a binder component and sufficiently dispersed. be able to. When the organic solvent contains a hydrocarbon-based solvent or an ester-based solvent, the dispersibility of the silicone compound is further enhanced, which is preferable.
Examples of silicone compounds include curable silicones. When the binder component is curable silicone, the conductive layer can be imparted with releasability by curing the curable silicone.

The curable silicone may be either an addition curable silicone or a condensation curable silicone. This aspect is preferable because curing inhibition is less likely to occur even when an addition-curable silicone is used.

Examples of addition-curable silicones include linear polymers having siloxane bonds and having polydimethylsiloxane having vinyl groups at both ends of the linear chain and hydrogensilane. Such addition-curable silicone forms a three-dimensional crosslinked structure through an addition reaction and cures. A platinum-based curing catalyst may be used to accelerate curing.
Specific examples of addition-curable silicones include KS-3703T, KS-847T, KM-3951, X-52-151, X-52-6068, and X-52-6069 (manufactured by Shin-Etsu Chemical Co., Ltd.). .
Addition-curable silicone dissolved or dispersed in an organic solvent is preferably used.

The content ratio of the silicone compound contained in the conductive polymer-containing liquid of this aspect is preferably 10 parts by mass or more and 10000 parts by mass or less, and 100 parts by mass or more and 5000 parts by mass or less with respect to 100 parts by mass of the conductive composite. is more preferable, and 500 parts by mass or more and 3000 parts by mass or less is even more preferable.
When it is at least the lower limit value of the above range, sufficient releasability can be imparted to the conductive layer formed by the conductive polymer-containing liquid of the present embodiment.
When it is equal to or less than the upper limit of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be ensured.

[Adhesive]
The conductive polymer-containing liquid of this embodiment may contain an adhesive as a binder component. By using a conductive polymer-containing liquid containing an adhesive, a conductive layer having adhesiveness can be formed.
When the conductive polymer-containing liquid of this embodiment contains an organic solvent, it can be easily mixed with the pressure-sensitive adhesive previously dispersed in the organic solvent. When the conductive polymer-containing liquid of this embodiment contains a hydrocarbon-based solvent or ester-based solvent, it can be easily mixed with an adhesive that has been dispersed in the hydrocarbon-based solvent or ester-based solvent in advance, and It is preferable because the conductive composite can be stably dispersed in.

The degree of adhesiveness possessed by the pressure-sensitive adhesive of this embodiment is not particularly limited, and may be such that it can be easily peeled off by hand after being applied, or to the extent that it is difficult to peel off after being applied. may be tacky. Tackiness that is difficult to peel off can be rephrased as adhesiveness. In other words, the tackiness may be such that it allows semi-permanent adhesion.

A known adhesive can be applied as the adhesive. An acrylic pressure-sensitive adhesive is preferable from the viewpoint of exhibiting good adhesiveness while maintaining conductivity.

(Acrylic adhesive)
Acrylic pressure-sensitive adhesives can be integrated by laminating surfaces of solids of the same type or different types. The acrylic pressure-sensitive adhesive contains acrylic resin (acrylic polymer).

Specific examples of acrylic monomers forming acrylic resins include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, ditri methylolpropane tetraacrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A/ethylene oxide-modified diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, dipropylene glycol diacrylate, Trimethylolpropane triacrylate, glycerin propoxy triacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, pentaerythritol Acrylates such as triacrylate, tetrahydrofurfuryl acrylate, and tripropylene glycol diacrylate; tetraethylene glycol dimethacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, allyl methacrylate, 1,3-butylene glycol 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 , methacrylates such as trimethylolpropane trimethacrylate; - isopropylacrylamide, Nt-butylacrylamide, N-phenylacrylamide, acryloylpiperidine, 2-hydroxyethyl and (meth)acrylamides such as tilacrylamide.
The number of acrylic monomers forming the acrylic resin may be one, or two or more. Adhesiveness can be adjusted by combining two or more acrylic monomers.

The acrylic resin may be a copolymer of an acrylic monomer and a vinyl monomer other than the acrylic monomer (excluding the polyanion).
Examples of vinyl monomers include styrene, α-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, maleic anhydride and the like.
The content of acrylic monomer units 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 acrylic monomer units is at least the above lower limit, adhesiveness can be easily expressed.
The content of vinyl-based monomer units in the copolymer can be, for example, 2 mol % or more and 20 mol % or less.

The glass transition temperature of the acrylic resin is preferably 80° C. or lower, more preferably 50° C. or lower, and even more preferably 0° C. or lower. An acrylic resin having a glass transition temperature exceeding 80°C has low adhesiveness. The glass transition temperature of acrylic resin is -80°C or higher, and it is difficult to obtain a resin with a glass transition temperature lower than that. The glass transition temperature of the acrylic resin can be determined by differential scanning calorimetry or dynamic viscoelasticity measurement.
Examples of acrylic monomers that tend to lower the glass transition temperature of acrylic resins include ethyl acrylate, butyl acrylate (particularly n-butyl acrylate), 2-ethylhexyl acrylate, and the like. In the acrylic resin, the higher the ratio of these monomer units, the lower the glass transition temperature.

The mass average molecular weight of the acrylic resin is preferably 10,000 or more and 2,000,000 or less, and more preferably 30,000 or more and 1,000,000 or less. If the mass-average molecular weight of the acrylic resin is at least the lower limit, sufficient cohesion can be ensured. If it is below the said upper limit, adhesiveness can be improved more.

When the acrylic resin has an acrylic monomer unit having a reactive functional group, it may be cured by reacting with a curing agent. When the acrylic resin is cured, the cohesive force of the conductive layer containing the pressure-sensitive adhesive is improved, and the strength can be improved. Further, by improving the cohesive force of the conductive layer, a re-peelable conductive layer that can be repeatedly adhered and peeled can be obtained.
Examples of the reactive functional group include a hydroxy group, a carboxyl group, an amino group, an amide group, an epoxy group and the like. When reacting with a polyfunctional isocyanate described later, the reactive functional group is preferably a hydroxy group, a carboxy group or an amino group, more preferably a hydroxy group.
Acrylic monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl acrylate. , 4-hydroxybutyl methacrylate and the like.
Examples of acrylic monomers having a carboxy group include acrylic acid, methacrylic acid and itaconic acid.
Acrylic monomers having an amino group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate and the like.
Acrylic monomers having an amide group include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.
Examples of acrylic monomers having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
When a polyfunctional isocyanate is used as a curing agent, among the acrylic monomers having a reactive functional group, acrylic monomers having a hydroxy group are preferable in consideration of curability and cost, and 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate is more preferred.
One type or two or more types of acrylic monomers having the reactive functional group may be used to form the acrylic resin.

The content of the adhesive contained in the conductive polymer-containing liquid of this aspect is preferably 10 parts by mass or more and 10000 parts by mass or less, and preferably 100 parts by mass or more and 5000 parts by mass or less with respect to 1 part by mass of the conductive composite. It is more preferably 300 parts by mass or more and 1000 parts by mass or less.
When it is at least the lower limit value of the above range, sufficient adhesiveness can be imparted to the conductive layer formed by the conductive polymer-containing liquid of the present embodiment.
When it is equal to or less than the upper limit of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be ensured.

(curing agent)
When the adhesive contained in the conductive polymer-containing liquid of this aspect has a reactive functional group, the conductive polymer-containing liquid of this aspect preferably contains a curing agent.
Examples of the curing agent include isocyanate curing agents such as polyfunctional isocyanates having two or more isocyanate groups in one molecule, and epoxy curing agents such as epoxy compounds having two or more epoxy groups in one molecule. Among these curing agents, polyfunctional isocyanates are preferred from the viewpoint of reactivity. In particular, when the pressure-sensitive adhesive has an acrylic monomer unit having a hydroxy group, the curing agent is preferably polyfunctional isocyanate.

Polyfunctional isocyanates include aliphatic polyfunctional isocyanates, alicyclic polyfunctional isocyanates and aromatic polyfunctional isocyanates.
Specific examples of polyfunctional isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, polyphenylene Polymethylene polyisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, 4,4'-dicyclomethane diisocyanate, 3,3 '-dimethyl-4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, tetramethyl xylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, bicyclohepta triisocyanate, trimethylhexamethylene diisocyanate and the like.
The polyfunctional isocyanate may be a modified diisocyanate formed from a modified polyfunctional isocyanate obtained by modifying the above diisocyanate so that the NCO/OH molar ratio is 2/1 or more.
A polyfunctional isocyanate may be a modified polyisocyanate. Modified polyisocyanates include, for example, polyurethane polyisocyanates obtained by reacting polyfunctional isocyanates with polyhydric alcohols, polyisocyanates containing isocyanurate rings obtained by polymerizing polyfunctional isocyanates, and polyfunctional isocyanates. and polyisocyanate containing burette bonds obtained by reacting with water.
The type of curing agent contained in the conductive polymer-containing liquid of this embodiment may be one type, or two or more types.

The content of the curing agent contained in the conductive polymer-containing liquid of this aspect is preferably, for example, 1 part by mass or more and 100 parts by mass or less, and 2 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the adhesive. is more preferable, and 3 parts by mass or more and 10 parts by mass or less is even more preferable.
Within the above range, sufficient adhesiveness can be imparted to the conductive layer formed by the conductive polymer-containing liquid of the present embodiment.

(high conductivity agent)
The conductive polymer-containing liquid of this embodiment may contain a conductivity enhancer.
Here, the above-described π-conjugated conductive polymer, polyanion, organic solvent, adhesive, curing agent, and binder component are not classified as high-conductivity agents. The epoxy compound, the amine compound, and the quaternary ammonium compound may correspond to the high-conductivity agent described here.
Conductive agents include sugars, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxyl groups, compounds having one or more hydroxyl groups and one or more carboxyl groups, compounds having an amide group, and imide groups. is preferably at least one compound selected from the group consisting of compounds having
The conductive polymer-containing liquid of the present embodiment may contain one type of conductivity enhancer, or two or more types thereof.
The content ratio of the highly conductive agent is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, and 100 parts by mass or more and 2500 parts by mass with respect to 100 parts by mass of the conductive composite. More preferred are:
If the content of the high-conductivity agent is at least the lower limit, the effect of improving conductivity by adding the high-conductivity agent is sufficiently exhibited, and if it is at or below the upper limit, the concentration of the conductive composite is reduced. A decrease in conductivity can be prevented.

(Other additives)
The conductive polymer-containing liquid of this embodiment may contain other known additives.
Additives are not particularly limited as long as the effects of the present invention can be obtained, and for example, surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, ultraviolet absorbers and the like can be used.
Examples of surfactants include nonionic, anionic, and cationic surfactants, with nonionic surfactants being preferred from the standpoint of storage stability. A polymeric surfactant such as polyvinylpyrrolidone may also be added.
Examples of inorganic conductive agents include metal ions and conductive carbon. Metal ions can be generated by dissolving a metal salt in water.
Antifoaming agents include silicone resins, polydimethylsiloxane, silicone oils and the like.
Examples of coupling agents include silane coupling agents having a vinyl group or an amino group.
Antioxidants include phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, sugars and the like.
UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. is mentioned.
When the conductive polymer-containing liquid of the present embodiment contains the additive, the content ratio thereof can be appropriately determined according to the type of the additive. It can be in the range of 0.001 part by mass or more and 5 parts by mass or less.

<<Method for producing polyanion>>
The polyanion (copolymer) is a reaction liquid containing the anionic compound, the isocyanuric acid derivative (1), an oxidizing agent, and a dispersion medium, and the anionic compound and the isocyanuric acid derivative (1) are polymerized. obtained by
Since each of the anionic compound and the isocyanuric acid derivative (1) has a vinyl group, a method of polymerizing a known vinyl compound with a known oxidizing agent can be applied. radical polymerization method.
When the anionic compound or isocyanuric acid derivative (1) contained in the reaction solution has an acid group, the acid group may be a salt to which a counter cation such as sodium ion or ammonium ion is bound.

The dispersion medium contained in the reaction liquid is preferably the aqueous dispersion medium, more preferably water.
When the dispersion medium contains water, the polymerization reaction proceeds stably, and the polyanion is easily obtained in a state of being stably dispersed in the dispersion medium.

In the formula (1) representing the isocyanuric acid derivative (1) to be subjected to the reaction solution, R ¹ is a substituent having a vinyl group, R ² is a substituent having an epoxy group, and R ³ is a hydrogen atom or In the case of a compound that is an arbitrary substituent, in the reaction solution, during the polymerization (immediately before, during, or immediately after the polymerization), the epoxy group is ring-opened to form a hydroxyl group by the action of the oxidizing agent. is preferred.
In the polyanion, it is preferable that the monomer unit derived from the isocyanuric acid derivative (1) has a hydroxyl group, because the dispersibility of the polyanion in water and alcohol solvents is improved.

It is preferable to remove the counter cation bonded to the acid group of the polyanion polymerized in the reaction solution and the catalyst and oxidizing agent added to the reaction solution from the reaction solution after the polyanion is polymerized. Removing the counter cation means removing the counter cation that binds to the acid group of the polyanion obtained by polymerization and replacing it with a proton.

Examples of the method for removing the counter cation or the like from the reaction solution include, for example, a method of contacting the reaction solution with an ion exchange resin to adsorb the ion exchange resin, and an ultrafiltration of the reaction solution while adding ion-exchanged water. A method of treating and removing together with replacement of the dispersion medium, and the like can be mentioned. Among these, the method of using an ion exchange resin is preferable because it is simple. The ion exchange resin is preferably a combination of a cation exchange resin and an anion exchange resin.

The above method for producing a polyanion may be performed as a preparatory step for the step of forming a conductive composite, which will be described later.

<<Method for producing liquid containing conductive polymer>>
<Conductive composite formation step>
A second aspect of the present invention includes the π-conjugated conductive polymer and the polyanion by polymerizing a monomer forming the π-conjugated conductive polymer in a reaction solution containing a polyanion and a dispersion medium. A method for producing a conductive polymer-containing liquid, comprising a conductive composite-forming step of obtaining a conductive polymer-containing liquid containing a conductive composite and the dispersion medium.
Here, the polyanion to be supplied to the reaction solution is a copolymer of the anionic compound and the isocyanuric acid derivative (1).
The conductive polymer-containing liquid of the first aspect can be produced by the production method of this aspect.

Synthesis of the conductive composite in the reaction solution can be carried out in the same manner as conventional synthesis of the conductive composite, except that the polyanion supplied to the reaction solution is the copolymer.

The dispersion medium contained in the reaction liquid is preferably the aqueous dispersion medium, more preferably water.
Since the dispersion medium contains water, the polymerization reaction of the monomers proceeds stably, and the obtained conductive composite is obtained in a state of being stably dispersed in the dispersion medium.

The monomers can be polymerized by chemically oxidizing the monomers. Chemical oxidative polymerization can be carried out using known catalysts and oxidizing agents. Examples of catalysts include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate. The oxidizing agent can return the reduced catalyst to its original oxidation state.

The content of the monomer with respect to the total mass of the reaction solution immediately before the start of the polymerization reaction is, for example, preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 5% by mass or less. 3 mass % or more and 2 mass % or less are more preferable.
The content of the polyanion relative to the total mass of the reaction solution immediately before the start of the polymerization reaction is, for example, preferably 0.2% by mass or more and 10% by mass or less, more preferably 0.4% by mass or more and 5% by mass or less. It is more preferably 6% by mass or more and 2% by mass or less.
By setting the concentration within the above preferable range, a conductive polymer-containing liquid having the concentration of the conductive composite in the above-described preferable content can be easily obtained.

In the conductive composite formed by the polymerization reaction, from the viewpoint of adjusting the content ratio of the π-conjugated conductive polymer and the polyanion to the above-mentioned suitable ratio, the monomer contained in the reaction solution immediately before the polymerization reaction is started. The content ratio of the polyanion is preferably in the range of 1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the monomer, more preferably 10 parts by mass or more and 700 parts by mass or less, and 100 parts by mass or more and 500 parts by mass or less. Ranges are more preferred.

By synthesizing the π-conjugated conductive polymer by chemical oxidation polymerization of the monomers, the desired conductive polymer-containing liquid of the first embodiment can be obtained.

It is preferable to remove the catalyst and oxidizing agent added to the reaction solution from the conductive polymer-containing solution after the chemical oxidative polymerization of the monomer.
As a method for removing, for example, a method of contacting the conductive polymer-containing liquid with an ion exchange resin to adsorb the catalyst and the oxidizing agent to the ion exchange resin, a method of ultrafiltrating the conductive polymer-containing liquid to remove the dispersion medium A method of removing with replacement of is mentioned. Among these, the method of using an ion exchange resin is preferable because it is simple. The ion exchange resin is preferably a combination of a cation exchange resin and an anion exchange resin.

The conductive polymer-containing liquid obtained in this step may be stirred for dispersion treatment. The stirring method is not particularly limited, and may be stirring with a weak shearing force such as a stirrer, or may be stirred using a high shearing force disperser (such as a homogenizer).

An optional component such as a binder component may be further added to the conductive polymer-containing liquid obtained above. It is preferable to apply the suitable range described in the first aspect to the type and content of the optional component.

<Modification process>
Adding one or more selected from an epoxy compound, an amine compound and a quaternary ammonium compound to the conductive polymer-containing liquid obtained in the conductive composite forming step, and reacting with the conductive composite. A modification step may be further performed to obtain a conductive polymer-containing liquid by precipitating a reaction product, collecting the precipitated reaction product, and adding a solvent.

When one or more epoxy compounds are added to the conductive polymer-containing liquid, the epoxy groups of the epoxy compound react with some of the anion groups of the polyanion. As a result, the substituent (A) is formed and the conductive composite becomes hydrophobic, which makes it difficult to stably disperse in the aqueous dispersion and precipitates as a precipitate.
When adding the epoxy compound, it may be heated to promote the reaction. The heating temperature is preferably 40° C. or higher and 100° C. or lower.
The amount of the epoxy 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 500 parts by mass or more and 3000 parts by mass or less with respect to 100 parts by mass of the conductive composite. is more preferred.
If it is at least the lower limit of the above range, the hydrophobicity of the conductive composite will be sufficiently high, and the dispersibility in organic solvents, particularly hydrocarbon-based solvents and ester-based solvents will be improved.
If it is at most the upper limit value of the above range, it is possible to prevent a decrease in conductivity due to an unreacted epoxy compound.

An organic solvent may be added before, simultaneously with, or after adding one or more selected from epoxy compounds, amine compounds, and quaternary ammonium compounds to the conductive polymer-containing liquid. As the organic solvent, a water-soluble organic solvent is preferable. Here, the water-soluble organic solvent is an organic solvent that dissolves in an amount of 1 g or more in 100 g of water at a temperature of 20°C. Examples of water-soluble organic solvents include alcohol-based solvents, ketone-based solvents, and ester-based solvents. The organic solvent to be added may be one kind, or two or more kinds.

When one or more amine compounds are added to the conductive polymer-containing liquid, the amine compound reacts with some of the anion groups of the polyanion. As a result, the substituent (B) is formed and the conductive composite becomes hydrophobic, making it difficult to stably disperse in the aqueous dispersion and depositing to form a precipitate.
The amount of the amine compound 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 100 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the conductive composite. More preferred.
If it is at least the lower limit of the above range, the hydrophobicity of the conductive composite will be sufficiently high, and the dispersibility in organic solvents, particularly hydrocarbon-based solvents and ester-based solvents will be improved.
If it is at most the upper limit value of the above range, it is possible to prevent a decrease in conductivity due to an unreacted amine compound.

When one or more quaternary ammonium compounds are added to the conductive polymer-containing liquid, the quaternary ammonium compound reacts with some anionic groups of the polyanion. Since the substituent (C) is formed and the conductive composite becomes hydrophobic, it becomes difficult to stably disperse in the aqueous dispersion, and precipitates as a precipitate.
The amount of the quaternary ammonium compound 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 50 parts by mass or more and 1000 parts by mass with respect to 100 parts by mass of the conductive composite. Part or less is more preferable.
If it is at least the lower limit of the above range, the hydrophobicity of the conductive composite will be sufficiently high, and the dispersibility in organic solvents will be improved.
If it is at most the upper limit value of the above range, it is possible to prevent a decrease in conductivity due to unreacted quaternary ammonium compounds.
A quaternary ammonium compound has a reaction mechanism similar to that of an amine compound, and exhibits good reactivity with the conductive composite at a smaller addition amount than the amine compound. The conductivity of conductive layers comprising conductive composites modified with quaternary ammonium compounds tend to be superior to those modified with amine compounds.

When adding both the epoxy compound and the amine compound or the quaternary ammonium compound to the conductive polymer-containing liquid, the order of addition is not particularly limited. Since the synthetic intermediates (reaction intermediates) are easy to handle, the epoxy compound is first added, reacted with some anionic groups of the polyanion, and then the amine compound or quaternary ammonium compound is added. It is preferable to react with the other anionic group of the polyanion.

The amount of water in the precipitate obtained in this step is preferably as low as possible, and most preferably it does not contain water at all.
Methods for reducing the amount of water include, for example, a method of washing away a precipitate separated from a solvent in a solid state such as powder with an organic solvent, a method of drying the precipitate, and the like.

<Washing>
A reaction product (precipitate) recovered from the reaction solution may be washed with an organic solvent for washing. This washing removes residual water, unreacted epoxy compounds, unreacted amine compounds, unreacted quaternary ammonium compounds, reactants of epoxy compounds and amine compounds, and hydrolysates of epoxy compounds. be able to.
The organic solvent for washing is preferably one that can wash the deposits without dissolving them as much as possible. The number of organic solvents contained in the cleaning organic solvent may be one, or two or more.
The washing method is not particularly limited. For example, the precipitate may be washed by pouring an organic washing solvent over the precipitate, or the precipitate may be washed by stirring the precipitate in the organic washing solvent. You may

<Addition of solvent>
A solvent is added to the obtained reaction product to obtain a conductive polymer-containing liquid. The solvent to be added is preferably an organic solvent capable of dispersing the reaction product.
As the organic solvent, the organic solvent contained in the conductive polymer-containing liquid of the first embodiment can be applied. Among them, one or more selected from alcohol-based solvents, ketone-based solvents, and ester-based solvents are preferable, and one or more selected from isopropanol, methyl ethyltone, and ethyl acetate are more preferable. By using these suitable organic solvents, the dispersibility of the conductive composite contained in the conductive polymer-containing liquid can be further enhanced.
The content of each solvent contained in the organic solvent is preferably within the preferred ranges exemplified in the first aspect.

After adding the solvent to the reaction product, the conductive polymer-containing liquid may be stirred for dispersion treatment. The stirring method is not particularly limited, and may be stirring with a weak shearing force such as a stirrer, or may be stirred using a high shearing force disperser (such as a homogenizer).

An optional component such as a binder component may be further added to the conductive polymer-containing liquid obtained above. It is preferable to apply the suitable range described in the first aspect to the type and content of the optional component.

<<Conductive laminate>>
A third aspect of the present invention is a conductive laminate comprising a base material and a conductive layer formed on at least a part of the surface of the base material. The conductive layer is made of a cured product of the conductive polymer-containing liquid of the first aspect.

[Conductive layer]
The formation range of the conductive layer may be the entire arbitrary surface of the substrate, or may be a part thereof. In the conductive film, it is preferable that a conductive layer having a substantially uniform thickness is formed on substantially the entire surface of one side or the other side of the film substrate. When the conductive layer is formed only on part of the surface of the substrate, for example, the conductive layer may be a fine conductive pattern such as a circuit or an electrode, or the area provided with the conductive layer may be provided. It is also possible that the non-stripped area exists on the same plane and is only roughly divided.

The average thickness of the conductive layer provided on at least part of the surface of the substrate is, for example, preferably 10 nm or more and 100 μm or less, more preferably 20 nm or more and 50 μm or less, and 30 nm or more and 30 μm or less. is more preferred.
If the average thickness of the conductive layer is at least the lower limit, sufficiently high conductivity can be exhibited, and if the average thickness is at most the upper limit, the adhesion of the conductive layer to the substrate is further improved.

The conductive layer included in the conductive laminate of this aspect contains the conductive composite.
When the conductive polymer-containing liquid applied to the substrate contains a binder component, the conductive layer contains the binder component or a cured product of the binder component.

[Base material]
The base material constituting the conductive laminate of this embodiment may be a base material made of an insulating material, or may be a base material made of a conductive material. The shape of the substrate is not particularly limited, and examples thereof include shapes mainly composed of planes such as films and substrates.
Examples of insulating materials include glass, synthetic resins, and ceramics.
Examples of conductive materials include metals, conductive metal oxides, and carbon.

(Film substrate)
When a film substrate is used as the substrate, the conductive laminate becomes a conductive film.
Examples of the film substrate include a plastic film made of a synthetic resin. Examples of the synthetic resin include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyacrylate. , polycarbonate, polyvinylidene fluoride, polyarylate, styrene elastomer, polyester elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate, and the like.
From the viewpoint of enhancing the adhesion between the film substrate and the conductive layer, the synthetic resin for the film substrate is preferably the same type of resin as the binder resin, and polyester resin such as polyethylene terephthalate is particularly preferable.

The synthetic resin for the film substrate may be amorphous or crystalline.
The film substrate may be unstretched or stretched.
The film substrate may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc., in order to further improve the adhesiveness of the conductive layer formed from the conductive polymer-containing liquid.

The average thickness of the film substrate is preferably 5 μm or more and 500 μm or less, more preferably 20 μm or more and 200 μm or less. When the average thickness of the film substrate is at least the lower limit, the film is less likely to break, and when it is at most the upper limit, sufficient flexibility as a film can be ensured.
The average thickness of the film substrate is the value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

(Glass substrate)
Examples of glass substrates include alkali-free glass substrates, soda-lime glass substrates, borosilicate glass substrates, quartz glass substrates, and the like. If the substrate contains an alkali component, the conductivity of the conductive layer tends to decrease, so among the above glass substrates, non-alkali glass is preferable. Here, the alkali-free glass is a glass composition in which the content of alkali components is 0.1% by mass or less with respect to the total mass of the glass composition.

The average thickness of the glass substrate is preferably 50 μm or more and 3000 μm or less, more preferably 100 μm or more and 1000 μm or less. If the average thickness of the glass substrate is at least the lower limit, it will be difficult to break, and if it is at most the upper limit, it can contribute to thinning of the conductive laminate.
The average thickness of the glass substrate is the value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

<<Method for manufacturing conductive laminate>>
A fourth aspect of the present invention is a method for producing a conductive laminate, comprising the step of applying the conductive polymer-containing liquid of the first aspect to at least a part of the surface of a substrate. By the production method of this aspect, the conductive laminate of the third aspect can be produced.

Methods for coating (applying) the conductive polymer-containing liquid to any surface of the substrate include, for example, gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, fountain coaters, Methods using coaters such as rod coaters, air doctor coaters, knife coaters, blade coaters, cast coaters, and screen coaters; methods using atomizers such as air spray, airless spray, and rotor dampening; and immersion methods such as dipping. can be applied.

The amount of the conductive polymer-containing liquid to be applied to the substrate is not particularly limited, but the solid content is 0.01 g/m ² or more in consideration of uniform coating, conductivity and film strength. It is preferably in the range of 10.0 g/m ² or less.

Conductivity in which a conductive layer (conductive film) is formed by drying a coating film made of a conductive polymer-containing liquid applied on a substrate and removing the dispersion medium, thereby curing the coating film. A laminate can be obtained.
Heat drying, vacuum drying, etc. are mentioned as a method of drying a coating film. As heat drying, for example, a method such as hot air heating or infrared heating can be employed.
When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium to be used, but is usually in the range of 50°C or higher and 200°C or lower. Here, the heating temperature is the set temperature of the drying device. A suitable drying time within the above heating temperature range is preferably 0.5 minutes or more and 30 minutes or less, more preferably 1 minute or more and 15 minutes or less.

When the conductive polymer-containing liquid contains an active energy ray-curable binder component, it may further include an active energy ray irradiation step of irradiating the dried coating film with an active energy ray. If the active energy ray irradiation step is included, the formation speed of the conductive layer can be increased, and the productivity of the conductive film is improved.
When having an active energy ray irradiation step, the active energy ray used includes ultraviolet rays, electron beams, visible rays, and the like. Ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps, and the like can be used as the ultraviolet light source.
The illuminance in ultraviolet irradiation is preferably 100 mW/cm ² or more. If the illuminance is less than 100 mW/cm ² , the active energy ray-curable binder component may not be sufficiently cured. In addition, the integrated amount of light is preferably 50 mJ/cm ² or more. If the integrated amount of light is less than 50 mJ/cm ² , sufficient cross-linking may not be achieved. In addition, the illuminance and the integrated amount of light in this specification are measured using Topcon UVR-T1 (industrial UV checker, light receiver; UD-T36, measurement wavelength range: 300 nm or more and 390 nm or less, peak sensitivity wavelength: about 355 nm). It is a measured value.

(Production example 1)
9 g of sodium styrenesulfonate, 90 g of ion-exchanged water, and 0.1 g of ammonium persulfate are added to 1 g of MA-DGIC (manufactured by Shikoku Kasei Kogyo Co., Ltd.) represented by the formula (1-1), and the mixture is stirred at room temperature for 1 hour. After stirring, it was confirmed that all of the MA-DGIC had dissolved, and the mixture was reacted at 80° C. for 8 hours. Next, 10 g of Duolite C255LFH (manufactured by Sumika Chemtex Co., Ltd., cation exchange resin) was added and stirred at room temperature for 16 hours. The resulting solution was filtered to remove Duolite C255LFH to obtain 100 g of a copolymer of MA-DGIC and styrenesulfonic acid (10 mass % aqueous solution). The weight average molecular weight of this copolymer was 300,000.

(Production example 2)
To 0.5 g of MA-DGIC represented by the formula (1-1), 9.5 g of sodium styrenesulfonate, 90 g of ion-exchanged water, and 0.1 g of ammonium persulfate were added, and the mixture was stirred at room temperature for 1 hour. , and MA-DGIC were all dissolved, and the mixture was reacted at 80° C. for 8 hours. Next, 10 g of Duolite C255LFH (manufactured by Sumika Chemtex Co., Ltd., cation exchange resin) was added and stirred at room temperature for 16 hours. The resulting solution was filtered to remove Duolite C255LFH to obtain 100 g of a copolymer of MA-DGIC and styrenesulfonic acid (10 mass % aqueous solution). The weight average molecular weight of this copolymer was 300,000.

(Production example 3)
To 1 g of DA-MGIC (manufactured by Shikoku Kasei Kogyo Co., Ltd.) represented by the formula (1-2), 9 g of sodium styrenesulfonate, 90 g of ion-exchanged water, and 0.1 g of ammonium persulfate are added, and the mixture is stirred at room temperature for 1 hour. After stirring, it was confirmed that DA-MGIC was completely dissolved, and the mixture was reacted at 80° C. for 8 hours. Next, 10 g of Duolite C255LFH (manufactured by Sumika Chemtex Co., Ltd., cation exchange resin) was added and stirred at room temperature for 16 hours. The obtained solution was filtered to remove Duolite C255LFH, and 100 g of a copolymer of DA-MGIC and styrenesulfonic acid (10 mass % aqueous solution) was obtained. The weight average molecular weight of this copolymer was 300,000.

(Production example 4)
To 0.5 g of DA-MGIC represented by the above formula (1-2), 9.5 g of sodium styrenesulfonate, 90 g of ion-exchanged water, and 0.1 g of ammonium persulfate were added and stirred at room temperature for 1 hour. , DA-MGIC was confirmed to be completely dissolved, and the mixture was reacted at 80° C. for 8 hours. Next, 10 g of Duolite C255LFH (manufactured by Sumika Chemtex Co., Ltd., cation exchange resin) was added and stirred at room temperature for 16 hours. The obtained solution was filtered to remove Duolite C255LFH, and 100 g of a copolymer of DA-MGIC and styrenesulfonic acid (10 mass % aqueous solution) was obtained. The weight average molecular weight of this copolymer was 300,000.

(Production example 5)
10 g of sodium styrenesulfonate, 90 g of ion-exchanged water, and 0.1 g of ammonium persulfate were mixed, stirred at air temperature for 1 hour, and reacted at 80° C. for 8 hours. Next, 10 g of Duolite C255LFH (a cation exchange resin manufactured by Sumika Chemtex Co., Ltd.) was added and stirred at room temperature for 16 hours. The resulting solution was filtered to remove Duolite C255LFH to obtain 100 g of a styrenesulfonic acid polymer (10 mass % aqueous solution). The weight average molecular weight of this copolymer was 200,000.

The mass-average molecular weight Mw of the copolymer synthesized above is the mass-based average molecular weight (may be referred to as mass-average molecular weight) measured by gel filtration chromatography using pullulan having a known mass-average molecular weight as a standard substance. .

(Example 1)
0.5 g of 3,4-ethylenedioxythiophene, 15 g of the copolymer of MA-DGIC and styrenesulfonic acid (10 mass % aqueous solution) of Production Example 1, and 84.5 g of deionized water were added. The resulting solution was kept at 20° C., and while stirring, an oxidizing agent solution of 0.03 g of ammonium persulfate dissolved in 4.97 g of ion-exchanged water and 1.1 g of ferric sulfate dissolved in 8.9 g of ion-exchanged water were added. The catalyst solution obtained was slowly added, and the resulting reaction solution was stirred for 24 hours to react.
By the above reaction, a conductive composite containing poly(3,4-ethylenedioxythiophene), which is a π-conjugated conductive polymer, and a copolymer of MA-DGIC and styrenesulfonic acid, and water as a dispersion medium. , the oxidizing agent and the catalyst were obtained.
13.2 g of Duolite C255LFH (manufactured by Sumika Chemtex Co., Ltd., cation exchange resin) and 13.2 g of Duolite A368S (manufactured by Sumika Chemtex Co., Ltd., anion exchange resin) were added to the conductive polymer-containing liquid and filtered. Then, the ion exchange resin was removed, and a conductive polymer-containing liquid from which the oxidizing agent and the catalyst were removed was obtained. Table 1 shows the results of measuring the mass, pH and particle size of the solid content (non-volatile component) of the obtained conductive polymer-containing liquid.
Next, the obtained conductive polymer-containing liquid was applied onto a PET film using a #4 bar coater and dried at 120° C. for 1 minute to obtain a conductive film.

(Example 2)
In Example 1, except that 15 g of the copolymer of MA-DGIC and styrenesulfonic acid (10% by mass aqueous solution) in Production Example 1 was changed to 10 g, and the amount of ion-exchanged water was changed to 89.5 g. A conductive polymer-containing liquid and a conductive film were obtained in the same manner.

(Example 3)
In Example 1, except that 15 g of the copolymer of MA-DGIC and styrenesulfonic acid (10% by mass aqueous solution) in Production Example 1 was changed to 20 g, and the amount of ion-exchanged water was changed to 79.5 g. A conductive polymer-containing liquid and a conductive film were obtained in the same manner.

(Example 4)
In Example 1, 15 g of the MA-DGIC/styrenesulfonic acid copolymer (10% by mass aqueous solution) of Production Example 1 was added to 15 g of the MA-DGIC/styrenesulfonic acid copolymer (10% by mass aqueous solution) of Production Example 2. A conductive polymer-containing liquid and a conductive film were obtained in the same manner as in Example 1, except for the changes.

(Example 5)
In Example 1, 15 g of the copolymer of MA-DGIC and styrenesulfonic acid (10% by mass aqueous solution) of Production Example 1 was added to 15 g of the copolymer of DA-MGIC and styrenesulfonic acid (10% by mass aqueous solution) of Production Example 3. A conductive polymer-containing liquid and a conductive film were obtained in the same manner as in Example 1, except for the changes.

(Example 6)
In Example 1, 15 g of the copolymer of MA-DGIC and styrenesulfonic acid (10% by mass aqueous solution) of Production Example 1 was added to 15 g of the copolymer of DA-MGIC and styrenesulfonic acid (10% by mass aqueous solution) of Production Example 4. A conductive polymer-containing liquid and a conductive film were obtained in the same manner as in Example 1, except for the changes.

(Comparative example 1)
Except that in Example 1, 15 g of the copolymer of MA-DGIC and styrenesulfonic acid (10% by mass aqueous solution) of Production Example 1 was changed to 15 g of the polymer of styrenesulfonic acid (10% by mass aqueous solution) of Production Example 5. A conductive polymer-containing liquid and a conductive film were obtained in the same manner as in Example 1.

<Evaluation>
The conductive film produced in each example was evaluated as follows. Table 1 shows the results.
[Surface resistance value]
The surface resistance value of the conductive layer was measured using a resistivity meter (Loresta manufactured by Nitto Seiko Analytic Tech Co., Ltd.) under the condition of an applied voltage of 10V. In the measurement results, 1.0E+07 represents 1.0×10 ⁷ and so on.
(Atmospheric exposure test)
The surface resistance value was measured immediately after the conductive film was produced (R ₀ ) and after being exposed to the atmosphere for 240 hours (R ₁ ), and the rate of change (R ₁ /R ₀ ) was calculated. . The closer the rate of change to 1, the higher the resistance to atmospheric exposure. Each measurement result is shown in Table 1.

[Measurement of pH]
The pH of the conductive polymer-containing liquid prepared in each example was measured at a temperature of 20° C. by a conventional method using a commercially available pH meter. Each measurement result is shown in Table 1.

[Method for measuring particle size]
The conductive polymer-containing liquid prepared in each example (the solid content concentration is shown in the table) was diluted with each dispersion medium to adjust the conductive composite concentration to 0.1% by mass. - Using a particle size/molecular weight measurement system (ELSZ-2000ZS, manufactured by Otsuka Electronics Co., Ltd.), the value obtained by measuring the cumulant average particle size at 25°C by the dynamic light scattering method was defined as the particle size.

<Result 1>
The resistance to atmospheric exposure of the conductive films of Examples 1 to 6 containing the conductive composite containing the polyanion having repeating units derived from isocyanuric acid (1) was remarkably improved. Moreover, compared with the conductive film of Comparative Example 1, the conductivity was excellent both immediately after production and after exposure to the atmosphere. A possible factor for this improvement in conductivity is the reduction in particle size.
Since the polyanion of Comparative Example 1 did not have a repeating unit derived from isocyanuric acid (1), it was inferior in air exposure resistance and electrical conductivity, and had a large particle size.

(Example 7)
To 100 g of the conductive polymer-containing liquid of Example 1, 50 g of isopropanol and 10 g of trioctylamine were added and stirred for 1 hour. The resulting reaction solution was filtered to obtain a reaction product of the conductive composite and trioctylamine as powder. Isopropanol was added to the resulting powder to make 500 g of a solution, and the solution was dispersed using a high-pressure homogenizer to obtain 500 g of an isopropanol dispersion containing the trioctylamine-modified conductive composite.
After measuring the solid content and particle size of the obtained dispersion, it was coated on a PET film using a #8 bar coater and dried at 100° C. for 1 minute to obtain a conductive film.

(Example 8)
A conductive film was obtained in the same manner as in Example 7, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 4.

(Example 9)
A conductive film was obtained in the same manner as in Example 7, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 5.

(Example 10)
A conductive film was obtained in the same manner as in Example 7, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 6.

(Comparative example 2)
A conductive film was obtained in the same manner as in Example 7 except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Comparative Example 1.

(Example 11)
To 100 g of the conductive polymer-containing liquid of Example 1, 25 g of an epoxy compound (Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether manufactured by Kyoeisha Chemical Co., Ltd.) was added, and the mixture was heated and stirred at 60° C. for 4 hours. At this time, a reaction product of the conductive composite and the epoxy compound was deposited. This precipitate was collected by filtration.
Methyl ethyl ketone was added to the resulting precipitate to make 300 g of a solution, and dispersed using a high-pressure homogenizer to obtain 300 g of methyl ethyl ketone dispersion containing the conductive composite modified with the epoxy compound.
After measuring the solid content and particle size of the obtained dispersion, it was coated on a PET film using a #8 bar coater and dried at 100° C. for 1 minute to obtain a conductive film.

(Example 12)
A conductive film was obtained in the same manner as in Example 11, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 4.

(Example 13)
A conductive film was obtained in the same manner as in Example 11, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 5.

(Example 14)
A conductive film was obtained in the same manner as in Example 11, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 6.

(Comparative Example 3)
A conductive film was obtained in the same manner as in Example 11, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Comparative Example 1.

(Example 15)
200 g of methanol and 2 g of tetraoctylammonium bromide were added to 100 g of the conductive polymer-containing liquid of Example 1, and the mixture was stirred for 1 hour. At this time, a reaction product of the conductive composite and the quaternary ammonium compound was deposited. The precipitate was filtered to recover 2.3 g of reaction product.
497.7 g of methyl ethyl ketone was added to the resulting precipitate and dispersed using a high-pressure homogenizer to obtain 500 g of a methyl ethyl ketone dispersion containing a conductive composite reacted with tetraoctylammonium bromide.
After measuring the solid content and particle size of the obtained dispersion, it was coated on a PET film using a #8 bar coater and dried at 100° C. for 1 minute to obtain a conductive film.

(Example 16)
A conductive film was obtained in the same manner as in Example 15, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 4.

(Example 17)
A conductive film was obtained in the same manner as in Example 15, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 5.

(Example 18)
A conductive film was obtained in the same manner as in Example 15, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 6.

(Comparative Example 4)
A conductive film was obtained in the same manner as in Example 15, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Comparative Example 1.

(Example 19)
To 100 g of the conductive polymer-containing liquid of Example 1, 25 g of an epoxy compound (Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether manufactured by Kyoeisha Chemical Co., Ltd.) was added, and the mixture was heated and stirred at 60° C. for 4 hours. Next, 50 g of isopropanol and 10 g of trioctylamine were added and stirred for 1 hour. At this time, a reaction product of the conductive composite, epoxy compound and trioctylamine was deposited. This precipitate was collected by filtration.
Ethyl acetate was added to the resulting precipitate to make 800 g of a solution, and dispersed using a high-pressure homogenizer to obtain an 800 g ethyl acetate dispersion containing the conductive composite modified with the epoxy compound and trioctylamine.
After measuring the solid content and particle size of the obtained dispersion, it was coated on a PET film using a #8 bar coater and dried at 100° C. for 1 minute to obtain a conductive film.

(Example 20)
A conductive film was obtained in the same manner as in Example 19, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 4.

(Example 21)
A conductive film was obtained in the same manner as in Example 19, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 5.

(Example 22)
A conductive film was obtained in the same manner as in Example 19, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Example 6.

(Comparative Example 5)
A conductive film was obtained in the same manner as in Example 19, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Comparative Example 1.

<Result 2>
Conductive Examples 7-22 comprising a conductive complex wherein the polyanion having repeating units derived from isocyanuric acid (1) is modified by one or more selected from epoxy compounds, amine compounds and quaternary ammonium compounds. The resistance to atmospheric exposure of the film was remarkably improved. Moreover, compared with the conductive films of Comparative Examples 2 to 5, the conductivity was excellent both immediately after production and after exposure to the atmosphere. A possible factor for this improvement in conductivity is the reduction in particle size.
Since the polyanions of Comparative Examples 2 to 5 did not have repeating units derived from isocyanuric acid (1), they were inferior in air exposure resistance and electrical conductivity, and had large particle sizes.

Claims (10)

A conductive polymer-containing liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, and a dispersion medium,
The conductive polymer-containing liquid, wherein the polyanion is a copolymer of an anionic compound having an anionic group and a vinyl group and an isocyanuric acid derivative represented by the following formula (1).

[In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom or an arbitrary substituent, and at least one of R ¹ , R ² and R ³ is a substituent having a vinyl group. ] 2. The conductive polymer-containing liquid according to claim 1, wherein a part of said anion groups constituting said polyanion are modified by reaction with an amine compound or a quaternary ammonium compound. 2. The conductive polymer-containing liquid according to claim 1, wherein a part of said anion group constituting said polyanion is modified by reaction with an epoxy compound. 2. The conductive polymer-containing liquid according to claim 1, wherein a part of said anionic groups constituting said polyanion are modified by reaction with an epoxy compound and an amine compound or a quaternary ammonium compound. 5. The method according to any one of claims 1 to 4, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene), or the compound having an anion group and a vinyl group is styrenesulfonic acid. The conductive polymer-containing liquid according to any one of items 1 and 2. By polymerizing a monomer forming a π-conjugated conductive polymer in a reaction liquid containing a polyanion and a dispersion medium, a conductive composite containing the π-conjugated conductive polymer and the polyanion and the dispersion A method for producing a conductive polymer-containing liquid, comprising a conductive composite forming step of obtaining a conductive polymer-containing liquid containing a medium,
A method for producing a conductive polymer-containing liquid, wherein the polyanion is a copolymer of an anionic compound having an anionic group and a vinyl group and an isocyanuric acid derivative represented by the following formula (1).

[In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom or an arbitrary substituent, and at least one of R ¹ , R ² and R ³ is a substituent having a vinyl group. ] A preparation step for obtaining the copolymer in advance by polymerizing the anionic compound and the isocyanuric acid derivative in a reaction solution containing the anionic compound, the isocyanuric acid derivative, an oxidizing agent, and a dispersion medium. death,
In the preparation step, the isocyanuric acid derivative to be supplied to the reaction solution has a substituent in which R ¹ in the formula (1) has a vinyl group, R ² has a substituent having an epoxy group, and R ³ is hydrogen. A compound that is an atom or any substituent,
7. The method for producing a conductive polymer-containing liquid according to claim 6, wherein in the reaction liquid, the epoxy group is ring-opened to form a hydroxyl group by the action of the oxidizing agent during the polymerization. Adding one or more selected from an epoxy compound, an amine compound and a quaternary ammonium compound to the conductive polymer-containing liquid obtained in the conductive composite forming step, and reacting with the conductive composite. The conductive polymer-containing liquid according to claim 6 or 7, further comprising a modification step of precipitating a reaction product, collecting the precipitated reaction product, and adding a solvent to obtain a conductive polymer-containing liquid. Liquid manufacturing method. A base material and a conductive layer formed on at least a part of the surface of the base material,
A conductive laminate, wherein the conductive layer is a cured product of the conductive polymer-containing liquid according to any one of claims 1 to 5. A method for producing a conductive laminate, comprising applying the conductive polymer-containing liquid according to any one of claims 1 to 5 to at least a part of a substrate to form a conductive layer. .