JP2023032463A - Conductive polymer-containing liquid and conductive laminate - Google Patents

Abstract

To provide a conductive laminate that includes a conductive layer having improved atmosphere exposure resistance, and a conductive polymer-containing liquid that can form the conductive layer.SOLUTION: A conductive polymer-containing liquid contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, an organic solvent, at least one acryl monomer, and urethane acrylate excluding the acryl monomer. The polyanion is modified by a reaction between some anion groups of the polyanion and a quaternary ammonium compound.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a conductive polymer-containing liquid containing a π-conjugated conductive polymer and a conductive laminate.

A π-conjugated conductive polymer whose main chain is composed of a π-conjugated system forms a conductive composite when doped 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. In addition, the conductive composite may be reacted with an epoxy compound for the purpose of increasing the wettability of the conductive polymer-containing liquid to the film substrate or increasing the conductivity of the conductive layer to be formed. Furthermore, as a technique for suppressing a decrease in conductivity over time in the atmosphere of a conductive layer containing a conductive composite, for example, Patent Document 1 discloses an aromatic compound represented by a specific chemical formula in a conductive layer. is disclosed.

Japanese Patent Application Laid-Open No. 2020-143202

The present invention provides a conductive laminate having a conductive layer with improved resistance to atmospheric exposure, and a conductive polymer-containing liquid capable of forming the conductive layer.

[1] A conductive polymer-containing liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an organic solvent, one or more acrylic monomers, and a urethane acrylate other than the acrylic monomer. A liquid containing a conductive polymer, wherein the polyanion is modified by reaction of a part of the anion group of the polyanion with a quaternary ammonium compound.
[2] The conductive polymer-containing liquid according to [1], which further contains a photopolymerization initiator.
[3] The conductive polymer-containing liquid according to [1] or [2], further containing a silica compound.
[4] The conductive polymer-containing liquid according to any one of [1] to [3], wherein the organic solvent contains at least one selected from isopropyl alcohol, methyl ethyl ketone, and propylene glycol monomethyl ether.
[5] At least the acrylic monomer is selected from pentaerythritol triacrylate, pentaerythritol tetraacrylate, 2-hydroxyethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and N-acryloylmorpholine The conductive polymer-containing liquid according to any one of [1] to [4], including 1 type.
[6] Any one of [1] to [5], wherein the π-conjugated conductive polymer contains poly(3,4-ethylenedioxythiophene), or the polyanion contains polystyrenesulfonic acid. The liquid containing the conductive polymer according to the item.
[7] The conductive polymer-containing liquid according to any one of [1] to [6], wherein the quaternary ammonium compound has at least one hydrocarbon group with 4 to 32 carbon atoms.
[8] The conductive polymer-containing liquid according to any one of [1] to [7], wherein the quaternary ammonium compound contains tetraoctylammonium.
[9] A conductive laminate comprising, on at least part of a substrate, a conductive layer comprising a cured product of the conductive polymer-containing liquid according to any one of [1] to [8].
[10] Before and after an atmospheric exposure experiment in which the conductive laminate is left in an environment of 25° C. and exposed to the atmosphere for 10 days, the increase in surface resistivity of the conductive layer of the conductive laminate is 10 times or less. is suppressed to, the conductive laminate according to [9].

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. The conductive laminate of the present invention comprises a conductive layer having excellent resistance to atmospheric exposure.

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 composite containing a π-conjugated conductive polymer and a polyanion, an organic solvent, one or more acrylic monomers, and urethane acrylate. be.
The polyanion has been modified by reaction of some of the anionic groups of the polyanion with a quaternary ammonium compound, resulting in particularly improved dispersibility in isopropyl alcohol.
In the conductive polymer-containing liquid of this aspect, the conductive composite may be in a dispersed state or in a dissolved state. In this specification, the dispersed state and the dissolved state are not distinguished from each other unless otherwise specified, and are simply referred to as the dispersed state.

[Conductive composite]
The conductive composite contained in the conductive polymer-containing liquid of this embodiment contains a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive composite forms a conductive composite having conductivity by doping the π-conjugated conductive polymer.
In the polyanion, only some of the anionic groups are doped into the π-conjugated conductive polymer, and there are surplus anionic groups that do not participate in the doping. Since the surplus anionic groups are hydrophilic groups, the conductive composite in which the surplus anionic groups are not modified has water dispersibility.

(π-conjugated conductive polymer)
The π-conjugated conductive polymer may be any organic polymer having a π-conjugated main chain. molecules, polyphenylene-based conductive polymers, polyphenylene-vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene-vinylene-based conductive polymers, copolymers thereof, and the like. 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 these π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred because of its excellent 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)
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 anionic group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such 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, Polymers having carboxy groups such as polyallylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, etc. A polyanion is a single monomer. may be a homopolymer obtained by polymerizing or a copolymer obtained by polymerizing two or more monomers.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be further increased.
One of the polyanions may be used alone, or two or more thereof may be used in combination.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, more preferably 100,000 or more and 500,000 or less. The mass-average molecular weight of the polyanion is the mass-based average molecular weight determined by pullulan conversion using gel filtration chromatography.

Assuming that the total number of anionic groups in the polyanion is 100 mol %, the excess anionic group is preferably 30 mol % or more and 90 mol % or less, more preferably 45 mol % or more and 75 mol % or less.

The polyanion of the present invention is modified by reacting surplus anionic groups of the polyanion that do not participate in doping (hereinafter also referred to as "partial anionic groups") with a quaternary ammonium compound. That is, the polyanion of the present invention has substituents (C) formed by reaction of the quaternary ammonium compound with some of the anionic groups.

(Substituent C)
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 32 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.

The quaternary ammonium compound preferably has a substituent having 3 or more carbon atoms on the nitrogen atom, and has a substituent of 5 or more, because the dispersibility in the organic solvent increases and the conductivity improves. It is more preferable to have a substituent having 7 or more carbon atoms on the nitrogen atom. The upper limit of the carbon number of each substituent on the nitrogen atom is not particularly limited, and in consideration of solubility and reactivity in solvents, for example, it is preferably 40 or less, more preferably 30 or less, and further 20 or less. 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.

Further, the quaternary ammonium compound preferably has at least one hydrocarbon group having 4 to 32 carbon atoms, since the dispersibility in organic solvents is increased and the conductivity is improved.

Preferably, the quaternary ammonium compound is a tetraalkylammonium halide. This is because the polyanion is highly reactive and the reaction product is difficult to dissolve in an aqueous dispersion medium and easily precipitates. The halogen ion of the counter anion is preferably a bromide ion or a chloride ion, more preferably a bromide ion.

Specific examples of quaternary ammonium compounds include tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, tetra-n-octylammonium 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.

The content of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer, and is 10 parts by mass or more and 700 parts by mass or less. is more preferable, and 100 parts by mass or more and 500 parts by mass or less is even more preferable. If the polyanion content is at least the above lower limit, the doping effect on the π-conjugated conductive polymer tends to be stronger, resulting in higher conductivity. On the other hand, if the polyanion content is equal to or less than the above upper limit, the amount of anionic groups that do not participate in doping is appropriately suppressed, and the anionic groups can be easily converted to hydrophobicity when the quaternary ammonium compound is reacted.

The content of the conductive composite with respect to the total mass of the conductive polymer-containing liquid is, for example, preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 1% by mass or less, 0.1% by mass or more and 0.6% by mass or less is more preferable. Within the above preferred range, the dispersion stability of the conductive composite is improved.

[Acrylic monomer]
The acrylic monomer of this embodiment is a known polymerizable compound having a (meth)acrylic group (also known as (meth)acryloyl group). Here, the notation of "(meth)acryl" means "acrylic or methacryl", and the notation of "(meth)acryloyl" means "acryloyl or methacryloyl". (Meth)acryl groups include (meth)acryloxy groups. Incidentally, the acrylic monomer of this aspect is a polymerizable acrylic compound other than urethane acrylate.

The molecular weight of the acrylic monomer is preferably 1000 or less, more preferably 500 or less, from the viewpoint of enhancing dispersibility in the conductive polymer-containing liquid and enhancing reactivity during curing of the conductive polymer-containing liquid. The lower limit of the molecular weight of the acrylic monomer is not particularly limited, and is usually 100 or more.

The number of (meth)acrylic groups in the molecule of the acrylic monomer may be one, or two or more. The above number is preferably 2 or more, more preferably 3 or more, from the viewpoint of increasing the hardness when the conductive polymer-containing liquid is cured. The upper limit of the above number is not particularly limited, and is preferably 6 or less, more preferably 5 or less, in terms of availability of commercial products.

Examples of acrylic monomers include (meth)acrylates (also known as (meth)acrylic acid esters) and (meth)acrylamides.
From the viewpoint of increasing the atmospheric exposure resistance of the conductive layer made of the conductive polymer-containing liquid of this embodiment, the conductive polymer-containing liquid preferably contains both (meth)acrylate and (meth)acrylamide.

(Meth)acrylates include, for example, (meth)acrylates having a linear, branched or cyclic monovalent hydrocarbon group (eg, alkyl group) having 1 to 12 carbon atoms at the end of an ester group. Here, one or more hydrogen atoms bonded to the monovalent hydrocarbon group may be substituted with another (meth)acryl group. If the (meth)acrylate has two or more (meth)acryl groups, arbitrarily select one (meth)acryl group, and assume that the remaining (meth)acryl groups are hydrogen atoms. , counting the number of carbon atoms of the monovalent hydrocarbon group ester-bonded to the selected (meth)acrylic group.
One or more hydrogen atoms (-H) constituting the monovalent hydrocarbon group of the (meth)acrylate may be substituted with a hydroxyl group.
One or more methylene groups ( _--CH.sub.2-- ) constituting the monovalent hydrocarbon group of the (meth)acrylate may be substituted with oxygen atoms as long as the oxygen atoms are not bonded to each other.

Examples of acrylates include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polyethylene glycol diacrylate. , 1,6-hexanediol diacrylate, bisphenol A/ethylene oxide-modified diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol monohydroxy pentaacrylate, tri Examples include methylolpropane triacrylate and glycerin propoxy triacrylate.
Examples of methacrylates include n-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, and glycidyl methacrylate. , tetrahydrofurfuryl methacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate and the like.
(Meth)acrylamides include, for example, methacrylamide, 2-hydroxyethylacrylamide, N-methylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N-phenylacrylamide, N-methylolacrylamide, dimethylaminopropylacrylamide, Dimethylaminopropylmethacrylamide, diacetoneacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-vinylformamide, N-acryloylmorpholine, acryloylpiperidine and the like.
Among these, pentaerythritol triacrylate, pentaerythritol tetraacrylate, 2-hydroxyethylacrylamide, N,N-dimethylacrylamide, At least one selected from N,N-diethylacrylamide and N-acryloylmorpholine is particularly preferred.

The total content of one or more acrylic monomers with respect to the total mass of the conductive polymer-containing liquid of this embodiment is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less. % by mass or more and 40% by mass or less is more preferable.
When it is at least the lower limit of the above range, the hardness and resistance to atmospheric exposure of the conductive layer comprising the conductive polymer-containing liquid can be further enhanced.
When it is equal to or less than the upper limit of the above range, it is possible to suppress deterioration in the conductivity of the conductive layer made of the conductive polymer-containing liquid.

The total content of the acrylic monomers contained in the conductive polymer-containing liquid of this embodiment is preferably 100 parts by mass or more and 1000 parts by mass or less, and 125 parts by mass or more and 700 parts by mass with respect to 1 part by mass of the conductive composite. The following are more preferable, and 150 parts by mass or more and 500 parts by mass or less are even more preferable.
When it is at least the lower limit of the above range, the hardness and resistance to atmospheric exposure of the conductive layer comprising the conductive polymer-containing liquid can be further enhanced.
When it is equal to or less than the upper limit of the above range, it is possible to suppress deterioration in the conductivity of the conductive layer made of the conductive polymer-containing liquid.

[Urethane acrylate]
The urethane acrylate of this aspect is a compound having at least one (meth)acryloyl group and at least one urethane group in the molecule. Urethane acrylates having two or more (meth)acryloyl groups are collectively referred to as polyfunctional urethane acrylates.
From the viewpoint of further increasing the hardness and atmospheric exposure resistance of the conductive layer made of the conductive polymer-containing liquid, the number of (meth)acryloyl groups (number of functional groups) in the molecule of the urethane acrylate is preferably 2 or more, and 6. 8 or more is more preferable, and 10 or more is particularly preferable. A guideline for the upper limit of this number is 20 or less.

Urethane acrylates are, for example, those obtained by reacting (meth)acrylates having one or more hydroxyl groups with one or more polyvalent isocyanates, (meth)acrylates having one or more isocyanate groups, and one Examples include those obtained by reacting the above polyols, and those obtained by reacting one or more hydroxyl group-containing (meth)acrylates, one or more polyvalent isocyanates, and one or more polyols.

(Meth)acrylates having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6- Hydroxyhexyl (meth)acrylate and the like.

Examples of polyvalent isocyanates include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; Aliphatic polyisocyanates such as diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis( and alicyclic polyisocyanates such as isocyanatomethyl)cyclohexane.

Examples of polyols include polyether-based polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol; polyols and the like.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylene. diol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.) and the like.

Examples of polyvalent carboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid, 1,4- Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid and trimellitic acid.

The mass average molecular weight of the urethane acrylate is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 50,000 or less, and even more preferably 3,000 or more and 10,000 or less. Here, the mass-average molecular weight of urethane acrylate is a mass-based average molecular weight obtained by measuring using gel filtration chromatography and calculated in terms of polystyrene.
When it is at least the lower limit of the above range, the degree of cure and resistance to atmospheric exposure of the conductive layer containing the conductive polymer-containing liquid can be further enhanced.
If it is equal to or less than the upper limit of the above range, the dispersibility of the urethane acrylate in the conductive polymer-containing liquid is improved, the reactivity of the conductive polymer-containing liquid during curing is enhanced, and the degree of cure of the conductive layer to be formed. and atmospheric exposure resistance can be further enhanced.

The content of urethane acrylate with respect to the total mass of the conductive polymer-containing liquid of this embodiment is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and 1% by mass. Above 5% by mass or less is more preferable.
When it is at least the lower limit of the above range, the hardness and resistance to atmospheric exposure of the conductive layer comprising the conductive polymer-containing liquid can be further enhanced.
When it is equal to or less than the upper limit of the above range, it is possible to suppress deterioration in the conductivity of the conductive layer made of the conductive polymer-containing liquid.

The content of the urethane acrylate contained in the conductive polymer-containing liquid of this embodiment is preferably 1 part by mass or more and 1000 parts by mass or less, and preferably 10 parts by mass or more and 500 parts by mass or less with respect to 1 part by mass of the conductive composite. It is more preferably 10 parts by mass or more and 100 parts by mass or less.
When it is at least the lower limit of the above range, the hardness and resistance to atmospheric exposure of the conductive layer comprising the conductive polymer-containing liquid can be further enhanced.
When it is equal to or less than the upper limit of the above range, it is possible to suppress deterioration in the conductivity of the conductive layer made of the conductive polymer-containing liquid.

[Silica compound]
The conductive polymer-containing liquid of this aspect preferably contains one or more silica compounds. By containing the silica compound, the hardness and atmospheric exposure resistance of the conductive layer made of the conductive polymer-containing liquid can be further increased.
Silica compounds are generally compounds containing silicon oxide. The silica compound of this embodiment is preferably colloidal silica that has been granulated to the extent that it can form a colloid in the dispersion medium.
When silanol groups are present on the surface of the silica compound, the dispersibility in organic solvents may deteriorate. From the viewpoint of improving the dispersibility in an organic solvent in the conductive polymer-containing liquid of this embodiment, it is preferable that at least a part of the silanol groups of the silica compound is hydrophobized by chemical modification. Silica compounds surface-treated in this way are sometimes generically referred to as organosilica. Organosilica includes, for example, those obtained by silylating colloidal silica with a disiloxane compound and/or a monoalkoxysilane compound.

Organosilica preferably has a reactive functional group capable of undergoing a radical polymerization reaction with the (meth)acryloyl group of the acrylic monomer and urethane acrylate described above. When the conductive polymer-containing liquid is cured, the silica compound is integrated with the acrylic monomer and urethane acrylate, and the hardness and resistance to atmospheric exposure can be further improved.
Examples of commercially available organosilica products having such reactive functional groups include surface-modified grades of organosilica sol manufactured by Nissan Chemical Industries, Ltd., and STA-SiA TAZ series manufactured by Taisei Fine Chemicals.

The content of the silica compound relative to the total mass of the conductive polymer-containing liquid of this embodiment is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 6% by mass or less, and 0.4% by mass. % by mass or more and 4% by mass or less is more preferable.
When it is at least the lower limit of the above range, the hardness and resistance to atmospheric exposure of the conductive layer comprising the conductive polymer-containing liquid can be further enhanced.
When it is equal to or less than the upper limit of the above range, it is possible to suppress deterioration in the conductivity of the conductive layer made of the conductive polymer-containing liquid.

The content of the silica compound contained in the conductive polymer-containing liquid of this embodiment is preferably 1 part by mass or more and 1000 parts by mass or less, and preferably 2 parts by mass or more and 500 parts by mass or less with respect to 1 part by mass of the conductive composite. It is more preferably 3 parts by mass or more and 100 parts by mass or less.
When it is at least the lower limit of the above range, the hardness and resistance to atmospheric exposure of the conductive layer comprising the conductive polymer-containing liquid can be further enhanced.
When it is equal to or less than the upper limit of the above range, it is possible to suppress deterioration in the conductivity of the conductive layer made of the conductive polymer-containing liquid.

(Polymerizable compound capable of copolymerization)
The conductive polymer-containing liquid of this embodiment may contain another polymerizable compound that can be copolymerized with the acrylic monomer as long as the effects of the present invention are not impaired. Known polymerizable compounds known to be copolymerizable with acrylic monomers include, for example, unsaturated carboxylic acids such as maleic acid and itaconic acid and derivatives thereof, and acid anhydrides such as maleic anhydride and itaconic anhydride. and derivatives thereof, vinyl esters such as vinyl acetate and vinyl benzoate, vinyl chloride, vinylidene chloride and derivatives thereof, and aromatic vinyl compounds such as styrene and α-methylstyrene.
When the conductive polymer-containing liquid of the present embodiment contains the polymerizable compound, the content thereof can be, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the acrylic monomer. .

[Polymerization initiator]
The conductive polymer-containing liquid of this aspect preferably contains a radical polymerization initiator. Radical polymerization initiators include photopolymerization initiators and thermal polymerization initiators. Among them, a photopolymerization initiator is preferable because the reaction control is easy.

(Photoinitiator)
A photoinitiator can be used individually by 1 type or in combination of 2 or more types.
Examples of photopolymerization initiators include benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photoactive oxime-based photopolymerization initiators. agents, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, etc. things are mentioned.
Specific benzoin ether-based photopolymerization initiators include, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1- ON [trade name: Irgacure 651, manufactured by BASF], anisole methyl ether, and the like. Acetophenone-based photopolymerization initiators include, for example, 1-hydroxycyclohexylphenyl ketone [trade name: Omnirad 184, manufactured by IGM Resins], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4-( 2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [trade name: Irgacure 2959, manufactured by BASF], 2-hydroxy-2-methyl-1-phenyl-propane- 1-one [trade name: Darocure 1173, manufactured by BASF], methoxyacetophenone, and the like.

(Thermal polymerization initiator)
A thermal polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
Examples of thermal polymerization initiators include known azo initiators, persulfates, peroxide initiators, and the like.

[Dispersion medium]
The organic solvent contained in the conductive polymer-containing liquid of this embodiment is a dispersion medium for dispersing the conductive composite hydrophobized by the reaction with the quaternary ammonium compound.

Examples of the organic solvent include hydrocarbon-based solvents, ketone-based solvents, alcohol-based solvents, ether-based solvents, and nitrogen atom-containing compound-based solvents.
Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of aliphatic hydrocarbon solvents include pentane, hexane, heptane, octane, decane, cyclohexane, and methylcyclohexane. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene 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 alcohol solvents include methanol, ethanol, isopropyl alcohol, 1-propanol, n-butanol, t-butanol, and allyl alcohol.
Examples of ether-based solvents include diethyl ether, dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether, and the like.
Examples of nitrogen atom-containing compound solvents include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.
Among them, one or more selected from methyl ethyl ketone, isopropyl alcohol and propylene glycol monomethyl ether are preferable.

From the viewpoint of enhancing the dispersion stability of the conductive composite in the conductive polymer-containing liquid of this embodiment, the organic solvent particularly preferably contains isopropyl alcohol.
The content of isopropyl alcohol with respect to the total mass of the conductive polymer-containing liquid is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the content of isopropyl alcohol is, for example, 90% by mass or less, leaving room for the conductive composite and other components. Within the above preferred range, the dispersion stability of the conductive composite is improved, and the wettability to the substrate is also excellent.

The conductive polymer-containing liquid of this embodiment may contain a small amount of water.
The water content relative to the total mass of the conductive polymer-containing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less. When the water content is low, the dispersion stability of the conductive composite is improved and the wettability to the substrate is also excellent.

(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 liquid containing conductive polymer>>
The conductive polymer-containing liquid of the first aspect of the present invention comprises a conductive composite that has been hydrophobized by reacting with a quaternary ammonium compound, an acrylic monomer, a urethane acrylate, an organic solvent, and optionally silica. It can be obtained by mixing a compound, a polymerization initiator and other additives in a conventional manner.

As a method for reacting the conductive composite with the quaternary ammonium compound, the following method is preferred. That is, an aqueous conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion is added dropwise to an organic solution (reaction solution) containing a quaternary ammonium compound, and one of the polyanions is added dropwise. A reaction precipitation step of reacting the anion group of the part with the quaternary ammonium compound to precipitate a reaction product, a recovery step of recovering the reaction product, and dispersing the recovered reaction product in an organic solvent. and a preparation step of obtaining an organic solvent solution of a conductive polymer is preferably performed in order.
A washing step may be further included between the recovery step and the preparation step.

[Reactive precipitation step]
In this step, an aqueous conductive polymer dispersion is added to an organic solution (reaction solution) containing a quaternary ammonium compound to form a reaction product of the conductive composite and the quaternary ammonium compound in the reaction solution. It is a process of precipitating inside.

When the conductive polymer aqueous dispersion is added to the reaction solution, the quaternary ammonium compound stably reacts with some anionic groups of the polyanions of the conductive composite. As a result, the above-described substituent (C) is formed, the conductive composite becomes hydrophobic, the dispersion stability in isopropyl alcohol is improved, and stable dispersion in the reaction solution becomes difficult. Precipitates to form precipitates.

The number of organic solvents contained in the reaction solution may be one, or two or more.
Examples of the organic solvent include organic solvents already exemplified, such as methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, t-butanol, and allyl alcohol.

The content of the quaternary ammonium compound in the reaction solution is 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 total mass of the conductive composite to be added. is more preferable, and 150 parts by mass or more and 500 parts by mass or less is even more preferable.
When it is at least the lower limit of the above range, the reaction efficiency between the conductive composite and the quaternary ammonium compound is enhanced, and the reaction product can be easily obtained.
If it is equal to or less than the upper limit of the above range, it is possible to prevent a decrease in conductivity of the conductive composite due to contamination with an unreacted quaternary ammonium compound.

The aqueous conductive polymer dispersion is a dispersion in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium.
Here, the aqueous dispersion medium is water or a mixture of water and a water-soluble organic solvent. A water-soluble organic solvent is one that dissolves 1 g or more in 100 g of water (20° C.). Examples of water-soluble organic solvents include alcohol-based solvents, ketone-based solvents, and ester-based solvents. The number of water-soluble organic solvents contained in the aqueous dispersion medium may be one, or two or more.
The water content relative to the total mass of the aqueous dispersion medium is preferably more than 50% by mass, more preferably 60% by mass or more, still more preferably 80% by mass or more, and may be 100% by mass. A high water content increases the dispersibility of the conductive composite, which in turn increases the reaction efficiency with the quaternary ammonium compound. Furthermore, the reaction product is easily precipitated in the reaction solution.

The conductive polymer aqueous dispersion can be obtained, for example, by chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous polyanion solution. A commercially available conductive polymer aqueous dispersion may also be used.
A known catalyst may be applied to the chemical oxidation polymerization. For example, catalysts and oxidants can be used. 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 content of the π-conjugated conductive polymer and the polyanion is preferably 0.1% by mass or more and 5% by mass or less, and 0.5% by mass or more and 2% by mass or less with respect to the total mass of the aqueous conductive polymer dispersion. is more preferable, and 0.8% by mass or more and 1.5% by mass or less is even more preferable.
Within the above preferred range, the dispersibility of the conductive composite increases, and the reaction efficiency with the quaternary ammonium compound increases.

The volume ratio (V1/V2) of the volume V2 of the conductive polymer aqueous dispersion to be added to the volume V1 of the reaction solution is preferably 0.3 to 3.0, more preferably 0.5 to 2.5. 0.8 to 2.0 is more preferable.
Within the above preferred range, the reaction proceeds stably and the reaction product easily precipitates.

The method of adding the conductive polymer aqueous dispersion to the reaction solution is not particularly limited, and the desired amount may be added at once in several seconds, or may be added dropwise slowly. From the viewpoint of obtaining a conductive composite with a small particle size and increasing the conductivity, the method of dropping slowly is preferred.
The speed at which the conductive polymer aqueous dispersion is dropped into the reaction solution is preferably 1 minute to 3 hours, more preferably 10 minutes to 2 hours, from the start of dropping to the end of dropping, assuming that a constant amount of water is continuously dropped. . It is preferable to gently stir the reaction solution during the dropping.
Within the above preferred range, the reaction proceeds stably and the reaction product easily precipitates.

The amount of the conductive polymer aqueous dispersion added dropwise to the reaction solution is preferably 0.1 to 100 ml/min, more preferably 1 to 10 ml/min. It is preferable to gently stir the reaction solution during the dropping.
Within the above preferred range, the reaction proceeds stably and the reaction product easily precipitates.

When the conductive polymer dispersion is added to the reaction solution and gently stirred, the reaction product is precipitated within several minutes to several hours. The completion of the reaction can be confirmed by visually observing the completion of precipitation of the reaction product.

The temperature of the reaction solution is not particularly limited, and may be, for example, 5 to 40°C.

[Recovery process]
This step is a step of recovering the reaction product as a precipitate.
The recovery method is not particularly limited, and can be recovered, for example, by decantation or filtration.
The amount of water in the recovered reaction product (precipitate) is preferably as low as possible, and most preferably no water at all.
Methods for reducing the water content include, for example, a method of washing away the precipitate with an organic solvent, a method of drying the precipitate, and the like.

[Washing process]
A washing step is preferably added between the recovery step and the preparation step. The washing step is a step of washing the precipitate with an organic solvent for washing. This washing process can remove residual water, unreacted quaternary ammonium compounds, impurities contained in the conductive polymer aqueous dispersion, and the like.

The organic solvent for washing is preferably one that can be washed while minimizing the dissolution of precipitates. Therefore, the organic solvent for cleaning is preferably an alcohol-based solvent other than isopropyl alcohol. 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

[Preparation process]
This step is a step of adding an organic solvent to the precipitate to obtain a conductive polymer-containing liquid.

As the organic solvent in this step, it is preferable to use the organic solvent contained in the conductive polymer-containing liquid of the first embodiment. Since the conductive composite is modified with a quaternary ammonium compound, it is preferred to use isopropyl alcohol to fully disperse the conductive composite. In addition to isopropyl alcohol, an optional organic solvent such as one or more selected from alcohol-based solvents other than isopropyl alcohol may be added.
The content of each solvent contained in the organic solvent is preferably within the preferred ranges exemplified in the first aspect.

It is preferable to subject the organic solvent solution of the conductive composite obtained by adding the organic solvent to the precipitate to dispersion treatment by stirring. 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).

The content of the conductive composite with respect to the total mass of the organic solvent solution dispersed with a high-pressure homogenizer is, for example, preferably 0.01% by mass or more and 5% by mass or less, and 0.05% by mass or more and 2% by mass or less. It is more preferably 0.1% by mass or more and 1% by mass or less.
When the concentration is within the above range, the dispersibility of the conductive composite can be sufficiently enhanced.

<<Conductive laminate>>
A second aspect of the present invention is a conductive laminate comprising a substrate and a conductive layer formed on at least one surface of the substrate and formed of a cured product of the conductive polymer-containing liquid of the first aspect. is.

[Conductive layer]
The average thickness of the conductive layer provided on at least one 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, 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 a conductive composite containing a π-conjugated conductive polymer and a polyanion. Furthermore, it contains cured products of acrylic monomers and urethane acrylates.

[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 100 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.

The conductive layer of the conductive laminate of this embodiment is excellent in resistance to atmospheric exposure. Specifically, before and after an atmospheric exposure experiment in which the conductive laminate is left to stand in an environment of 25 ° C. and exposed to the atmosphere for 10 days (240 hours), the increase in the surface resistivity of the conductive layer is preferably 10 times. Below, it is desirable to be suppressed to 2 times or less, more preferably 1.5 times or less.
Here, the increase is represented by a ratio (R1/R0) obtained by dividing the surface resistivity R1 after the air exposure test by the surface resistivity R0 before the air exposure test.

<<Method for manufacturing conductive laminate>>
The conductive laminate of the second aspect of the invention is obtained by the following method. That is, the method includes applying the conductive polymer-containing liquid of the first aspect to at least one surface of a substrate.

Methods for coating (coating) the conductive polymer-containing liquid of the first aspect onto any surface of the substrate include, for example, a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, and a kiss coater. , methods using coaters such as fountain coaters, 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; An immersion method or the like 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.

The coating film made of the conductive polymer-containing liquid coated on the substrate is dried to remove the dispersion medium, and the coating film is cured by polymerizing the acrylic monomer and urethane acrylate. A conductive laminate having a conductive layer (conductive film) formed thereon 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 150°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 1 minute or more and 30 minutes or less, more preferably 1 minute or more and 10 minutes or less.

As a method for polymerizing the acrylic monomers and urethane acrylate contained in the coating film, radical polymerization is easy and reliable, and therefore preferred. When applying radical polymerization, it is preferable to add a polymerization initiator to the conductive polymer-containing liquid in advance. Polymerization can be carried out by heating or irradiating with light (active energy ray) depending on the type of polymerization initiator. Examples of active energy rays include 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.

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

(Production Example 2) Synthesis of Conductive Polymer Dispersion Containing π-Conjugated Conductive Polymer and Polyanion 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid were dissolved in 2000 ml of ion-exchanged water. was mixed at 20°C.
The mixed solution thus obtained was kept at 20° C., and while stirring, 29.64 g of ammonium persulfate and 8.0 g of ferric sulfate oxidation catalyst solution dissolved in 200 ml of ion-exchanged water were slowly added, The mixture was stirred for 3 hours to react.
2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated three times.
Next, 200 ml of 10 mass % diluted sulfuric acid and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solvent was removed by ultrafiltration. 2000 ml of ion-exchanged water was added to the residual liquid, and about 2000 ml of the solution was removed by ultrafiltration. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the resulting solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated five times to obtain an aqueous dispersion of poly(3,4-ethylenedioxythiophene) (PEDOT-PSS) doped with polystyrenesulfonic acid having a concentration of 1.2% by mass. The PSS content in PEDOT-PSS was 75% by mass.

(Production Example 3) Reaction with quaternary ammonium salt 100 g of the PEDOT-PSS aqueous dispersion prepared in Production Example 2 was added dropwise to an organic layer (organic solution) in which 2.4 g of tetraoctylammonium bromide was dissolved in 200 g of ethanol. and stirred for 30 minutes. As a result, a reaction product of tetraoctylammonium bromide and the conductive composite was deposited. This precipitate was collected by filtration, added with 100 g of isopropyl alcohol and stirred for 30 minutes while lightly suspending the precipitate, and then collected by filtration again and washed. As a result, 1.1 g of the conductive composite having the aforementioned substituent (C) was obtained.
Next, 1.1 g of the conductive composite obtained above and 274 g of isopropyl alcohol were mixed and dispersed with a high-pressure homogenizer to obtain an isopropyl alcohol solution of the conductive composite.

(Production Example 4) Reaction with Amine Compound To an organic layer prepared by dissolving 5 g of trioctylamine in 200 g of ethanol, 100 g of the PEDOT-PSS aqueous dispersion prepared in Production Example 2 was added dropwise and stirred for 30 minutes. As a result, a reaction product of trioctylamine and the conductive composite was deposited. This precipitate was collected by filtration and washed in the same manner as in Production Example 3 to obtain 1.1 g of a conductive composite reacted with trioctylamine.
Next, 1.1 g of the conductive composite obtained above and 274 g of isopropyl alcohol were mixed and dispersed with a high-pressure homogenizer to obtain an isopropyl alcohol solution of the conductive composite.

(Example 1)
16 g of pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate PE-3A) and 2.8 g of urethane acrylate (manufactured by Negami Kogyo Co., Ltd., product name: Artresin 904M, nonvolatile content concentration of 80% by mass, 10 functions) Then, 5 g of propylene glycol monomethyl ether was added to 50 g of isopropyl alcohol and stirred for 30 minutes. After that, 1.6 g of 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins, product name: Omnirad 184), which is a photopolymerization initiator, was added and stirred for 30 minutes. By adding 25 g of the solution and stirring for 30 minutes, a target conductive polymer-containing liquid was obtained.
The conductive polymer-containing liquid thus obtained was passed through a bar coater No. 1. 8 was applied to a polyester film (Cosmo Shine A4300 manufactured by Toray Industries, Inc.), and the coating film (conductive layer) was dried at 100° C. for 1 minute. Subsequently, the coating film was cured by irradiating the coating film with ultraviolet rays using an ultraviolet irradiation machine to obtain a conductive hard coat film (conductive film). Table 1 shows the results of measuring the surface resistivity R0 of this conductive film.
Next, this conductive film was allowed to stand in a 25° C. environment and exposed to the atmosphere for 10 days. Table 1 shows the results of measuring the surface resistivity R1 of the conductive film after exposure to the atmosphere and the amount of change represented by the ratio of R1/R0. The numerical value of this variation (common logarithm: x) means that the closer to 0, the smaller the variation, and the better the atmospheric exposure resistance.

(Example 2)
A conductive hard coat film was prepared in the same manner as in Example 1 except that 2.8 g of urethane acrylate in Example 1 was changed to 2.3 g of Acryt 8UX-122A (manufactured by Taisei Fine Chemical Co., Ltd., non-volatile content concentration 99.9% by mass). was obtained and the surface resistivities R0 and R1 were measured.

(Example 3)
A conductive hard coat film was obtained in the same manner as in Example 1, except that 15 g of 2-hydroxyethylacrylamide was further added to the conductive polymer-containing liquid, and the surface resistivities R0 and R1 were measured.

(Example 4)
A conductive hard coat film was obtained in the same manner as in Example 3, except that 15 g of 2-hydroxyethylacrylamide was changed to 15 g of N,N-dimethylacrylamide, and the surface resistivities R0 and R1 were measured.

(Example 5)
A conductive hard coat film was obtained in the same manner as in Example 3, except that 15 g of 2-hydroxyethylacrylamide was changed to 15 g of N,N-diethylacrylamide, and the surface resistivities R0 and R1 were measured.

(Example 6)
A conductive hard coat film was obtained in the same manner as in Example 3, except that 15 g of 2-hydroxyethylacrylamide was changed to 15 g of N-acryloylmorpholine, and the surface resistivities R0 and R1 were measured.

(Example 7)
Conductivity was obtained in the same manner as in Example 1, except that 3 g of an organosilica compound (manufactured by Nissan Chemical Industries, Ltd., MEK-AC-2140Y, nonvolatile concentration: 40% by mass, methyl ethyl ketone dispersion type) was further added to the conductive polymer-containing liquid. A flexible hard coat film was obtained and the surface resistivities R0 and R1 were measured.

(Example 8)
Pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate PE-3A) 16 g, STA-SiA TAZ-136 (manufactured by Taisei Fine Chemical Co., Ltd., non-volatile content concentration 40% by weight, urethane acrylate: 15% by weight, Organosilica compound: 25% by mass) (8.6 g) and propylene glycol monomethyl ether (5 g) were added to isopropanol (43.8 g) and stirred for 30 minutes. After that, 1.6 g of 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins, product name: Omnirad 184), which is a photopolymerization initiator, was added and stirred for 30 minutes. By adding 25 g of an isopropyl alcohol solution and stirring for 30 minutes, a target conductive polymer-containing liquid was obtained.
The conductive polymer-containing liquid thus obtained was passed through a bar coater No. 1. 8 was applied to a polyester film (Cosmo Shine A4300 manufactured by Toray Industries, Inc.), and the coating film (conductive layer) was dried at 100° C. for 1 minute. Subsequently, the coating film was cured by irradiating the coating film with ultraviolet rays using an ultraviolet irradiation machine to obtain a conductive hard coat film (conductive film). The surface resistivities R0 and R1 of this conductive film were measured in the same manner as in Example 1.

(Example 9)
A conductive hard coat film was obtained in the same manner as in Example 8, except that 15 g of N,N-dimethylacrylamide was further added to the conductive polymer-containing liquid, and the surface resistivities R0 and R1 were measured.

(Comparative example 1)
A conductive hard coat film was obtained in the same manner as in Example 1, except that Artresin 904M was not contained in the conductive polymer-containing liquid, and the surface resistivities R0 and R1 were measured.

(Comparative example 2)
A conductive hard coat film was obtained in the same manner as in Example 1 except that the isopropyl alcohol solution of the conductive composite obtained in Production Example 4 was used, and the surface resistivities R0 and R1 were measured.

[Measurement of surface resistivity]
For the conductive film produced in each example, the surface resistivity of the conductive layer was measured using a resistivity meter (Hiresta manufactured by Nitto Seiko Analyticc Co., Ltd.) under the condition of an applied voltage of 10V.

In the conductive polymer-containing liquid of each example according to the present invention, the surplus anion containing the conductive composite, the acrylic monomer and the urethane acrylate, and not involved in the doping of the polyanion possessed by the conductive composite. The group has been modified by reacting with a quaternary ammonium compound. The surface resistivity of the conductive layer formed using this conductive polymer-containing liquid was maintained at a sufficiently low level even after exposure to the atmosphere, and was excellent in resistance to exposure to the atmosphere.
From the comparison between Examples 1 and 2 and Examples 3 and 6, it is understood that the atmospheric exposure resistance is improved when two or more acrylic monomers are contained rather than when only one acrylic monomer is contained.
Also, from a comparison between Examples 1 to 6 and Examples 7 to 9, it is clear that when the conductive polymer-containing liquid contains an organosilica compound, the atmospheric exposure resistance is remarkably excellent.

In Comparative Example 1, since the conductive polymer-containing liquid did not contain urethane acrylate, the air exposure resistance was poor.
In Comparative Example 2, since the conductive composite was reacted with a tertiary amine, the resistance to atmospheric exposure was poor.

Claims (10)

A conductive polymer-containing liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an organic solvent, one or more acrylic monomers, and a urethane acrylate other than the acrylic monomer,
A conductive polymer-containing liquid, wherein the polyanion is modified by reaction of a part of the anion group of the polyanion with a quaternary ammonium compound. 2. The conductive polymer-containing liquid according to claim 1, further comprising a photopolymerization initiator. 3. The conductive polymer-containing liquid according to claim 1, further comprising a silica compound. The conductive polymer-containing liquid according to any one of claims 1 to 3, wherein the organic solvent contains at least one selected from isopropyl alcohol, methyl ethyl ketone, and propylene glycol monomethyl ether. The acrylic monomer is at least one selected from pentaerythritol triacrylate, pentaerythritol tetraacrylate, 2-hydroxyethylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, and N-acryloylmorpholine. The conductive polymer-containing liquid according to any one of claims 1 to 4, comprising: The conductive polymer according to any one of claims 1 to 5, wherein the π-conjugated conductive polymer contains poly(3,4-ethylenedioxythiophene), or the polyanion contains polystyrenesulfonic acid. Liquid containing high molecular weight. The conductive polymer-containing liquid according to any one of claims 1 to 6, wherein the quaternary ammonium compound has at least one hydrocarbon group having 4 to 32 carbon atoms. The conductive polymer-containing liquid according to any one of claims 1 to 7, wherein the quaternary ammonium compound contains tetraoctylammonium. A conductive laminate comprising a conductive layer comprising a cured product of the conductive polymer-containing liquid according to any one of claims 1 to 8 on at least part of a substrate. Before and after an atmospheric exposure experiment in which the conductive laminate was allowed to stand in an environment of 25° C. and exposed to the atmosphere for 10 days, the increase in the surface resistivity of the conductive layer of the conductive laminate was suppressed to 10 times or less. 10. The electrically conductive laminate of claim 9, wherein the