JP2022106558A - Conductive polymer liquid composition and its manufacturing method, conductive laminate and its manufacturing method, manufacturing method of conductive film, as well as, conductive molding - Google Patents

Abstract

To provide a conductive polymer liquid composition having improved dispersibility to a solvent-free type acryl solution and its manufacturing method, a manufacturing method of conductive films using the liquid composition, a conductive laminate and its manufacturing method, as well as a conductive molding.SOLUTION: A conductive polymer liquid composition containing a π-conjugated conductive polymer and a polyanion, and a polymerizable acrylic compound having a (meth) acrylic group, in which a portion of an anionic group of the polyanions is decorated through a reaction with an epoxy compound, and an amine compound or a tertiary ammonium compound.SELECTED DRAWING: None

Description

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

Acrylic resin obtained by polymerizing (meth) acrylic acid or an ester compound thereof is excellent in durability and transparency, and is easy to be molded, so that it is used in various products. For example, there is an application of protecting the surface of the base material by forming a hard coat layer containing an acrylic resin on the surface of the base material. A conductive film to which antistatic property is imparted by further containing a conductive polymer in such a hardcoat layer is disclosed (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 200-100689

As exemplified in Patent Document 1, in order to disperse the conductive composite composed of the π-conjugated conductive polymer and the polyanion in the organic solvent, the excess anion group of the polyanion is modified in advance to make it hydrophobic. Processing is required. However, as shown in the comparative example described later, even a hydrophobic conductive complex is difficult to disperse in the liquid of the acrylic monomer, and even if it is treated with a high-pressure homogenizer, it precipitates in a few minutes. It ends up. Therefore, it is necessary to add a large amount of an organic solvent, and it is not realistic to disperse the conductive complex in a solvent-free acrylic solution. Similarly, the dispersion of the conductive complex in the non-polar silicone solution was also insufficient.

The present invention relates to a conductive polymer liquid composition and a method for producing the same, which comprises a conductive composite having improved dispersibility in a solvent-free acrylic solution, a method for producing a conductive film using the liquid composition, and conductivity. Provided are a sex laminate, a method for producing the same, and a conductive molded body.

[1] A conductive composite containing a π-conjugated conductive polymer and a polyanion and a polymerizable acrylic compound having a (meth) acrylic group are contained, and some of the anionic groups of the polyanion are an epoxy compound and an epoxy compound. A conductive polymer liquid composition modified by reaction with an amine compound or a quaternary ammonium compound.
[2] The conductive polymer liquid composition according to [1], wherein 95% by mass or more of the total mass of the conductive polymer liquid composition is the polymerizable acrylic compound.
[3] The conductivity according to [1] or [2], wherein the π-conjugated conductive polymer contains poly (3,4-ethylenedioxythiophene), or the polyanion contains polystyrene sulfonic acid. Polystyrene liquid composition.
[4] The conductive polymer liquid composition according to any one of [1] to [3], wherein the polymerizable acrylic compound is an ultraviolet curable silicone.
[5] After adding an epoxy compound and an amine compound or a quaternary ammonium compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, precipitation is performed to recover the precipitated reaction product. A method for producing a conductive polymer liquid composition, comprising a recovery step and an addition step of adding a polymerizable acrylic compound having a (meth) acrylic group to the reaction product to obtain a conductive polymer liquid composition.
[6] The method for producing a conductive polymer liquid composition according to [5], wherein the method for recovering the reaction product is filtration.
[7] A coating material obtained by adding a polymerization initiator to the conductive polymer liquid composition according to any one of [1] to [4] is applied to at least one surface of the base material, and then applied to the coating film. A method for producing a conductive laminate, which comprises a step of polymerizing the contained polymerizable acrylic compound.
[8] A coating material obtained by adding a thermal polymerization initiator to the conductive polymer liquid composition according to any one of [1] to [4] is applied to at least one surface of an amorphous film substrate. A method for producing a conductive film, which comprises a coating step of obtaining a coating film and a stretching step of heating and stretching the coating film to obtain a stretched film.
[9] A substrate and a conductive layer formed on at least one surface of the substrate and composed of a cured layer of the conductive polymer liquid composition according to any one of [1] to [4]. A conductive laminate provided.
[10] A conductive molded product obtained by molding a cured product of the conductive polymer liquid composition according to any one of [1] to [4].

In the conductive polymer liquid composition of the present invention, the polymerizable acrylic compound and the conductive composite are stably dispersed even if the organic solvent is not contained. This makes it possible to obtain a solvent-free liquid acrylic composition containing a conductive composite. The conductive polymer liquid composition of this embodiment can be used not only as a coating material but also for all applications of acrylic resin molding using a conventional acrylic monomer.
According to the method for producing a conductive polymer liquid composition of the present invention, the conductive polymer liquid composition of the present invention can be easily produced.
According to the method for producing a conductive laminate and a conductive film of the present invention, the conventionally required step of drying the coating film (step of drying the organic solvent contained in the coating film) may be omitted, so that the conductive film is conductive. The sex laminate and the conductive film can be easily formed.
Since the conductive molded product of the present invention contains a conductive composite not only near the surface but also inside, it is possible to impart conductivity to various products.

The present invention is considered to contribute to SDGs Goal 12, “Responsibility to Create and Responsibility to Use”.

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

≪Conductive polymer liquid composition≫
The first aspect of the present invention contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, and a polymerizable acrylic compound having a (meth) acrylic group, and a part of the anionic groups of the polyanion is contained. , An epoxy compound, and a conductive polymer liquid composition modified by reaction with an amine compound or a quaternary ammonium compound.
In the conductive polymer liquid composition of this embodiment, the conductive composite may be in a dispersed state or a dissolved state. In the present specification, unless otherwise specified, the dispersed state and the dissolved state are not distinguished and are simply referred to as the dispersed state.

[Conductive complex]
The conductive composite contained in the conductive polymer liquid composition of this embodiment contains a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive complex is doped with a π-conjugated conductive polymer to form a conductive composite having conductivity.
In the poly anion, only a part of the anion groups are doped in the π-conjugated conductive polymer, and the poly anion has a surplus anion group that is not involved in the doping. Since the surplus anion group is a hydrophilic group, the conductive complex in which the surplus anion group is not modified has water dispersibility.

(Pi-conjugated conductive polymer)
The π-conjugated conductive polymer may be an organic polymer whose main chain is composed of a π-conjugated system. For example, a polypyrrole-based conductive polymer, a polythiophene-based conductive polymer, and a polyacetylene-based conductive polymer have high conductivity. Examples thereof include molecules, polyphenylene-based conductive polymers, polyphenylene vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophenine vinylene-based conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-hexylthiophene). , Poly (3-heptylthiophene), Poly (3-octylthiophene), Poly (3-decylthiophene), Poly (3-dodecylthiophene), Poly (3-octadecylthiophene), Poly (3-bromothiophene), Poly (3-Chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene) , Poly (3-hydroxythiophene), Poly (3-methoxythiophene), Poly (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-didodecyloxythiophene) 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-carboxyphene) Butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and poly (3-butyl). Pyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3) -Carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole) , Poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole).
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
Among these π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable because it is excellent in conductivity, transparency, and heat resistance.
The π-conjugated conductive polymer contained in the conductive complex may be of one type or two or more types.

(Polyanion)
A polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anionic group of this polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ester having a sulfo group, and polymethacrylic acid ester having a sulfo group (for example, poly (4-sulfobutyl methacrylate). , Polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprenesulfonic acid and other polymers with sulfo groups, polyvinylcarboxylic acid, polystyrenecarboxylic acid, etc. Examples thereof include polymers having a carboxy group such as polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), and polyisoprenecarboxylic acid. The polyanion is a single monomer. It may be a homopolymer obtained by polymerizing the above, or it may be a copolymer obtained by polymerizing two or more kinds of monomers.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be made higher.
The polyanion may be used alone or in combination of two or more.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight is a mass-based average molecular weight measured by gel filtration chromatography and obtained in terms of pull run.

When the number of all anion groups contained in the poly anion is 100 mol%, the excess anion group is preferably 30 mol% or more and 90 mol% or less, and more preferably 45 mol% or more and 75 mol% or less.

In this embodiment, the excess anion group (hereinafter, also referred to as “some anion groups”) that does not participate in the doping of the polyanion is modified by the reaction with the epoxy compound and the quaternary ammonium compound or amine compound. Has been done. That is, the polyanion of the present invention comprises a substituent (A) formed by a reaction of an epoxy compound and a part of an anion group, and a substituent (B) formed by a reaction of an amine compound and a part of an anion group. Alternatively, it has a substituent (C) formed by the reaction of the quaternary ammonium compound with some anionic groups.

(Substituent A)
It is presumed that the substituent (A) is a group represented by the following formula (A1) or a group represented by the following formula (A2).

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

[In 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 independently hydrogen atoms or arbitrary substituents. Yes, a plurality of R ^5s may be the same or different, a plurality of R ^6s may be the same or different, a plurality of R ^7s may be the same or different, and a plurality of R ^8s may be the same or different. You may. ]

In the formulas (A1) and (A2), the leftmost bond represents that the substituent (A) is substituted with the proton of the anion group. Examples of the anion group having a proton to be substituted include an anion group having an active proton bonded to an oxygen atom such as "-SO ₃ H".

In the formula (A1), as arbitrary substituents of ^R1 , ^R2 , R3 ^, and ^R4 , an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, and a substituent are used. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be possessed. R ¹ and R ³ may be bonded to form a ring which may have a substituent. For example, R ¹ and R ³ are the above-mentioned hydrogen groups, and a divalent hydrogen group excluding any one hydrogen atom of the monovalent hydrogen group of R ¹ and a monovalent carbonization of R ³ A case may be mentioned in which a divalent hydrocarbon group excluding any one hydrogen atom of a hydrogen group is bonded to each other by carbon atoms from which the hydrogen atom has been removed to form a ring.
In the formula (A2), as arbitrary substituents of R ⁵ , R ⁶ , R ⁷ , and R ⁸ , an aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, and a substituent are used. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be possessed. R ⁵ and R ⁷ may be bonded to form a ring which may have a substituent. The example of forming a ring is the same as above.
In the present specification, "may have a substituent" means that the hydrogen atom (-H) is replaced with a monovalent group and the methylene group (-CH _2- ) is replaced with a divalent group. Includes both cases of replacement.
The monovalent group as a substituent includes an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), and a trialkoxysilyl group. (Trimethoxysilyl group, etc.), and the like.
Examples of the divalent group as the substituent include 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. When m is not more than the above lower limit value, the hydrophobicity of the conductive complex becomes sufficiently high. When m is not more than the upper limit value, it is possible to suppress that the hydrophobicity becomes too high or the conductivity decreases.

The 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.
The epoxy compound that reacts with the conductive complex may be one kind or two or more kinds.

Examples of the monofunctional epoxy compound having one epoxy group in one molecule include ethylene oxide, propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, and 1 , 2-Epoxy heptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monooxide, 1,2-epoxytetradecane, glycidylmethyl ether, 1,2- Epoxy octadecane, 1,2-epoxy hexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxy eikosan, 2- (chloromethyl) -1,2-epoxy propane, 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-epoxy tetrahydrofuran, 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-cyclododecadien, 4-tert-butyl glycidyl benzoate, 2,2-bis (4-glycidyloxyphenyl) propane, 2 -Tert-Butyl-2- [2- (4-chlorophenyl) )] Ethyloxylane, styrene oxide, glycidyl trityl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α, 6α-epoxide, stillbenoxide, glycidyl p-toluenesulfonate , 3-Methyl-3-phenylglycidate ethyl, N-propyl-N- (2,3-epoxypropyl) perfluoro-n-octylsulfonamide, (2S, 3S) -1,2-epoxy-3-( tert-butoxycarbonylamino) -4-phenylbutane, 3-nitrobenzene sulfonic acid (R) -glycidyl, 3-nitrobenzene sulfonic acid-glycidyl, parthenolide, N-glycidyl phthalimide, endolin, dildrin, 4-glycidyl oxycarbazole, 7, Examples thereof include 7-dimethyloctanoic acid [oxylanylmethyl], 1,2-epoxide-4-vinylcyclohexane, and higher alcohol glycidyl ether having 10 to 16 carbon atoms.

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, and C12 (12 carbon atoms) higher grade. At least one of alcohol glycidyl ether and C13 (13 carbon atoms) higher alcohol glycidyl ether is more preferable.

Examples of the polyfunctional epoxy compound 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, 1,2-cyclohexanedicarboxylate diglycidyl, 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, Trimethylol Propane Triglycidyl Ether, Trimethylol Propane Polyglycidyl Ether, Hydrogenated Bisphenol A Diglycidyl Ether, Hexahydrophthalate Diglycidyl Ether, Glycerin Polyglycidyl Ether, Diglycerin Polyglycidyl Ether, Polyglycerin Polyglycidyl Ether, Sorbitol Poly Examples thereof include glycidyl ether and ethylene oxide lauryl alcohol glycidyl ether.

The epoxy compound preferably has a molecular weight of 50 or more and 2000 or less because the epoxy compound has high dispersibility in an organic solvent. Further, since the dispersibility in low-polarity hydrocarbon solvents and ester solvents is high, the epoxy compound preferably has 4 or more and 120 or less carbon atoms, and more preferably 7 or more and 100 or less carbon atoms. Those of 80 or more and 80 or less are more preferable, and those of 15 or more and 50 or less are 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 the formula (B), R ¹¹ to R ¹³ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, except that at least one of R ¹¹ to R ¹³ is a substituent. It is a hydrocarbon group which may have. ]

In the substituent (B), the leftmost bond indicates that the negative charge of the anion group and the positive charge of the amine compound are bonded. Examples of the anion group that can be negatively charged include an anion group in which an active proton is bonded to an oxygen atom ^, such as "-SO _3- ".

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

The amine compound is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. The amine compound that reacts with the conductive complex may be one kind or two or more kinds.
Examples of the primary amine include aniline, toluidine, benzylamine, ethanolamine and the like.
Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, trinaphthylamine and the like.
Of the amine compounds, tertiary amines are preferable, and at least one of trioctylamine and tributylamine is more preferable, because the conductivity of the conductive complex of this embodiment can be enhanced.

Since the dispersibility in an organic solvent, particularly in a low-polarity hydrocarbon solvent and an ester solvent is high, the amine compound may have a substituent having 4 or more carbon atoms on the nitrogen atom. It is more preferable to have a substituent of 6 or more, and further preferably to have a substituent having 8 or more carbon atoms on the nitrogen atom. The upper limit of the number of carbon atoms of the substituent on the nitrogen atom is not particularly limited, and in consideration of solubility in a solvent and reactivity, for example, 50 or less is preferable, 40 or less is more preferable, and 30 or less is further preferable. ..
The total carbon number of R ¹¹ to R ¹³ contained in the amine compound is preferably 6 to 33, more preferably 9 to 30, and even more preferably 12 to 27.
The number of carbon atoms of each substituent on the nitrogen atom may be the same or different.

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). (Also referred to as) 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 easy to balance dispersibility and conductivity. The mass of [substituent (A)] is [(mass of reactant A obtained by reacting epoxy compound with conductive composite)-(mass of conductive composite before reacting with epoxy compound). )] Can be calculated. Further, the mass of [substituent (B)] can be calculated from [(mass of reactant B obtained by reacting the reactant A with the amine compound)-(mass of the 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 the formula (C), R ¹¹ to R ¹⁴ are hydrocarbon groups that may independently have substituents. ]

In the substituent (C), the leftmost bond indicates that the negative charge of the anion group and the positive charge of the quaternary ammonium cation are bonded. Examples of the anion group that can be negatively charged include an anion group in which an active proton is bonded to an oxygen atom ^, such as "-SO _3- ".

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

The quaternary ammonium compound preferably has a substituent having 3 or more carbon atoms on the nitrogen atom, and has 5 or more substituents, because the dispersibility in the organic solvent is increased and the conductivity is improved. It is more preferable to have a substituent having 7 or more carbon atoms on the nitrogen atom. The upper limit of the number of carbon atoms of each substituent on the nitrogen atom is not particularly limited, and for example, 40 or less is preferable, 30 or less is more preferable, and 20 or less is further considered in consideration of solubility in a solvent and reactivity. preferable.
The total carbon number of R ¹¹ to R ¹⁴ contained in the quaternary ammonium compound is preferably 8 to 44, more preferably 12 to 40, and even more preferably 16 to 36.
The number of carbon atoms of each substituent on the nitrogen atom may be the same or different.

Specific examples of the quaternary ammonium compound include tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tetra-n-octylammonium salt, tetraphenylammonium salt, tetrabenzylammonium salt, and tetranaphthyl. Examples thereof include quaternary ammonium salts such as ammonium salts.
Examples of the counter anion of the ammonium cation include halogen ions such as bromine ion and chloride ion and hydroxy ion.

In the polyanion, the mass ratio represented by [substituent (A)]: [substituent (C)] (hereinafter, also referred to as A / C ratio) is preferably 10:90 to 90:10, preferably 20:80 to 20:80. 80:20 is more preferable, and 25:75 to 75:25 is even more preferable. When the A / C ratio is within the above range, it becomes easy to balance dispersibility and conductivity. The mass of [substituent (A)] is [(mass of reactant A obtained by reacting epoxy compound with conductive composite)-(mass of conductive composite before reacting with epoxy compound). )] Can be calculated. Further, the mass of [anionic group to which the substituent (C) is bonded] is [(the mass of the reactant C obtained by reacting the reactant A with the quaternary ammonium compound)-(the mass of the reactant A. Mass)] can be calculated.

The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer, and 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 further preferable. When the content ratio of the polyanion is at least the above lower limit value, the doping effect on the π-conjugated conductive polymer tends to be strong, and the conductivity becomes higher. On the other hand, when the content of the polyanion is not more than the above upper limit value, the amount of the anion group not involved in the doping is appropriately suppressed, and the anion group is hydrophobic when the epoxy compound and the quaternary ammonium compound or the amine compound are reacted. Can be easily converted to sex.

The content of the conductive composite with respect to the total mass of the conductive polymer liquid composition of this embodiment is, for example, preferably 0.01% by mass or more and 10% by mass or less, and 0.1% by mass or more and 5% by mass or less. Is more preferable, and 0.2% by mass or more and 2% by mass or less is further preferable.

[Dispersion medium]
The conductive polymer liquid composition of this embodiment may contain a dispersion medium. Examples of the dispersion medium include an organic solvent or a mixed solution of water and an organic solvent. As described above, since the polyanion of the conductive complex is hydrophobically modified, a dispersion medium containing an organic solvent is preferable.
The content of the organic solvent with respect to the total mass of the dispersion medium is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and further preferably 95% by mass or more and 100% by mass or less.

<Organic solvent>
The organic solvent is preferably an ester group-containing compound (ester solvent) having an ester group (-C (= O) -O-). The ester solvent can easily disperse the modified conductive composite of this embodiment.

From the viewpoint of enhancing the dispersibility of the conductive complex of this embodiment, it is preferable to contain one or more kinds of ester solvents represented by the following formula 1.
Equation 1: 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 complex of this embodiment, R ²¹ is preferably a methyl group or an ethyl group, and more preferably a methyl group. The carbon number of R ²² is preferably 2 to 5, and more preferably 2 to 4.

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

The content of the ester solvent contained in the organic solvent is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and 70% by mass or more, based on the total mass of the organic solvent. Is even more preferable, 80% by mass or more is particularly preferable, 90% by mass or more is most preferable, and 100% by mass may be used. When the content of the ester solvent is within the above range, the dispersibility of the conductive complex can be enhanced.

The conductive polymer liquid composition of this embodiment may further contain one or more organic solvents other than the ester solvent.
Examples of the organic solvent other than the ester-based organic solvent include hydrocarbon-based solvents, ketone-based solvents, alcohol-based solvents, ether-based solvents, nitrogen atom-containing compound-based solvents, and the like.
Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent. Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane and the like. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
Examples of the ketone solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, allyl alcohol and the like.
Examples of the ether solvent include diethyl ether, dimethyl ether, propylene glycol dialkyl ether and the like.
Examples of the nitrogen atom-containing compound solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.

When the conductive polymer liquid composition of this embodiment contains a hydrocarbon solvent, the wettability to the plastic film base material is increased, and a low-polarity binder component can be easily added, which is preferable.

Among the hydrocarbon solvents, toluene is preferable because it is versatile. Further, when a silicone compound is added as a binder component, at least one of heptane and toluene is preferable because the silicone compound is excellent in solubility.

It is preferable to further contain methyl ethyl ketone in addition to the hydrocarbon solvent because the dispersibility of the conductive complex becomes higher. For example, the content of methyl ethyl ketone is preferably 20 parts by mass or more and 120 parts by mass or less, more preferably 30 parts by mass or more and 100 parts by mass or less, and 40 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the hydrocarbon solvent. Is even more preferable.

The content of the hydrocarbon solvent is preferably 10% by mass or more and 80% by mass or less, preferably 20% by mass or more and 70% by mass or less, based on the total mass of the organic solvent contained in the conductive polymer liquid composition of this embodiment. More preferably, it is more preferably 30% by mass or more and 60% by mass or less. When the content of the hydrocarbon solvent is within the above range, the dispersibility of the conductive complex can be enhanced.

The conductive polymer liquid composition of this embodiment can be a solvent-free liquid composition. Therefore, the content of the dispersion medium with respect to the total mass of the conductive polymer liquid composition can be, for example, 0% by mass or more and 20% by mass or less, and 0% by mass or more and 10% by mass or less. It can be 0% by mass or more and 5% by mass or less, or 0.1% by mass or more and 3% by mass or less.

[Polymerizable acrylic compound]
The polymerizable acrylic compound contained in the conductive polymer liquid composition of this embodiment is a known polymerizable compound having a (meth) acrylic group (also known as (meth) acryloyl group). Here, the notation of "(meth) acrylic" means "acrylic or methacrylic", and the notation of "(meth) acryloyl" means "acryloyl or methacrylic". The polymerizable acrylic compound is another compound different from the conductive composite.

Examples of the polymerizable acrylic compound include (meth) acrylic acid, (meth) acrylate (also known as (meth) acrylic acid ester), and (meth) acrylamide.
The polymerizable acrylic compound may have one (meth) acrylic group or two or more (meth) acrylic groups. The (meth) acrylic group is preferably a (meth) acrylicoxy group.
Examples of the (meth) acrylate include a (meth) acrylate having a linear, branched or cyclic alkyl group or monovalent hydrocarbon group having 1 to 12 carbon atoms at the end of the ester group. Here, another (meth) acrylic group may replace one or more hydrogen atoms bonded to an alkyl group or a monovalent hydrocarbon group. If the (meth) acrylate has more than one (meth) acrylic group, optionally select one (meth) acrylic group and assume that the remaining (meth) acrylic group is a hydrocarbon atom. , Count the number of carbon atoms of the alkyl group or monovalent hydrocarbon group ester-bonded to the selected (meth) acrylic group.
One or more hydrogen atoms (—H) constituting the alkyl group or monovalent hydrocarbon group of the (meth) acrylate may be substituted with a hydroxyl group.
The one or more methylene groups (-CH _2- ) constituting the alkyl group or 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 the acrylate 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, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol monohydroxypentaacrylate, trimethylolpropantriacrylate, Glycerin propoxytriacrylate and the like can be mentioned.
Examples of the methacrylate 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, trimethylpropantrimethacrylate and the like.
Examples of (meth) acrylamide include methacrylamide, 2-hydroxyethylacrylamide, N-methylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N-phenylacrylamide, N-methylolacrylamide, and dimethylaminopropylacrylamide. Examples thereof include dimethylaminopropyl methacrylamide, diacetone acrylamide, N, N-dimethylacrylamide, N-vinylformamide, acryloylmorpholin, acryloylpiperidin and the like.

The polymerizable acrylic compound may be an acrylate obtained by reacting an acrylic monomer with another compound, such as epoxy acrylate, urethane acrylate, polyester acrylate, or polyacrylic acrylate.

The polymerizable acrylic compound may be an ultraviolet curable silicone.
Examples of the ultraviolet curable silicone include linear polymers having a siloxane bond, having polydimethylsiloxane having a (meth) acrylic group at both ends of the straight chain, and hydrogensilane. Such an ultraviolet curable silicone forms a three-dimensional crosslinked structure by a radical polymerization reaction and is cured. It is preferable to add a photopolymerization initiator for initiating the polymerization.
Specific examples of the ultraviolet curable silicone include KF-2005 and X-62-7205 (manufactured by Shin-Etsu Chemical Co., Ltd.).
The UV curable silicone may be dissolved or dispersed in an organic solvent.
The UV curable silicone is preferably included with another polymerizable acrylic compound. The mass-based content ratio (M2 / M1) represented by (content M2 of another polymerizable acrylic compound) / (content of ultraviolet curable silicone M1) is preferably 2 or more and 100 or less, and 4 or more and 50 or less. Is more preferable, 6 or more and 30 or less is further preferable, and 8 or more and 20 or less is particularly preferable.

The polymerizable acrylic compound contained in the conductive polymer liquid composition of this embodiment may be one kind or two or more kinds.
The total content of the polymerizable acrylic compound with respect to the total mass of the conductive polymer liquid composition of this embodiment is, for example, 50% by mass or more, 70% by mass or more, or 80% by mass or more. , 90% by mass or more, 95% by mass or more, or 99% by mass or more. That is, it can be a substantially solvent-free liquid composition. The upper limit of the content may be adjusted according to the content of the conductive complex, and is less than 100% by mass.

The polymerizable acrylic compound is preferably one that can be radically polymerized. In this case, it is preferable to include a radical polymerization initiator that generates radicals together with the radically polymerizable acrylic compound. Examples of the radical polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Hereinafter, a specific example will be given.

(Photopolymerization initiator)
When the polymerizable acrylic compound is polymerized by active energy rays (radiation) such as ultraviolet rays, it is preferable to contain a photopolymerization initiator together with the polymerizable acrylic compound. The photopolymerization initiator may be used alone or in combination of two or more.
Examples of the photopolymerization initiator include a benzoin ether type photopolymerization initiator, an acetophenone type photopolymerization initiator, an α-ketol type photopolymerization initiator, an aromatic sulfonyl chloride type photopolymerization initiator, and a photoactive oxime type photopolymerization initiator. Known 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, and the like. Things can be mentioned.
Specific examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1-. On [trade name: Irgacure 651, manufactured by BASF], anisole methyl ether and the like can be mentioned. Examples of the acetophenone-based photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone [trade name: Irgacure 184, manufactured by BASF], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4-( 2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one [trade name: Irgacure 2959, manufactured by BASF], 2-hydroxy-2-methyl-1-phenyl-propane- 1-on [trade name: DaroCure 1173, manufactured by BASF], methoxyacetophenone and the like can be mentioned.

(Thermal polymerization initiator)
When the polymerizable acrylic compound is polymerized by heating, it is preferable to contain a thermal polymerization initiator together with the polymerizable acrylic compound. The thermal polymerization initiator may be used alone or in combination of two or more.
Examples of the thermal polymerization initiator include known azo-based initiators, persulfates, peroxide-based initiators, and the like.

(Copolymerizable polymerizable compound)
The conductive polymer liquid composition of this embodiment may contain another polymerizable compound copolymerizable with the polymerizable acrylic compound. As another polymerizable compound, a known compound known to be copolymerizable with an acrylic monomer can be applied.
Specifically, for example, unsaturated carboxylic acids such as maleic acid and itaconic acid and derivatives thereof, acid anhydrides such as maleic anhydride and itaconic anhydride and derivatives thereof, vinyl esters such as vinyl acetate and vinyl benzoate, and chlorides. Examples thereof include vinyl, vinylidene chloride and derivatives thereof, and aromatic vinyl compounds such as styrene and α-methylstyrene.

<Binder component>
The conductive polymer liquid composition of this embodiment may contain a binder component other than the above-mentioned polymerizable acrylic compound. By using the conductive polymer liquid composition containing a binder component, it is possible to improve the strength of the conductive layer and the conductive molded product to be formed, and to impart adhesiveness and releasability.
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 can be optionally cured. The thermoplastic resin becomes a binder resin as it is, and the curable monomer or oligomer becomes a binder resin when the resin formed by curing becomes a binder resin.
The binder component contained in the conductive polymer liquid composition of this embodiment may be one kind or two or more kinds.

(Silicone compound)
In the conductive polymer liquid composition of this embodiment, a low-polarity silicone compound can be added as a binder component to sufficiently disperse the composition.
Examples of the silicone compound include curable silicone. When the binder component is a curable silicone, the conductive layer and the conductive molded body can be imparted with releasability by curing the curable silicone. Here, the ultraviolet curable silicone corresponding to the polymerizable acrylic compound is not classified as a binder component.

The curable silicone may be either an addition curable silicone or a condensation curable silicone. In this embodiment, curing inhibition is unlikely to occur even if addition-curing silicone is used.

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

The content ratio of the silicone compound to the total mass of the conductive polymer liquid composition of this embodiment is, for example, 0.1% by mass or more and 20% by mass or less.
When it is at least the lower limit of the above range, sufficient releasability can be imparted to the conductive layer and the conductive molded body formed by the conductive polymer liquid composition of this embodiment.
When it is not more than the upper limit value of the above range, sufficient conductivity can be imparted to the conductive layer and the conductive molded body.

(Other additives)
The conductive polymer liquid composition of this embodiment may contain other known additives.
The additive is not particularly limited as long as the effect of the present invention can be obtained, and for example, a surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like can be used.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferable from the viewpoint of storage stability. Further, a polymer-based surfactant such as polyvinylpyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving the metal salt in water.
Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the coupling agent include a silane coupling agent having a vinyl group or an amino group.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and sugars.
Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxanilide-based UV absorbers, hindered amine-based UV absorbers, benzoate-based UV absorbers, etc. Can be mentioned.
When the conductive polymer liquid composition of this embodiment contains the above-mentioned additive, the content ratio thereof is appropriately determined according to the type of the additive, but is based on the total mass of the conductive polymer liquid composition. For example, it can be in the range of 0.01% by mass or more and 5% by mass or less.

<< Manufacturing method of conductive polymer liquid composition >>
A second aspect of the present invention is an aqueous dispersion of a conductive composite containing a π-conjugated conductive polymer and a polyanion (hereinafter, may be referred to as a conductive polymer aqueous dispersion), an epoxy compound, and an amine. A precipitation recovery step of recovering the precipitated reaction product after adding a compound or a quaternary ammonium compound, and a conductive polymer liquid composition by adding a polymerizable acrylic compound having a (meth) acrylic group to the precipitate. It is a method for producing a conductive polymer liquid composition having an addition step of obtaining a product.
By the production method of this aspect, the conductive polymer liquid composition of the first aspect can be produced.

The production method of this embodiment may further include a washing step between the precipitation recovery step and the addition step. Further, in the addition step, a binder component or the like may be further added.

[Precipitation recovery process]
In the precipitation recovery step, an epoxy compound and an amine compound or a quaternary ammonium compound are added to the conductive polymer aqueous dispersion to form the conductive composite, the epoxy compound, and the amine compound or the fourth. This is a step of precipitating a reaction product with a secondary ammonium compound and then recovering the reaction product as a precipitate.
The recovery method is not particularly limited, and for example, recovery can be performed by filtration treatment or decantation (solvent substitution method).

When one or more of the epoxy compounds are added to the conductive polymer aqueous dispersion, the epoxy groups of the epoxy compounds react with some of the anionic groups of the polyanions. As a result, the substituent (A) is formed and the conductive complex becomes hydrophobic, which makes it difficult to stably disperse in the aqueous dispersion, and precipitates to form 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. More preferred.
When it is at least the lower limit of the above range, the hydrophobicity of the conductive complex becomes sufficiently high.
When it is not more than the upper limit of the above range, the decrease in conductivity due to the unreacted epoxy compound can be prevented.

An organic solvent may be added before, simultaneously with, or after the addition of one or more selected from an epoxy compound, an amine compound, and a quaternary ammonium compound to the conductive polymer aqueous dispersion. As the organic solvent, a water-soluble organic solvent is preferable. Here, the water-soluble organic solvent is an organic solvent having a dissolution amount of 1 g or more with respect to 100 g of water at a temperature of 20 ° C. Examples of the water-soluble organic solvent 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 aqueous dispersion, the amine compound reacts with some anionic groups of the polyanion. As a result, the substituent (B) is formed and the conductive complex becomes hydrophobic, which makes it difficult to stably disperse in the aqueous dispersion, and precipitates 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 80 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.
When it is at least the lower limit of the above range, the hydrophobicity of the conductive complex becomes sufficiently high.
When it is not more than the upper limit of the above range, the decrease in conductivity due to the unreacted amine compound can be prevented.

When one or more of the quaternary ammonium compounds are added to the conductive polymer aqueous dispersion, the quaternary ammonium compounds react with some anion groups of the polyanion. As a result, the substituent (C) is formed and the conductive complex becomes hydrophobic, which makes it difficult to stably disperse in the aqueous dispersion, and precipitates to form 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. Less than a part is more preferable.
When it is at least the lower limit of the above range, the hydrophobicity of the conductive complex becomes sufficiently high.
When it is not more than the upper limit of the above range, the decrease in conductivity due to the unreacted quaternary ammonium compound can be prevented.
The quaternary ammonium compound has a reaction mechanism similar to that of the amine compound, and exhibits good reactivity with the conductive complex with a smaller amount of addition than the amine compound. The conductivity of a conductive layer or a conductive molded product containing a conductive composite modified with a quaternary ammonium compound tends to be better than when modified with an amine compound.

In the precipitation recovery step, the order of addition of the epoxy compound and the amine compound or the quaternary ammonium compound is not particularly limited. Since the synthetic intermediate (reaction intermediate) is easy to handle, an epoxy compound is added to the conductive polymer aqueous dispersion and reacted with a part of the excess anionic group of the polyanion, and then the amine compound or It is preferable to add a quaternary ammonium compound to react with the remainder of the excess anionic group of the polyanion.

The conductive polymer aqueous dispersion is a dispersion in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is contained in the aqueous dispersion medium.
Here, the aqueous dispersion medium is water or a mixed solution of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol-based solvents, ketone-based solvents, and ester-based solvents. The water-soluble organic solvent contained in the aqueous dispersion medium may be one kind or two or more kinds.
The content of water with respect to the total mass of the aqueous dispersion medium is preferably more than 50% by mass, more preferably 60% by mass or more, further preferably 80% by mass or more, and may be 100% by mass.

The conductive polymer aqueous dispersion is obtained, for example, by chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous solution of a polyanion. Further, as the conductive polymer aqueous dispersion, a commercially available one may be used. The content of the conductive composite with respect to the total mass of the conductive polymer aqueous dispersion is, for example, 0.1% by mass or more and 2% by mass or less.
A known catalyst may be applied to the chemical oxidative polymerization. For example, catalysts and oxidizing agents can be used. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidant can restore the reduced catalyst to its original oxidized state.

The water content of the reaction product (precipitate) recovered by the precipitation recovery step is preferably as small as possible, and most preferably does not contain any water, but from a practical point of view, the water content is contained in the range of 10% by mass or less. It may be.
Examples of the method for reducing the amount of water include a method of washing away the precipitate with an organic solvent, a method of drying the precipitate, and the like.

[Washing process]
The cleaning step between the precipitation recovery step and the addition step is a step of cleaning the precipitate with a cleaning organic solvent. By this washing step, residual water, unreacted epoxy compound, unreacted amine compound or quaternary ammonium compound, hydrolyzate of epoxy compound and the like are removed.
The organic solvent for cleaning is preferably one that can be washed while minimizing the dissolution of precipitates. Therefore, an alcohol solvent is preferable as the organic solvent for cleaning. The organic solvent for cleaning may contain one type or two or more types.
The cleaning method is not particularly limited. For example, the organic solvent for cleaning may be poured over the precipitate to clean the precipitate, or the precipitate may be stirred in the organic solvent for cleaning to clean the precipitate. You may.

[Addition process]
The addition step is a step of adding the polymerizable acrylic compound to the precipitate to obtain a conductive polymer liquid composition.

As the polymerizable acrylic compound in this step, the polymerizable acrylic compound contained in the conductive polymer liquid composition of the first aspect can be applied. Since the conductive composite is modified with an epoxy compound and an amine compound or a quaternary ammonium compound, the conductive composite and the polymerizable acrylic compound can be stably dispersed. At this time, an organic solvent may be added, but since the dispersibility between them is high, it is not necessary to add the organic solvent.
Examples of the organic solvent that may be optionally added include the organic solvent exemplified in the first aspect.

The conductive polymer liquid composition obtained by adding the polymerizable acrylic compound to the precipitate may be stirred and dispersed. The method of stirring is not particularly limited, and stirring may be performed with a weak shearing force such as a stirrer, or may be stirred using a disperser (homogenizer or the like) having a high shearing force.

The content of the conductive composite with respect to the total mass of the conductive polymer liquid composition dispersed by the 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. The following is more preferable, and 0.1% by mass or more and 1% by mass or less is further preferable.
When the concentration is in the above range, the dispersibility of the conductive complex can be sufficiently enhanced.

[Solvent substitution method]
The following solvent substitution method may be applied in the precipitation recovery step and the addition step of this embodiment.
The reaction product precipitated in the reaction solution to which the amine compound or the quaternary ammonium compound is added tends to naturally settle in the lower layer in the reaction solution. The details of the mechanism of sedimentation have not been clarified, but it is considered that the relationship between the specific density of the reaction product and the specific gravity of the reaction solution has an effect.

When the reaction product settles in the lower layer of the reaction solution, the reaction product is hardly contained in the upper layer of the reaction solution. By removing this upper layer by suction, decantation, or the like, the concentration of the precipitated reaction product is increased, and a residual liquid having a reduced volume can be obtained. This operation corresponds to the step of recovering the reaction product.
The obtained residual liquid contains an aqueous dispersion medium derived from the conductive polymer aqueous dispersion. Then, by adding the polymerizable acrylic compound to the residual liquid, the desired conductive polymer liquid composition can be obtained. This operation corresponds to the addition step.
Here, when the amount of the aqueous dispersion medium in the residual liquid is large or the amount of the removed upper layer liquid is small, the reaction product (conductive composite) in the mixed liquid after adding the polymerizable acrylic compound. The body) can be settled in the lower layer again without being dispersed. In this case, by removing the upper layer again, the concentration of the reaction product is increased, the amount of the aqueous dispersion medium is reduced, and a residual liquid having a reduced volume is obtained. By adding the polymerizable acrylic compound to the residual liquid again, the concentration of the polymerizable acrylic compound was increased (the content of the aqueous dispersion medium was reduced) as compared with the first solvent substitution, and the conductive polymer liquid was used. The composition is obtained.
This "solvent substitution method" is not limited to once, and may be repeated twice or more.

By the solvent substitution method described above, the content of the aqueous dispersion medium is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 10% by mass or less, based on the total mass of the target conductive polymer liquid composition. It is possible to obtain a conductive polymer liquid composition having an amount of 5% by mass or less.
For the purpose of enhancing the dispersibility of the conductive composite in the obtained conductive polymer liquid composition, it is preferable to carry out the dispersion treatment using a disperser such as a high-pressure homogenizer.

(Addition of optional ingredients)
Optional components such as the polymerization initiator, the binder component, the catalyst, the organic solvent, and other additives may be added to the conductive polymer liquid composition.
It is preferable to stir after adding any component to enhance the dispersibility of each component.

≪Conductive laminate≫
A third aspect of the present invention comprises a base material and a conductive layer formed on at least one surface of the base material and composed of a cured layer of the conductive polymer liquid composition of the first aspect. It is a laminated body.

[Conductive layer]
The average thickness of the conductive layer provided on at least one surface of the base material 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 even more preferable.
When the average thickness of the conductive layer is at least the lower limit value, high conductivity can be exhibited, and when it is at least the upper limit value, the adhesion of the conductive layer to the substrate is further improved.

The conductive layer included in the conductive laminate of this embodiment contains a conductive composite containing a π-conjugated conductive polymer and a polyanion. Further, it contains a cured product obtained by polymerizing a polymerizable acrylic compound.
When the conductive polymer liquid composition applied to the base material contains a binder component, the conductive layer contains a binder component or a cured product obtained by curing 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 a base material made of a conductive material. The shape of the base material is not particularly limited, and examples thereof include a shape mainly composed of a flat surface such as a film or a substrate.
Examples of the insulating material include glass, synthetic resin, and ceramics.
Examples of the conductive material include metals, conductive metal oxides, carbon and the like.

(Film base material)
When a film base material is used as the base material, the conductive laminate becomes a conductive film.
Examples of the film base material 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-based elastomer, polyester-based elastomer, polyether sulfone, polyetherimide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate and the like.
From the viewpoint of enhancing the adhesion between the film base material and the conductive layer, the synthetic resin for the film base material is preferably a resin of the same type as the binder resin, and among them, a polyester resin such as polyethylene terephthalate is preferable.

The synthetic resin for the film base material may be amorphous or crystalline.
The film base material 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 liquid composition.

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

(Glass substrate)
Examples of the glass base material include a non-alkali glass base material, a soda lime glass base material, a borosilicate glass base material, a quartz glass base material, and the like. When the base material contains an alkaline component, the conductivity of the conductive layer tends to decrease. Therefore, among the glass base materials, non-alkali glass is preferable. Here, the non-alkali glass is a glass composition in which the content of the alkaline component 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, and 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 value, it is less likely to be damaged, and if it is at least the upper limit value, it can contribute to thinning the conductive laminate.
The average thickness of the glass substrate is a value obtained by measuring the thickness at 10 randomly selected points and averaging the measured values.

≪Manufacturing method of conductive laminate≫
A fourth aspect of the present invention is a method for producing a conductive laminate, which comprises applying the conductive polymer liquid composition of the first aspect to at least one surface of a base material. By the production method of this aspect, the conductive laminate of the third aspect can be produced.

Examples of the method of applying (applying) the conductive polymer liquid composition of the first aspect to an arbitrary surface of a base material include a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, and a reverse coater. Methods using coaters such as kiss coaters, fountain coaters, rod coaters, air doctor coaters, knife coaters, blade coaters, cast coaters, screen coaters, methods using atomizers such as air spray, airless spray, rotor dampening, dips, etc. The dipping method and the like can be applied.

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

When the conductive polymer liquid composition contains a dispersion medium, it is preferable to remove the dispersion medium by drying the coating film composed of the conductive polymer liquid composition coated on the base material.
Examples of the method for drying the coating film include heat drying and vacuum drying. As the heat drying, for example, a method such as hot air heating or infrared heating can be adopted.
When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium used, 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. The preferable drying time in the above heating temperature range is preferably 1 minute or more and 30 minutes or less, and more preferably 5 minutes or more and 15 minutes or less.
When the applied conductive polymer liquid composition is a solvent-free type, no drying treatment is required.

A conductive laminate having a conductive layer (conductive film) formed by polymerizing the polymerizable acrylic compounds contained in the coating film after drying the coating film as necessary to cure the coating film. Can be obtained.
A method for polymerizing the polymerizable acrylic compound contained in the coating film is preferable because radical polymerization is easy and reliable. When radical polymerization is applied, it is preferable to add a polymerization initiator to the conductive polymer liquid composition in advance. Depending on the type of polymerization initiator, polymerization can be carried out by heating or irradiating with light (active energy rays).
Examples of the active energy ray include ultraviolet rays, electron beams, visible rays and the like. As the light source of ultraviolet rays, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used.
The illuminance in ultraviolet irradiation is preferably 100 mW / cm ² or more. The integrated light intensity is preferably 50 mJ / cm ² or more. In addition, the illuminance and the integrated light amount in this specification use UVR-T1 (industrial UV checker, receiver; UD-T36, measurement wavelength range; 300 nm or more and 390 nm or less, peak sensitivity wavelength; about 355 nm) manufactured by Topcon. It is a measured value.

≪Manufacturing method of conductive film≫
In the fifth aspect of the present invention, a coating material obtained by adding a thermal polymerization initiator to the conductive polymer liquid composition of the first aspect is applied to at least one surface of an amorphous film substrate to obtain a coating film. A method for producing a conductive film, which comprises a coating step and a stretching step of heating and stretching the coating film to obtain a stretched film.

[Coating process]
The film base material used in this step is not particularly limited as long as it is amorphous, and can be arbitrarily selected from the film base materials exemplified as the material of the conductive laminate described above.
The method of applying the paint to the amorphous film base material in this step to obtain the coated film is not particularly limited, and the coating method exemplified in the above-described method for producing the conductive laminate can be applied.

[Stretching process]
The stretching step is a step of heating and stretching the coating film to obtain a stretched film. When the coating material contains a dispersion medium, it may be dried by heating in this step, or may be dried by providing a separate drying step before being subjected to this step.
By heating and stretching the coating film, a large-area conductive film can be obtained even if the coating area is reduced, and the productivity of the conductive film is improved.
The stretching may be uniaxial stretching or biaxial stretching, but when a uniaxially stretched film is used as the amorphous film base material, it is preferably stretched in a direction perpendicular to the stretching direction. For example, when a uniaxially stretched film stretched along the longitudinal direction is used as an amorphous film base material, it is preferably stretched along the width direction.
The draw ratio of the coating film is preferably 2 times or more and 20 times or less, more preferably 3 times or more and 15 times or less, and further preferably 4 times or more and 10 times or less.

As the heating method, for example, a normal method such as hot air heating or infrared heating can be adopted.
The heating temperature in the stretching step is preferably lower than the crystallization temperature of the amorphous film substrate and is in the range of 50 ° C. or higher and 120 ° C. or lower. Here, the heating temperature is the set temperature of the drying device. If the heating temperature in the stretching step is higher than the crystallization temperature of the amorphous film substrate, the film may become too soft and difficult to stretch.

The polymerization of the polymerizable acrylic compound contained in the coating film of the coating film is promoted by heating the thermal polymerization initiator. When the stretching step is completed, the polymerization curing of the polymerizable acrylic compound contained in the coating film may be completed, or the polymerization curing of the polymerizable acrylic compound contained in the coating film is completed in the crystallization step described below. You may.

[Crystallization process]
The production method of this embodiment may further include a crystallization step.
The crystallization step is a step of heating the stretched film and then cooling it to crystallize the amorphous film base material.
The heating temperature of the stretched film in the crystallization step is equal to or higher than the crystallization temperature of the amorphous film substrate, preferably 200 ° C. or higher, more preferably 220 ° C. or higher, and 240 ° C. or higher. Is even more preferable. When the heating temperature of the stretched film is at least the above lower limit value, the amorphous film base material can be sufficiently crystallized. On the other hand, from the viewpoint of preventing the film substrate from melting, the heating temperature of the stretched film is preferably 300 ° C. or lower.

Since it is easy to crystallize by heating at 200 ° C. or higher, the amorphous film base material is preferably an amorphous polyethylene terephthalate film.
When heated to 200 ° C. or higher, at least a part of the amorphous polyethylene terephthalate constituting the film substrate begins to melt. After its melting, when it is cooled to a temperature lower than the crystallization temperature of polyethylene terephthalate, a part of the melted amorphous polyethylene terephthalate crystallizes and solidifies. As a result, the film base material can be made into a crystalline polyethylene terephthalate film. The film base material made of crystalline polyethylene terephthalate film is excellent in mechanical properties such as tensile strength.

The cooling method after heating is not particularly limited, and air at room temperature may be blown or allowed to cool. Since the amorphous film base material is easily crystallized, the temperature lowering rate at the time of cooling is preferably slow, and specifically, it is preferably 200 ° C./min or less.

≪Conductive molded body≫
A sixth aspect of the present invention is a conductive molded body obtained by molding a cured product of the conductive polymer liquid composition of the first aspect.
In the cured product, the polymerizable acrylic compounds polymerize with each other to form an acrylic resin. Therefore, the conductive molded product can be a conductive acrylic resin molded product.
The shape of the conductive molded body is not particularly limited, and as one embodiment, a plate-shaped resin plate can be used. The thickness of the resin plate is not particularly limited, and can be, for example, 1 mm or more and 30 mm or less. The conductive molded body may be one in which the resin plate is secondarily processed by hot press molding or the like.

The method for producing the conductive molded body of this embodiment is not particularly limited, and a known method for producing a resin molded body by polymerizing and curing an acrylic monomer can be applied. For example, a casting polymerization method, an injection molding method, a 3D printer molding method and the like can be mentioned.
According to the casting polymerization method, a conductive molded product can be formed by injecting a conductive polymer liquid composition into a mold and polymerizing the mold, and the conductive molded product can be peeled off from the mold.
The mold for casting polymerization is not particularly limited, and a known mold can be used. Examples of the mold for obtaining the plate-shaped conductive molded body include a mold for cell casting and a mold for continuous casting.
As a mold for cell casting, for example, two plate-shaped bodies (glass plate, metal plate, etc.) are arranged facing each other at predetermined intervals, and a gasket is arranged at the edge (periphery) thereof, and the plate-shaped body and the gasket are arranged. An example is one in which a sealed space is formed by.
As a mold for continuous casting, for example, a sealed space is formed by facing surfaces of a pair of endless belts traveling in the same direction at the same speed and gaskets traveling at the same speed as the endless belts on both sides of the endless belt. The ones that have been made can be mentioned.
The distance between the voids of the mold is appropriately adjusted so as to obtain a resin plate having a desired thickness, but is generally 1 to 30 mm.

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

(Production Example 2) Synthesis of conductive polymer aqueous dispersion containing π-conjugated conductive polymer and polyanion 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid are added to 2000 ml of ions. The solution dissolved in exchange water was mixed at 20 ° C.
Keeping the obtained mixed solution at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added for 3 hours. The mixture was stirred and reacted.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. This operation was repeated 3 times.
Next, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. 2000 ml of ion-exchanged water was added to the residual liquid, and about 2000 ml of the solvent was removed by an ultrafiltration method. This operation was repeated 3 times.
Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. This operation was repeated 5 times to obtain an aqueous dispersion of polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS) having a concentration of 1.2% by mass.

(Example 1)
To 100 g of the aqueous dispersion of PEDOT-PSS obtained in Production Example 2, 200 g of methanol and 25 g of an epoxy compound (Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether manufactured by Kyoeisha Chemical Co., Ltd.) were added, and the temperature was 60 ° C. for 4 hours. It was heated and stirred. At this time, in PEDOT-PSS, the epoxy compound reacted and bonded to the surplus sulfonic acid group not bonded to PEDOT in PSS. Next, 100 g of isopropanol and 1.0 g of trioctylamine were added. At this time, in PEDOT-PSS, the amine compound was bound to the surplus sulfonic acid group not bound to PEDOT in PSS. As a result, the water dispersibility of PEDOT-PSS was lowered, and a conductive composite containing PEDOT-PSS modified by the reaction of the epoxy compound and the amine compound was precipitated. This precipitate was collected by filtration to obtain 1.8 g of a conductive complex.
Next, the above conductive composite was added to 798.2 g of pentaerythritol triacrylate and dispersed using a high-pressure homogenizer to obtain a conductive polymer liquid composition (paint) containing the above conductive composite. rice field.
3.2 g of Irgacure 184 (BASF's photopolymerization initiator) was added to the obtained paint, applied on a PET film (Toray's Lumirror T60) using a # 12 bar coater, and irradiated with 400 mJ of ultraviolet rays. .. Table 1 shows the results of measuring the surface resistance value of the obtained film.

(Example 2)
The measurement was carried out in the same manner as in Example 1 except that pentaerythritol triacrylate was replaced with the same amount of hydroxyethyl acrylamide in Example 1. The results are shown in Table 1.

(Example 3)
The measurement was carried out in the same manner as in Example 1 except that the pentaerythritol triacrylate was replaced with the same amount of hydroxyethyl acrylate in Example 1. The results are shown in Table 1.

(Example 4)
The measurement was carried out in the same manner as in Example 1 except that the pentaerythritol triacrylate was replaced with the same amount of butyl acrylate in Example 1. The results are shown in Table 1.

(Example 5)
The measurement was carried out in the same manner as in Example 1 except that pentaerythritol triacrylate was replaced with the same amount of 4-acroylmorpholine in Example 1. The results are shown in Table 1.

(Example 6)
The measurement was carried out in the same manner as in Example 1 except that pentaerythritol triacrylate was replaced with the same amount of trimethylolpropane triacrylate in Example 1. The results are shown in Table 1.

(Example 7)
The measurement was carried out in the same manner as in Example 1 except that pentaerythritol triacrylate was replaced with the same amount of methyl methacrylate (methyl methacrylate) in Example 1. The results are shown in Table 1.

(Example 8)
To 100 g of the aqueous dispersion of PEDOT-PSS obtained in Production Example 2, 200 g of methanol and 25 g of butyl glycidyl ether were added, and the mixture was heated and stirred at 60 ° C. for 4 hours. At this time, in PEDOT-PSS, the epoxy compound reacted and bonded to the surplus sulfonic acid group not bonded to PEDOT in PSS. Next, 100 g of isopropanol and 1.0 g of trioctylamine were added. At this time, in PEDOT-PSS, the amine compound was bound to the surplus sulfonic acid group not bound to PEDOT in PSS. As a result, the water dispersibility of PEDOT-PSS was lowered, and a conductive composite containing PEDOT-PSS modified by the reaction of the epoxy compound and the amine compound was precipitated. This precipitate was collected by filtration to obtain 1.7 g of a conductive complex.
Next, the above conductive composite was added to 798.3 g of pentaerythritol triacrylate and dispersed using a high-pressure homogenizer to obtain a conductive polymer liquid composition (paint) containing the above conductive composite. rice field.
3.2 g of Irgacure 184 (BASF's photopolymerization initiator) was added to the obtained paint, applied on a PET film (Toray's Lumirror T60) using a # 12 bar coater, and irradiated with 400 mJ of ultraviolet rays. .. Table 1 shows the results of measuring the surface resistance value of the obtained film.

(Example 9)
To 100 g of the aqueous dispersion of PEDOT-PSS obtained in Production Example 2, 200 g of methanol and 25 g of an epoxy compound (Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether manufactured by Kyoeisha Chemical Co., Ltd.) were added, and the temperature was 60 ° C. for 4 hours. It was heated and stirred. At this time, in PEDOT-PSS, the epoxy compound reacted and bonded to the surplus sulfonic acid group not bonded to PEDOT in PSS. Next, 100 g of isopropanol and 1.0 g of tributylamine were added. At this time, in PEDOT-PSS, the amine compound was bound to the surplus sulfonic acid group not bound to PEDOT in PSS. As a result, the water dispersibility of PEDOT-PSS was lowered, and a conductive composite containing PEDOT-PSS modified by the reaction of the epoxy compound and the amine compound was precipitated. This precipitate was collected by filtration to obtain 1.7 g of a conductive complex.
Next, the above conductive composite was added to 798.3 g of pentaerythritol triacrylate and dispersed using a high-pressure homogenizer to obtain a conductive polymer liquid composition (paint) containing the above conductive composite. rice field.
3.2 g of Irgacure 184 (BASF's photopolymerization initiator) was added to the obtained paint, applied on a PET film (Toray's Lumirror T60) using a # 12 bar coater, and irradiated with 400 mJ of ultraviolet rays. .. Table 1 shows the results of measuring the surface resistance value of the obtained film.

(Example 10)
To 100 g of the aqueous dispersion of PEDOT-PSS obtained in Production Example 2, 200 g of methanol and 25 g of an epoxy compound (Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether manufactured by Kyoeisha Chemical Co., Ltd.) were added, and the temperature was 60 ° C. for 4 hours. It was heated and stirred. At this time, in PEDOT-PSS, the epoxy compound reacted and bonded to the surplus sulfonic acid group not bonded to PEDOT in PSS. Next, 1.0 g of trioctylamine was added. At this time, in PEDOT-PSS, the amine compound was bound to the surplus sulfonic acid group not bound to PEDOT in PSS. As a result, the water dispersibility of PEDOT-PSS was lowered, and the conductive composite containing PEDOT-PSS modified by the reaction of the epoxy compound and the amine compound was precipitated and precipitated.
150 g of the upper layer of this solution was removed, 300 g of methyl methacrylate was added, and the mixture was gently mixed. After allowing this mixed solution to stand to allow the conductive composite to settle again, 300 g of the upper layer containing no conductive composite was removed, 700 g of methyl methacrylate was further added, and the mixture was dispersed using a high-pressure homogenizer. , A conductive polymer liquid composition (paint) containing the above conductive composite was obtained.
3.2 g of Irgacure 184 (BASF's photopolymerization initiator) was added to the obtained paint, applied on a PET film (Toray's Lumirror T60) using a # 12 bar coater, and irradiated with 400 mJ of ultraviolet rays. .. Table 1 shows the results of measuring the surface resistance value of the obtained film.

(Comparative Example 1)
To 100 g of the aqueous dispersion of PEDOT-PSS obtained in Production Example 2, 200 g of methanol and 25 g of an epoxy compound (Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether manufactured by Kyoeisha Chemical Co., Ltd.) were added, and the temperature was 60 ° C. for 4 hours. It was heated and stirred. At this time, in PEDOT-PSS, the epoxy compound reacted and bonded to the surplus sulfonic acid group not bonded to PEDOT in PSS. Next, 100 g of isopropanol was added. As a result, the water dispersibility of PEDOT-PSS was lowered, and a conductive composite containing PEDOT-PSS and an epoxy compound bonded thereto was precipitated. This precipitate was collected by filtration to obtain 1.5 g of a conductive complex.
Next, the above-mentioned conductive composite was added to 798.5 g of pentaerythritol triacrylate and dispersed using a high-pressure homogenizer to obtain a mixed solution containing the above-mentioned conductive composite, and all of them were obtained in a few minutes. The study was discontinued because the conductive composite settled and separated.

(Comparative Example 2)
To 100 g of the aqueous dispersion of PEDOT-PSS obtained in Production Example 2, 200 g of methanol, 100 g of isopropanol, and 1 g of trioctylamine were added. As a result, the water dispersibility of PEDOT-PSS was lowered, and a conductive complex containing PEDOT-PSS and an amine compound bonded thereto was precipitated. This precipitate was collected by filtration to obtain 1.6 g of a conductive complex.
Next, the above-mentioned conductive composite was added to 798.4 g of pentaerythritol triacrylate and dispersed using a high-pressure homogenizer to obtain a mixed solution containing the above-mentioned conductive composite, and all of them were obtained in a few minutes. The study was discontinued because the conductive composite settled and separated.

[Measurement of surface resistance value]
For the conductive films produced in each example, the surface resistance value of the conductive layer was measured using a resistivity meter (High Restor manufactured by Nittoseiko Analytech Co., Ltd.) under the condition of an applied voltage of 10 V. In the table, "1.0E + 10" means "1.0 × 10 ¹⁰ ", and the same applies to the others.

(Example 11)
3. To 90 g of the conductive polymer liquid composition obtained in Example 1, 10 g of KF-2005 (manufactured by Shin-Etsu Chemical Co., Ltd., solvent-free ultraviolet curable silicone) and Irgacure 184 (manufactured by BASF, photopolymerization initiator). 0 g was added, coated on a PET film using a # 4 bar coater, and irradiated with 400 mJ of ultraviolet light. Table 2 shows the results of measuring the surface resistance value and the peeling force of the obtained film.

[Measurement of peeling force]
With respect to the conductive film produced in Example 11, the peeling force was measured by the following method to evaluate the releasability.
According to JIS Z0237, a PET film (width 10 mm) pressure-bonded to the surface of the conductive layer is peeled off at an angle of 180 ° (peeling speed 0.3 m / min) using a tensile tester, and the peeling force (unit: N). Was measured. The smaller the peeling force, the higher the releasability of the coating film.

(Example 12)
To 100 g of the conductive polymer liquid composition obtained in Example 1, 4.0 g of a water-soluble azo-based polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-501) was added, and a # 12 bar coater was used. Then, it was coated on a non-crystalline polyethylene terephthalate film to obtain a coated film.
The obtained coating film was stretched four times at 100 ° C. using a biaxial stretching device (manufactured by Imoto Seisakusho Co., Ltd., 11A9) to obtain a stretched film. During this stretching, the water-soluble azo polymerization initiator in the coating film promoted the polymerization of the polymerizable acrylic compound in the coating film. Subsequently, the stretched film was heated at 240 ° C. for 30 seconds to completely polymerize the polymerizable acrylic compound in the coating film, and then slowly cooled so that the temperature lowering rate was 100 ° C./min or less. As a result, the amorphous polyethylene terephthalate film was crystallized to obtain a conductive film having a conductive layer on the surface of the crystalline polyethylene terephthalate film. Table 3 shows the results of measuring the surface resistance value of the obtained film.

Claims (10)

It contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, and a polymerizable acrylic compound having a (meth) acrylic group.
A conductive polymer liquid composition in which some anionic groups of the polyanion are modified by a reaction with an epoxy compound and an amine compound or a quaternary ammonium compound. The conductive polymer liquid composition according to claim 1, wherein 95% by mass or more of the total mass of the conductive polymer liquid composition is the polymerizable acrylic compound. The conductive polymer liquid composition according to claim 1 or 2, wherein the π-conjugated conductive polymer contains poly (3,4-ethylenedioxythiophene), or the polyanion contains polystyrene sulfonic acid. thing. The conductive polymer liquid composition according to any one of claims 1 to 3, wherein the polymerizable acrylic compound is an ultraviolet curable silicone. A precipitation recovery step of adding an epoxy compound, an amine compound or a quaternary ammonium compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, and then recovering the precipitated reaction product. ,
A method for producing a conductive polymer liquid composition, comprising an addition step of adding a polymerizable acrylic compound having a (meth) acrylic group to the reaction product to obtain a conductive polymer liquid composition. The method for producing a conductive polymer liquid composition according to claim 5, wherein the method for recovering the reaction product is filtration. A coating material obtained by adding a polymerization initiator to the conductive polymer liquid composition according to any one of claims 1 to 4 is applied to at least one surface of a base material, and then the polymerizable property contained in the coating film. A method for producing a conductive laminate, which comprises a step of polymerizing an acrylic compound. A coating material obtained by adding a thermal polymerization initiator to the conductive polymer liquid composition according to any one of claims 1 to 4 is applied to at least one surface of an amorphous film substrate to obtain a coating film. The coating process to obtain and
A method for producing a conductive film, which comprises a stretching step of heating and stretching the coating film to obtain a stretched film. A conductive layer comprising a base material and a cured layer of the conductive polymer liquid composition according to any one of claims 1 to 4 formed on at least one surface of the base material. Laminated body. A conductive molded product obtained by molding a cured product of the conductive polymer liquid composition according to any one of claims 1 to 4.