JP6562548B2 - Conductive polymer dispersion and conductive film - Google Patents

Description

  The present invention relates to a conductive polymer dispersion and a conductive film containing a π-conjugated conductive polymer.

A conductive polymer dispersion containing a π-conjugated conductive polymer and a polyanion may be applied to a film substrate and cured to form a conductive layer.
The conductive layer formed from the conductive polymer dispersion has insufficient light resistance, and when irradiated with visible light or ultraviolet light for a long time, the surface resistance value may increase and the conductivity may decrease. .
Therefore, there are cases where the conductive polymer dispersion contains a light-resistant agent such as gallic acid (gallic acid) or a benzophenone compound (Patent Documents 1 and 2).

JP 2008-031204 A JP 2008-297484 A

However, even the methods described in Patent Documents 1 and 2 cannot be said to have sufficient light resistance, and when the content of the light proofing agent is increased in order to obtain sufficient light resistance, the conductivity tends to decrease.
In addition, when an active energy ray-curable acrylic compound is contained in the conductive polymer dispersion in order to improve the scratch resistance of the conductive layer, the active energy can be obtained by using the light-proofing agent described in Patent Documents 1 and 2. The linear curable acrylic compound tended to be hard to be cured. Therefore, the scratch resistance could not be fully exhibited.
An object of the present invention is to provide a conductive polymer dispersion capable of easily forming a conductive layer having excellent conductivity, light resistance, and scratch resistance. Moreover, an object of this invention is to provide a conductive film provided with the conductive layer which was excellent in electroconductivity, light resistance, and scratch resistance.

[1] A conductive complex containing a polyanion having an anionic group and a π-conjugated conductive polymer, a substituent-containing aromatic compound, an active energy ray-curable acrylic compound, and a dispersion medium, In the group-containing aromatic compound, at least one hydrogen atom of the aromatic ring is substituted with a substituent having an amide bond, and at least one of the remaining hydrogen atoms of the aromatic ring is substituted with a hydroxy group , Conductive polymer dispersion.
[2] The conductive polymer dispersion according to [1], in which an amine compound or an epoxy compound is coordinated or added to the anion group of the polyanion, and the dispersion medium is an organic solvent.
[3] The substituent-containing aromatic compound is a compound represented by the following formula (1), a compound represented by the following formula (2), a compound represented by the following formula (3), and the following formula (4). The conductive polymer dispersion according to [1] or [2], which is at least one selected from the group consisting of compounds represented by:
(R ¹ in formulas (1) to (4) is each a hydrogen atom or any monovalent substituent, and R ² in formulas (2) and (4) is each an arbitrary divalent substitution. Group.)

[4] The conductive polymer dispersion according to any one of [1] to [3], wherein the substituent-containing aromatic compound has a (meth) acryloyl group.
[5] The conductive polymer dispersion according to [4], wherein the compound represented by the formula (3) is a compound represented by the following formula (5).
(R ³ in Formula (5) is a hydrogen atom or a methyl group.)

[6] The conductive polymer dispersion according to [4], wherein the compound represented by the formula (4) is a compound represented by the following formula (6).
(R ² in Formula (6) is an arbitrary divalent substituent, and R ⁴ is a hydrogen atom or a methyl group.)

[7] The substituent-containing aromatic compound is at least one selected from the group consisting of 4-hydroxyphenylacetamide, 4-hydroxybenzamide, dihydroxybenzamide, 4-hydroxyacetanilide, and 3-hydroxyacetanilide. [1] The conductive polymer dispersion according to any one of to [3].
[8] The compound represented by the formula (5) is at least one selected from the group consisting of N- (4-hydroxyphenyl) -acrylamide and N- (4-hydroxyphenyl) -methacrylamide. 5]. The conductive polymer dispersion according to [5].
[9] The π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene), and the polyanion is polystyrene sulfonic acid, according to any one of [1] to [8] The conductive polymer dispersion described.
[10] A film substrate and a conductive layer formed by curing the conductive polymer dispersion according to any one of [1] to [9], which is formed on at least one surface of the film substrate. A conductive film provided.

According to the conductive polymer dispersion of the present invention, it is possible to easily form a conductive layer having excellent conductivity, light resistance, and scratch resistance.
The conductive film of the present invention includes a conductive layer having excellent conductivity, light resistance, and scratch resistance.

The conductive polymer dispersion of one embodiment of the present invention includes a conductive complex including a π-conjugated conductive polymer and a polyanion, a substituent-containing aromatic compound, an active energy ray-curable acrylic compound, and a dispersion medium. A dispersion containing
The dispersion is used as a paint for forming a conductive layer.

(Conductive composite)
[Π-conjugated conductive polymer]
The π-conjugated conductive polymer is not particularly limited as long as it has the effect of the present invention as long as the main chain is an organic polymer composed of π-conjugated system. For example, polypyrrole-based conductive polymer, polythiophene-based polymer Conductive polymer, polyacetylene conductive polymer, polyphenylene conductive polymer, polyphenylene vinylene conductive polymer, polyaniline conductive polymer, polyacene conductive polymer, polythiophene vinylene conductive polymer, and These copolymers are exemplified. 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 ( -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-dioctyl) Oxythiophene), poly (3,4-didecyloxythiophene), poly (3, -Didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butenedioxythiophene), 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-carboxybutylthiophene) is mentioned.
Examples of the polypyrrole conductive polymer 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-hexyl) Oxy pyrrole), poly (3-methyl-4-hexyloxy-pyrrole) and the like.
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), and poly (3-anilinesulfonic acid).
Among the π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity, transparency, and heat resistance. In the present specification, poly (3,4-ethylenedioxythiophene) is sometimes referred to as “PEDOT”.
The π-conjugated conductive polymer may be used alone or in combination of two or more.

[Polyanion]
The polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anion group of the 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, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene sulfone. Polymers having a sulfonic acid group such as acid, polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzenesulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid , Polymers having a carboxylic acid group such as polymethacrylcarboxylic acid, poly (2-acrylamido-2-methylpropanecarboxylic acid), polyisoprene carboxylic acid, polyacrylic acid and the like. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
Among these polyanions, a polymer having a sulfonic acid group is preferable and polystyrene sulfonic acid is more preferable because antistatic properties can be further increased. In the present specification, polystyrene sulfonic acid may be referred to as “PSS”.
The said polyanion may be used individually by 1 type, and may use 2 or more types together.
The mass average molecular weight of the polyanion is preferably 20,000 to 1,000,000, and more preferably 100,000 to 500,000.
The mass average molecular weight in the present specification is a value obtained by measuring with gel permeation chromatography and obtaining the standard substance as polystyrene.

  The content ratio of the polyanion in the conductive composite is preferably in the range of 1 to 1000 parts by mass, more preferably 10 to 700 parts by mass with respect to 100 parts by mass of the π-conjugated conductive polymer. More preferably, it is in the range of 100 to 500 parts by mass. If the polyanion content is less than the lower limit, the doping effect on the π-conjugated conductive polymer tends to be weak, the conductivity may be insufficient, and the conductivity in the conductive polymer dispersion may be insufficient. The dispersibility of the sex complex decreases. On the other hand, when the content of the polyanion exceeds the upper limit, the content of the π-conjugated conductive polymer is decreased, and it is difficult to obtain sufficient conductivity.

The polyanion is coordinated and doped to the π-conjugated conductive polymer to form a conductive composite.
However, in the polyanion in this embodiment, not all anion groups are doped into the π-conjugated conductive polymer, but have excess anion groups that do not contribute to doping. Since the surplus anionic group has high hydrophilicity, it plays a role of improving the water dispersibility of the conductive composite.

  The conductive complex may be hydrophobized by coordinating or adding an amine compound or an epoxy compound to the anion group of the polyanion, particularly an excess anion group not involved in the dope. The hydrophobic conductive composite has high dispersibility in an organic solvent.

The amine compound may be any of primary amine, secondary amine, tertiary amine, and quaternary ammonium salt. Moreover, an amine compound may be used individually by 1 type, and may use 2 or more types together.
The amine compound is a linear or branched alkyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an alkylene group having 2 to 12 carbon atoms, or 6 carbon atoms. It may have a substituent selected from an -12 arylene group, an aralkylene group having 7 to 12 carbon atoms, and an oxyalkylene group having 2 to 12 carbon atoms.

Specific examples of the primary amine include aniline, toluidine, benzylamine, and ethanolamine.
Specific examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, and dinaphthylamine.
Specific examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine.
Specific examples of the quaternary ammonium salt include tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetraphenylammonium salt, tetrabenzylammonium salt, tetranaphthylammonium salt and the like. A hydroxide ion is mentioned as an anion which becomes a pair of ammonium.

  Among these amine compounds, a tertiary amine is preferable, and tributylamine and trioctylamine are more preferable because dispersibility of the conductive complex in an organic solvent is higher.

(Epoxy compound)
The epoxy compound is a compound having one or more epoxy groups. Epoxy groups can react with anionic groups such as carboxy groups.
Specific examples of the epoxy compound include, for example, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A diglycidyl ether, Propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, fatty acid-modified epoxy, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether , Sorbitol polyglycidyl ether, ethylene oxide laur Alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, C12, C13 mixed higher alcohol glycidyl ether, 1,2-epoxy-4-vinylcyclohexane, adipic acid glycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate.

  The total content of the amine compound and the epoxy compound is preferably 10 to 300 parts by mass, and more preferably 50 to 150 parts by mass, when the conductive composite is 100 parts by mass. If the total content ratio of the amine compound and the epoxy compound is equal to or higher than the lower limit value, the dispersibility of the conductive composite in the organic solvent becomes higher. it can.

(Substituent-containing aromatic compound)
In the substituent-containing aromatic compound in this embodiment, at least one of the hydrogen atoms of the aromatic ring is substituted with a substituent having an amide bond, and at least one of the remaining hydrogen atoms of the aromatic ring is substituted with a hydroxy group. It is a substituted compound. Here, the aromatic ring includes not only a benzene ring but also a naphthalene ring and an anthracene ring. The substituent-containing aromatic compound is not an amine compound.
This substituent-containing aromatic compound has the effect of improving the light resistance of the conductive layer and improving the conductivity, and further hardly inhibits the curing of the active energy ray-curable acrylic compound.

Since the substituent-containing aromatic compound can be easily synthesized and can sufficiently exhibit the above effects, the compound represented by the above formula (1), the compound represented by the above formula (2), the above formula ( It is preferably at least one selected from the group consisting of the compound represented by 3) and the compound represented by the above formula (4).
R ¹ in the formulas (1) to (4) is each a hydrogen atom or an arbitrary monovalent substituent, and R ² is an arbitrary divalent substituent.
Examples of the monovalent substituent include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, and a butyl group), an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group), and an alkenyl group (for example, , Ethylenyl group, propylenyl group, butyrenyl group, etc.), alkynyl group (eg, ethynyl group, propynyl group, butynyl group, etc.), aryl group (eg, phenyl group, naphthalene group, etc.), etc., and these groups are substituted. It may have a group (for example, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, a hydroxy group, an amino group, a carboxy group, etc.).
Examples of the divalent substituent include alkylene groups (eg, methylene group, ethylene group, propylene group, butylene group), oxyalkylene groups (eg, oxyethylene group, oxypropylene group, etc.), and these groups. May have a substituent (for example, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, a hydroxy group, an amino group, a carboxy group, etc.).
A substituent-containing aromatic compound may be used individually by 1 type, and may use 2 or more types together.

Specific examples of the compound represented by the formula (1) include 4-hydroxybenzamide.
Specific examples of the compound represented by the formula (2) include 4-hydroxyphenylacetamide and the like.
Specific examples of the compound represented by formula (3) include, for example, 4-hydroxyacetanilide, 3-hydroxyacetanilide, N- (4-hydroxyphenyl) -acrylamide, N- (4-hydroxyphenyl) -methacrylamide and the like. Is mentioned.
One of the above specific substituent-containing aromatic compounds may be used alone, or two or more thereof may be used in combination.

The substituent-containing aromatic compound preferably has a (meth) acryloyl group. When the substituent-containing aromatic compound has a (meth) acryloyl group, the substituent-containing aromatic compounds can be polymerized and cured. Further, the substituent-containing aromatic compound reacts with the active energy ray-curable acrylic compound to become a part of the cured product of the acrylic compound. From these facts, when a substituent-containing aromatic compound having a (meth) acryloyl group is used, the scratch resistance of the conductive layer formed from the conductive polymer dispersion can be further improved.
Note that non-polymerizable light-proofing agents as described in Patent Documents 1 and 2 do not contribute to the improvement of scratch resistance.

A substituent-containing aromatic compound having a (meth) acryloyl group, and the compound represented by the above formula (3) is preferably a compound represented by the formula (5) because it can be easily produced. R ³ in Formula (5) is a hydrogen atom or a methyl group. Specific examples of the compound represented by the formula (5) include N- (4-hydroxyphenyl) -acrylamide, N- (4-hydroxyphenyl) -methacrylamide and the like.
A substituent-containing aromatic compound having a (meth) acryloyl group, and the compound represented by the above formula (4) is preferably a compound represented by the formula (6) because it can be easily produced. R ² in Formula (6) is an arbitrary divalent substituent similarly to Formulas (2) and (4), and R ⁴ is a hydrogen atom or a methyl group.

  The content ratio of the substituent-containing aromatic compound is preferably 100 parts by mass or more, more preferably 300 to 2000 parts by mass, and 400 to 1600 parts by mass with respect to 100 parts by mass of the conductive composite. More preferably it is. If the content rate of a substituent containing aromatic compound is more than the said lower limit, the light resistance and electroconductivity of the conductive layer formed from this conductive polymer dispersion liquid can be made higher. On the other hand, if the content ratio of the substituent-containing aromatic compound is not more than the above upper limit value, the conductive composite can be sufficiently contained, so that sufficiently high conductivity can be ensured.

(Active energy ray-curable acrylic compound)
The active energy ray-curable acrylic compound is an acrylic compound that is cured by radical polymerization upon irradiation with active energy rays (ultraviolet rays, electron beams, visible rays).
Examples of the active energy ray-curable acrylic compound include acrylate, methacrylate, (meth) acrylamide, vinyl ether, carboxylic acid vinyl ester and the like. The active energy ray-curable acrylic compound may be a monofunctional monomer having only one vinyl group, a polyfunctional monomer having two or more vinyl groups, or a combination of a monofunctional monomer and a polyfunctional monomer. . When the monofunctional acrylic monomer and the polyfunctional acrylic monomer are used in combination, the conductive layer is cross-linked, so that the scratch resistance of the conductive layer can be further improved.

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, trimethylolpropane triacrylate, Such as glycerin propoxytriacrylate It is below.
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, trimethylolpropane trimethacrylate and the like.
Examples of (meth) acrylamide include methacrylamide, 2-hydroxyethylacrylamide, N-methylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N-phenylacrylamide, N-methylolacrylamide, dimethylaminopropylacrylamide, Examples thereof include dimethylaminopropyl methacrylamide, diacetone acrylamide, N, N-dimethylacrylamide, N-vinylformamide, acryloylmorpholine, acryloylpiperidine and the like.
Examples of the vinyl ether include 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, and the like.
Examples of the vinyl carboxylate include vinyl butyrate, vinyl monochloroacetate, vinyl pivalate and the like.
The active energy ray-curable acrylic compound may be a polyfunctional acrylate obtained by reacting an acrylic monomer with another compound, such as epoxy acrylate, urethane acrylate, polyester acrylate, or polyacryl acrylate.
The active energy ray-curable acrylic compound may be used alone or in combination of two or more.
In addition to the active energy ray-curable acrylic compound, a photopolymerization initiator that generates radicals by irradiation with active energy rays may be contained.

  The content ratio of the active energy ray-curable acrylic compound is preferably 1000 to 100,000 parts by mass, and more preferably 3000 to 50000 parts by mass with respect to 100 parts by mass of the conductive composite. If the content ratio of the active energy ray-curable acrylic compound is not less than the lower limit value, the scratch resistance of the resulting conductive layer can be sufficiently improved, and if it is not more than the upper limit value, sufficient conductivity is ensured. it can.

(Dispersion medium)
The dispersion medium in this embodiment is a liquid for dispersing the conductive polymer composite, and is composed of at least one of water and an organic solvent. When an amine compound or an epoxy compound is coordinated or added to the anion group of the polyanion, the conductive composite loses its hydrophilicity and becomes hydrophobic, so use an organic solvent as the dispersion medium. Is preferred.
Organic solvents include ketone solvents such as 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; diethyl ether, dimethyl ether, ethylene Ether solvents such as glycol, propylene glycol, propylene glycol monoalkyl ether, propylene glycol dialkyl ether; ester solvents such as ethyl acetate, propyl acetate, butyl acetate; benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, etc. Aromatic solvents: ethanol, propanol, isopropanol, n-butanol, t-butanol, allyl alcohol Alcohol solvents such Lumpur; N- methylpyrrolidone, dimethylacetamide, amide solvents such as dimethylformamide, including without being limited to the above. These organic solvents may be used individually by 1 type, and may use 2 or more types together.
The content of the dispersion medium is such that the solid content concentration of the conductive polymer dispersion is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass.

(Additive)
The conductive polymer dispersion may contain a known additive.
The additive is not particularly limited as long as it has the effect of the present invention, and for example, a surfactant, an inorganic conductive agent, an antifoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like can be used. However, the additive comprises a compound other than the polyanion, the substituent-containing aromatic compound, the amine compound, the epoxy compound, the active energy ray-curable acrylic compound, and the dispersion medium.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferred from the viewpoint of storage stability. Moreover, you may add polymer type surfactants, such as polyvinyl alcohol and polyvinylpyrrolidone.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving a metal salt in water.
Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone resin.
Examples of the coupling agent include silane coupling agents having a vinyl group, an amino group, an epoxy group, and the like.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, saccharides, vitamins and the like.
Examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. Is mentioned.

(Method for producing conductive polymer dispersion)
In the case where the dispersion medium is water, a conductive polymer dispersion is produced by polymerizing a monomer that forms a π-conjugated conductive polymer in an aqueous solution of polyanion, and then a substituent-containing aromatic compound and activity. A method of adding an energy ray-curable acrylic compound can be mentioned.
As a method for producing a conductive polymer dispersion in the case where the dispersion medium is an organic solvent, in a polyanion aqueous solution, a monomer that forms a π-conjugated conductive polymer is polymerized to obtain an aqueous dispersion, The aqueous dispersion is freeze-dried to prepare a freeze-dried product, and an organic solvent and an amine compound or an epoxy compound are added to the freeze-dried product, followed by dispersion treatment, and then a substituent-containing aromatic compound and active energy ray curability. The method of adding an acrylic compound is mentioned.

<Conductive film>
The conductive film of one embodiment of the present invention includes a film substrate and a conductive layer formed on at least one surface of the film substrate and cured from the conductive polymer dispersion.

(Film substrate)
A plastic film can be used as the film substrate.
Examples of the resin material constituting the plastic film include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, and styrene. Examples include elastomers, polyester-based elastomers, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, and cellulose acetate propionate. Among these resin materials, polyethylene terephthalate is preferable and amorphous polyethylene terephthalate is more preferable from the viewpoints of transparency, flexibility, antifouling property, strength, and the like.
The plastic film may be an unstretched film, a uniaxially stretched film, or a biaxially stretched film. In terms of excellent mechanical properties, the plastic film is preferably a biaxially stretched film.

As average thickness of the film base material which comprises an electroconductive film, it is preferable that it is 5-400 micrometers, and it is more preferable that it is 10-200 micrometers. If the average thickness of the film base material constituting the conductive film is equal to or greater than the lower limit value, it is difficult to break, and if it is equal to or smaller than the upper limit value, sufficient flexibility as a film can be ensured.
The average thickness in the present specification is a value obtained by measuring thicknesses at arbitrary 10 locations and averaging the measured values.

(Conductive layer)
The conductive layer contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, a substituent-containing aromatic compound, and a cured product of an active energy ray-curable acrylic compound. When the substituent-containing aromatic compound has a (meth) acryloyl group, the substituent-containing aromatic compounds are polymerized to form a cured product.
The surface resistance value of the exposed surface of the conductive layer is in the range of 1.0 × 10 ^{3 to} 1.0 × 10 ⁹ Ω / □. The surface resistance value in the present invention is a value measured by a resistivity meter.
The average thickness of the conductive layer is preferably 0.1 to 50 μm, and more preferably 0.2 to 20 μm. If the average thickness of the conductive layer is equal to or higher than the lower limit, sufficiently high conductivity can be exhibited, and if the average thickness is equal to or lower than the upper limit, the conductive layer can be easily formed.

Examples of the method for forming the conductive layer include a method in which a conductive polymer dispersion is applied to a film substrate and then cured.
Coating methods for conductive polymer dispersions include gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, fountain coaters, rod coaters, air doctor coaters, knife coaters, blade coaters. A coating method using a coater such as a cast coater or a screen coater, a spraying method using a sprayer such as air spray, airless spray, or rotor dampening, a dipping method or the like can be applied.
After applying the conductive polymer dispersion and before curing, it may be dried as necessary. As a drying method, for example, a normal method such as a drying method by hot air heating or a drying method by infrared heating can be employed.
Examples of a method for curing the conductive polymer dispersion include a method of irradiating an active energy ray to a coating film formed by coating.
Among the active energy rays, ultraviolet light (ultraviolet light) is preferable in terms of general use. In the irradiation with ultraviolet light, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used.
The illuminance upon irradiation with ultraviolet light is preferably 100 mW / cm ² or more. When the illuminance is less than 100 mW / cm ² , the active energy ray-curable acrylic compound may not be sufficiently cured. Further, the integrated light quantity is preferably 50 mJ / cm ² or more. If the integrated light quantity is less than 50 mJ / cm ² , crosslinking may not be sufficient. In addition, the illumination intensity and integrated light quantity in this invention were measured using Topcon Co., Ltd. UVR-T1 (Industrial UV checker, light receiver; UD-T36, measurement wavelength range; 300-390 nm, peak sensitivity wavelength; about 355 nm). Value.

(Function and effect)
As a result of investigation by the present inventor, it has been found that the inclusion of the substituent-containing aromatic compound in addition to the conductive composite increases the conductivity and light resistance of the conductive layer. Further, as a result of investigation by the present inventor, it was found that the active energy ray-curable acrylic compound is sufficiently cured because the substituent-containing aromatic compound hardly inhibits the curing of the active energy ray-curable resin. Therefore, the conductive layer in the present invention has high scratch resistance.

(Production Example 1)
Dissolve 206 g of sodium styrenesulfonate in 1000 ml of ion-exchanged water and, while stirring at 80 ° C., add dropwise 1.14 g of ammonium persulfate oxidizer solution previously dissolved in 10 ml of water for 20 minutes. Stir.
To the obtained sodium styrenesulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, about 1000 ml of the polystyrenesulfonic acid-containing solution was removed by ultrafiltration, and 2000 ml of ion-exchanged water was added to the remaining liquid. About 2000 ml of solution was removed by ultrafiltration. The above ultrafiltration operation was repeated three times. Further, about 2000 ml of ion-exchanged water was added to the obtained filtrate, and about 2000 ml of the solution was removed by ultrafiltration. This ultrafiltration operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Production Example 2)
14.2 g of 3,4-ethylenedioxythiophene and a solution of 36.7 g of polystyrene sulfonic acid dissolved in 2000 ml of ion-exchanged water were mixed at 20 ° C.
While maintaining the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added, The reaction was stirred for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of solution was removed by ultrafiltration. This operation was repeated three times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the resulting solution, about 2000 ml of solution is removed by ultrafiltration, and 2000 ml of ion-exchanged water is added to this solution. About 2000 ml of solution was removed by external filtration. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed by ultrafiltration. This operation was repeated 5 times to obtain a 1.2% by mass polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) aqueous dispersion (PEDOT-PSS aqueous dispersion).

(Production Example 3)
1000 g of the above PEDOT-PSS aqueous dispersion was freeze-dried to obtain 12 g of a freeze-dried product.

(Production Example 4)
4.0 g of the lyophilized product and 3.5 g of trioctylamine were added to 1000 g of isopropylamine, and dispersed using a high-pressure homogenizer to obtain a mixed solution A containing PEDOT-PSS and trioctylamine.

(Production Example 5)
4.0 g of the lyophilized product and 1.8 g of tributylamine were added to 1000 g of isopropylamine and dispersed using a high-pressure homogenizer to obtain a mixed solution B containing PEDOT-PSS and trioctylamine.

(Production Example 6)
To 100 g of PEDOT-PSS aqueous dispersion, 300 g of methanol and 25 g of Epolite M-1230 (Kyoeisha Chemical Co., Ltd., C12, C13 mixed higher alcohol glycidyl ether) were added, and the mixture was heated and stirred at 60 ° C. for 4 hours. By this stirring, a composite precipitate containing PEDOT-PSS and the higher alcohol glycidyl ether is generated. This precipitate was collected by filtration to recover 1.575 g of the composite.
Next, the above complex was added to 315 g of methyl ethyl ketone and dispersed using a high-pressure homogenizer to obtain a mixed solution C containing PEDOT-PSS and higher alcohol glycidyl ether.

Example 1
To 53.5 g of the mixed liquid A obtained in Production Example 4, 10 g of Art Resin UN-904M (manufactured by Negami Kogyo Co., Ltd., urethane acrylate), 20 g of pentaerythritol triacrylate, 15 g of diacetone alcohol, and a photopolymerization initiator ( 1.2 g of BASF Corporation, Irgacure 127) and 2.0 g of 4-hydroxyphenylacetamide (930 parts by mass with respect to 100 parts by mass of PEDOT-PSS solid content) were added, and a conductive polymer organic solvent dispersion liquid was added. Was prepared.
The obtained conductive polymer organic solvent dispersion was applied to one surface of a polyethylene terephthalate film (PET film, manufactured by Toray Industries Inc., Lumirror T60), dried at 120 ° C. for 1 minute, and then irradiated with 400 mJ ultraviolet rays. Then, the conductive polymer organic solvent dispersion was cured. Thereby, the electroconductive film in which the electroconductive layer was formed in one surface of the film base material was obtained.

(Example 2)
A conductive film was obtained in the same manner as in Example 1 except that 2.0 g of 4-hydroxyphenylacetamide in Example 1 was changed to 1.0 g (470 parts by mass with respect to 100 parts by mass of PEDOT-PSS solid content). Obtained.

(Example 3)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was changed to 3-hydroxyacetanilide in Example 1.

Example 4
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was changed to 4-hydroxyacetanilide in Example 1.

(Example 5)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was changed to 4-hydroxybenzamide in Example 1.

(Example 6)
A conductive film was obtained in the same manner as in Example 1 except that the amount of the mixed solution A was changed to 33.5 g in Example 1.

(Example 7)
A conductive film was obtained in the same manner as in Example 1 except that the amount of the mixed solution A was changed to 73.5 g in Example 1.

(Example 8)
A conductive film was obtained in the same manner as in Example 1 except that the mixed liquid A obtained in Production Example 4 in Example 1 was changed to the mixed liquid B obtained in Production Example 5.

Example 9
A conductive film was obtained in the same manner as in Example 1 except that the mixed liquid A obtained in Production Example 4 in Example 1 was changed to the mixed liquid C obtained in Production Example 6.

(Example 10)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was changed to N- (4-hydroxyphenyl) -methacrylamide in Example 1.

(Comparative Example 1)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was not added in Example 1.

(Comparative Example 2)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was changed to hexahydroxybenzophenone in Example 1.

(Comparative Example 3)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was changed to methyl gallate in Example 1.

(Comparative Example 4)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was changed to catechol in Example 1.

(Comparative Example 5)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was changed to 4-hydroxyacetophenone in Example 1.

(Comparative Example 6)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was changed to hydroxyethylacrylamide in Example 1.

(Comparative Example 7)
A conductive film was obtained in the same manner as in Example 1 except that 4-hydroxyphenylacetamide was changed to 2,4-dihydroxybenzamide in Example 1.

<Evaluation>
The conductive film of each Example and each Comparative Example was irradiated with ultraviolet light generated by a carbon arc for 48 hours using an ultraviolet fade meter. The surface resistance value of the conductive layer before and after the ultraviolet light irradiation was measured using a resistivity meter (Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Corporation). The measurement results are shown in Table 1. The smaller the degree of increase in surface resistance after irradiation with ultraviolet light (B / A in the table), the better the light resistance.
Moreover, scratch resistance was evaluated about the conductive layer of the conductive film in each Example and each comparative example. Specifically, the surface of the conductive layer was rubbed 10 times with steel wool to which a load of 1 kgf (98.1 kPa) was applied. Thereafter, the surface of the conductive layer was visually observed. The observation results are shown in Table 1.

In the conductive films of Examples 1 to 10 in which the conductive layer contains the substituent-containing aromatic compound defined in claim 1 of the present application, both the surface resistance value before irradiation with ultraviolet light and the surface resistance value after irradiation with ultraviolet light are both Was small and excellent in electrical conductivity. Further, the degree of increase in surface resistivity after irradiation with ultraviolet light was small, and the light resistance was excellent. Furthermore, the scratch resistance of the conductive layer was also excellent.
The conductive film of Comparative Example 1 in which the conductive layer did not contain a substituent-containing aromatic compound had low conductivity and light resistance.
The conductive films of Comparative Examples 2 to 7 in which the conductive layer contains a substituent-containing aromatic compound different from that defined in claim 1 of the present invention has a large increase in surface resistivity after irradiation with ultraviolet light, and light resistance. Was low. In Comparative Examples 2 to 5 containing hexahydroxybenzophenone, methyl gallate, catechol or 4-hydroxyacetophenone, the conductivity was also low. In Comparative Examples 2 to 4 and 7 containing hexahydroxybenzophenone, methyl gallate, catechol or 2,4-dihydroxybenzamide, the scratch resistance of the conductive layer was also low.
Examples 5 and 10 are comparative examples.

Claims (7)

A conductive complex comprising a polyanion having an anion group and a π-conjugated conductive polymer, a substituent-containing aromatic compound, an active energy ray-curable acrylic compound different from the substituent-containing aromatic compound, and a dispersion medium And containing
The substituent-containing aromatic compound is at least one selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula (4). A conductive polymer dispersion which is a seed .

(R ¹ in Formula (2) and Formula (4) is each a hydrogen atom or any monovalent substituent, and R ² in Formula (2) and Formula (4) is each an arbitrary divalent group. A substituent of
R ¹ in Formula (3) is a methyl group, an ethyl group, a propyl group, or a butyl group. )   The conductive polymer dispersion according to claim 1, wherein an amine compound or an epoxy compound is coordinated or added to the anion group of the polyanion, and the dispersion medium is an organic solvent. The conductive polymer dispersion according to claim 1 or 2 , wherein the compound represented by the formula (4) has a (meth) acryloyl group. The conductive polymer dispersion according to claim 3 , wherein the compound represented by the formula (4) is a compound represented by the following formula (6).

(R ² in Formula (6) is an arbitrary divalent substituent, and R ⁴ is a hydrogen atom or a methyl group.) The electrical conductivity according to any one of claims 1 to 3, wherein the substituent-containing aromatic compound is at least one selected from the group consisting of 4-hydroxyphenylacetamide , 4-hydroxyacetanilide, and 3-hydroxyacetanilide. Polymer dispersion. The conductive high polymer according to any one of claims 1 to 5 , wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene), and the polyanion is polystyrene sulfonic acid. Molecular dispersion. A conductive film comprising: a film substrate; and a conductive layer formed by curing the conductive polymer dispersion according to any one of claims 1 to 6 formed on at least one surface of the film substrate. .