WO2014065314A1

WO2014065314A1 - Organic solvent dispersoid for conductive polymer/polyanion complex, conductive composition containing said dispersoid, and conductive film obtained from said composition

Info

Publication number: WO2014065314A1
Application number: PCT/JP2013/078683
Authority: WO
Inventors: 実村田; 澤田　浩
Original assignee: 荒川化学工業株式会社
Priority date: 2012-10-23
Filing date: 2013-10-23
Publication date: 2014-05-01
Also published as: KR20150080524A; CN104755556A; CN104755556B; JP6131960B2; TW201420670A; JPWO2014065314A1; TWI636092B

Abstract

The purpose of the present invention is to provide a novel organic solvent dispersoid for a conductive polymer/polyanion complex with which a film having exceptional conductivity and minimal decline thereof over time can be formed on a variety of substrates when the dispersoid is used as an additive to a variety of coating agents. The invention comprises using an organic solvent dispersoid containing a conductive polymer/polyanion complex that comprises a polythiophene and a sulfoanion-group-containing polymer and has a prescribed structure, an amine compound having a prescribed structure, an alcohol-soluble compound having a prescribed structure, and an alcohol-containing organic solvent.

Description

Conductive polymer / polyanion complex organic solvent dispersion, conductive composition containing the organic solvent dispersion, and conductive film obtained from the conductive composition

The present invention relates to an organic solvent dispersion obtained by dispersing or dissolving a conductive polymer / polyanion complex comprising polythiophene and a sulfoanion group-containing polymer in an organic solvent, and a conductive composition comprising the organic solvent dispersion and a binder component. And a conductive film obtained from the conductive composition.

Polythiophene, a kind of π-conjugated conductive polymer, exhibits good electrical conductivity when doped with various anionic substances, so it can be applied to various industrial products (touch panels, capacitors, solar cells, etc.) as a conductive agent. Has been. In particular, a conductive polymer / polyanion complex obtained by doping poly (3,4-ethylenedioxythiophene) with a polymer containing a sulfoanion group such as polystyrene sulfonic acid has relatively stable conductivity, Therefore, it is also used as an additive for various antistatic coating agents and conductive coating agents.

By the way, such a conductive polymer / polyanion complex is often distributed as an aqueous dispersion or an aqueous solution. However, since most of the solvent is water, it is difficult to spread on a plastic substrate. The coating agent contained as an agent is generally difficult to apply to plastic substrates.

Therefore, in this field, there is a demand for an organic solvent dispersion liquid of a conductive polymer / polyanion complex. For example, in Japanese Patent Application Laid-Open No. 2004-86400, the applicant of the present invention describes a conductive polymer / polyanion complex in an organic solvent in the presence of polyoxyalkyleneamine. It has been proposed that an organic solvent dispersion can be obtained by dispersing in an organic solvent, which provides a film having good storage stability and excellent conductivity and antistatic properties. However, depending on the coating agent in which the dispersion is blended as an antistatic agent, it may be difficult to obtain a film having a small decrease in conductivity over time.

As a method for stabilizing the conductivity and antistatic property of the coating film containing the conductive polymer / polyanion complex over time, for example, a hydroxy group-containing compound such as alkyl gallate is added as a conductivity improver ( Patent Documents 2 and 3), antioxidants such as bisphenol antioxidants and phosphorus antioxidants are used (see Patent Document 4), and ultraviolet absorbers such as benzophenone compounds are used. However, the effect was not sufficient.

JP 2008-45116 A JP 2006-169494 A JP 2006-131873 A JP 2008-45116 A

When used as an additive for various coating agents, the present invention makes it possible to form a coating film on various substrates that is excellent in electrical conductivity and has a small decrease with time. The main object is to provide a polymer / polyanion complex organic solvent dispersion.

Another object of the present invention is to provide a novel conductive composition that is capable of forming a film having excellent conductivity on a variety of substrates and having a small decrease with time.

Another object of the present invention is to provide a film that is excellent in conductivity and has a small decrease with time.

As a result of diligent study, the present inventor has obtained an organic solvent dispersion obtained by dispersing or dissolving a conductive polymer / polyanion complex comprising a polythiophene and a sulfoanion group-containing polymer in an organic solvent in the presence of a predetermined amine compound. It has been found that an organic solvent dispersion capable of solving the above problems can be obtained by further adding a predetermined polycyclic compound.

Further, the present inventor has found that a conductive composition capable of solving the above-mentioned problems can be obtained by combining a predetermined binder component with the organic solvent dispersion.

Further, the present inventor has found that a conductive film capable of solving the above problems can be obtained by the conductive composition.

That is, the present invention relates to the following organic solvent dispersion, conductive composition and conductive film.

1. Conductive polymer / polyanion complex (A) comprising polythiophene (a1) and sulfoanion group-containing polymer (a2) having a structure represented by the following general formula (1), amine represented by the following general formula (2) An organic solvent dispersion containing the compound (B), an alcohol-soluble compound (C) among the compounds represented by the following general formula (3), and an organic solvent (D) containing the alcohol (d1).

(In the formula (1), A represents an alkylene group having 1 to 12 carbon atoms.)

(In Formula (2), X ¹ represents any of an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 3 to 40 carbon atoms, and an aralkyl group having 3 to 40 carbon atoms. Y represents oxyethylene, respectively. And any one of a group, an oxypropylene group, and an oxyethylene-oxypropylene group, and m represents an integer of 1 to 20.)

(In formula (3), the broken line portion represents a carbon-carbon single bond or a carbon-carbon double bond. X ₁ to X ₇ are all selected from the group consisting of hydrogen, a hydroxyl group and an alkoxy group. (However, at least two of X ₁ to X ₇ are hydroxyl groups.) Y represents a methylene group or a carbonyl group.)

2. (C) The organic solvent dispersion according to item 1, wherein the component is a compound represented by the following general formula (3-1).

(In the formula (3-1), a broken line part represents a carbon-carbon single bond or a carbon-carbon double bond, X ₁ represents a hydroxyl group or an alkoxy group, and any one of X ₃ , X ₄ and X ₅ represents (One is a hydroxyl group, and the other two are hydrogen or a hydroxyl group, respectively, and Y represents a methylene group or a carbonyl group.)

3. Conductive polymer / polyanion complex (A) comprising polythiophene (a1) and sulfoanion group-containing polymer (a2) having a structure represented by the following general formula (1), amine represented by the following general formula (2) Among the compounds represented by the compound (B) and the following general formula (3), an alcohol-soluble compound (C), an organic solvent (D) containing an alcohol (d1), an active energy ray radical polymerization compound ( α), an epoxy resin (β), and one binder component selected from the group consisting of an inactive energy ray radical polymerization acrylic copolymer (γ), and a conductive composition

4). (C) The conductive composition according to item 3, wherein the component is a compound represented by the following general formula (3-1).

5. The above-mentioned item, wherein the component (α) is a bifunctional to hexafunctional (meth) acrylate compound (α1) and / or a (meth) acrylic polymer (α2) having a free (meth) acryloyl group in the molecule. 3 or 4 conductive compositions.

6). Item 6. The conductive composition according to any one of Items 3 to 5, further comprising a photopolymerization initiator.

7). 7. A conductive film obtained by coating the conductive composition according to any one of items 3 to 6 on a substrate and irradiating with active energy rays.

8). (Β) The conductive composition according to item 3 or 4, wherein the component is at least one selected from the group consisting of an aromatic epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin.

9. Item 9. The conductive composition according to any one of Items 3, 4, and 8, wherein the alicyclic epoxy resin is an epoxy resin and / or a hydrogenated epoxy resin obtained by epoxidizing an alicyclic olefin.

10. Furthermore, the electroconductive composition in any one of said claim | item 3, 4, 8, 9 containing an epoxy-group reactive crosslinking agent.

11. Item 11. The conductive composition according to any one of Items 3, 4, and 8 to 10, further comprising a neutralizing agent.

12 Item 12. The conductive composition according to any one of Items 3, 4, and 8 to 11, further comprising a cationic polymerization catalyst.

13. 13. A conductive film obtained by applying the conductive composition according to any one of items 3, 4, and 8 to 12 to a base material and curing it by heating.

14 13. A conductive film obtained by applying the conductive composition according to any one of items 3, 4, and 8 to 12 to a substrate, and irradiating and curing the active energy ray.

15. The (γ) component is obtained by reacting an α, β unsaturated carboxylic acid (γ1), a (meth) acrylic acid alkyl ester (γ2) and, if necessary, a (meth) acrylic acid hydroxyalkyl ester (γ3). Item 5. The conductive composition according to Item 3 or 4, which is an acrylic copolymer.

16. Furthermore, the electroconductive composition in any one of said claim | item 3, 4, 15 containing a carboxyl group reactive crosslinking agent.

17. Furthermore, the electrically conductive composition in any one of said claim | item 3, 4, 15, 16 containing a neutralizing agent.

18. Item 18. A conductive film obtained by applying the conductive composition according to any one of Items 3, 4, 15 to 17 to a substrate.

The organic solvent dispersion of the present invention is excellent in storage stability, and by combining with various binder components, a conductive composition capable of forming a conductive film that is excellent in conductivity and has a small decrease with time. Can be provided.

In addition, the conductive composition of the present invention is excellent in storage stability, and is cured with active energy rays such as ultraviolet rays and electron beams, or heat, so that the conductivity is excellent, and the decrease width with time. Can be obtained. Therefore, the conductive composition is used as various conductive coating agents for various plastic films, electronic component carrier tapes, magnetic cards, magnetic tapes, magnetic disks, release film IC trays, organic EL, solar cells, and the like. Can do.

The conductive coating of the present invention is excellent in conductivity and has a small decrease with time. Therefore, the conductive coating is useful as a material for various plastic films, electronic component carrier tapes, magnetic cards, magnetic tapes, magnetic disks, release film IC trays, organic EL, solar cells, and the like.

The organic solvent dispersion of the present invention comprises a predetermined conductive polymer / polyanion complex (A) (hereinafter referred to as component (A)), a predetermined amine compound (B) (hereinafter referred to as component (B)), Among the compounds represented by the following general formula (3), alcohol-soluble compounds (C) (hereinafter referred to as (C) component) include alcohols (d1) (hereinafter referred to as (d1) component). It is a composition containing an organic solvent (D) (hereinafter referred to as component (D)), and takes a form in which component (A) is dispersed in component (D).

Component (A) is a substance that imparts conductivity to the conductive composition of the present invention. Polythiophene (a1) (hereinafter referred to as component (a1)) that is a conductive polymer and sulfoanion that is a dopant. Group-containing polymer (a2) (hereinafter referred to as component (a2)).

The component (a1) is a π-conjugated conductive polymer having a structure represented by the following general formula (1).

Specific examples of the component (a1) include poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butenedioxythiophene) and the like. It is done. Among these, poly (3,4-ethylenedioxythiophene) (hereinafter referred to as PEDOT) is particularly preferable from the viewpoint of conductivity.

In the present invention, as necessary, as the conductive polymer other than the component (a1), for example, polythiophenes other than the component (a1), polythiophene vinylenes, polypyrroles, polyfurans, polyanilines, and other π-conjugated systems A conductive polymer can be used in combination.

Examples of the polythiophene other than the component (a1) include poly (thiophene), alkoxy group-substituted poly (thiophene) s [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-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly ( 3,4-dihexyloxythiophene), poly (3,4-diheptyloxy) Offene), poly (3,4-dioctyloxythiophene), poly (3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene), poly (3-methyl-4-methoxythiophene), Poly (3-methyl-4-ethoxythiophene) and the like], alkyl group-substituted poly (thiophene) s [poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3 -Butylthiophene), poly (3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecyl) Thiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), etc.] Boxyl group-substituted poly (thiophene) s [poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4- Carboxybutylthiophene)], hydroxy group-substituted poly (thiophene) s [poly (3-hydroxythiophene), poly (3,4-dihydroxythiophene), etc.], phenyl group-substituted poly (thiophene) s [poly (3-phenyl) Thiophene), etc.], cyano group-substituted poly (thiophene) s [poly (3-cyanothiophene), etc.], halogen-substituted poly (thiophene) s [poly (3-bromothiophene), poly (3-chlorothiophene), poly ( 3-iodothiophene) and the like.

Examples of polythiophene vinylenes include poly (thiophene vinylene), alkylenedioxy group-substituted poly (thiophene) [poly (3,4-ethylenedioxythiophene vinylene), poly (3,4-propylene dioxythiophene vinylene) , Poly (3,4-butenedioxythiophene vinylene)], alkoxy group-substituted poly (thiophene vinylene) s [poly (3-methoxythiophene vinylene), poly (3-ethoxythiophene vinylene), poly (3-butoxythiophene] Vinylene), poly (3-hexyloxythiophene vinylene), poly (3-heptyloxythiophene vinylene), poly (3-octyloxythiophene vinylene), poly (3-decyloxythiophene vinylene), poly (3-dodecyloxythiophene) Vinyle ), Poly (3-octadecyloxythiophene vinylene), poly (3,4-dimethoxythiophene vinylene), poly (3,4-diethoxythiophene vinylene), poly (3,4-dipropoxythiophene vinylene), poly (3 , 4-dibutoxythiophene vinylene), poly (3,4-dihexyloxythiophene vinylene), poly (3,4-diheptyloxythiophene vinylene), poly (3,4-dioctyloxythiophene vinylene), poly (3,4 4-didecyloxythiophene vinylene), poly (3,4-didodecyloxythiophene vinylene), poly (3-methyl-4-methoxythiophene vinylene), poly (3-methyl-4-ethoxythiophene vinylene), etc.] Alkyl group-substituted poly (thiophene vinylene) s [poly (3-methyl Thiophene vinylene), poly (3-ethylthiophene vinylene), poly (3-propylthiophene vinylene), poly (3-butyl thiophene vinylene), poly (3-hexylthiophene vinylene), poly (3-heptylthiophene vinylene), poly (3-octylthiophene vinylene), poly (3-decylthiophene vinylene), poly (3-dodecylthiophene vinylene), poly (3-octadecylthiophene vinylene), poly (3,4-dimethylthiophene vinylene), poly (3 4-dibutylthiophene vinylene)], carboxyl group-substituted poly (thiophene vinylenes) [poly (3-carboxythiophene vinylene), poly (3-methyl-4-carboxythiophene vinylene), poly (3-methyl-4-carboxy) Ethylthiophene Nylene), poly (3-methyl-4-carboxybutylthiophenevinylene)], hydroxy group-substituted poly (thiophenevinylene) s [poly (3-hydroxythiophenevinylene), poly (3,4-dihydroxythiophenevinylene), etc.] , Phenyl group-substituted poly (thiophene) [poly (3-phenylthiophenvinylene), etc.], cyano group-substituted poly (thiophene) [poly (3-cyanothiophenevinylene), etc.], halogen-substituted poly (thiophene) [poly (3-bromothiophene vinylene), poly (3-chlorothiophene vinylene), poly (3-iodothiophene vinylene) and the like.

Examples of the polypyrrole include poly (pyrrole), alkoxy group-substituted poly (pyrrole) [poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyl). Oxypyrrole), poly (3-methyl-4-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), etc.], alkyl group-substituted poly (pyrrole) s [poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole, etc.), carboxyl group-substituted poly (pyrrole) s (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), etc.], hydroxy group substitution And poly (pyrrole) [poly (3-hydroxypyrrole) and the like].

Examples of the poly (furan) include poly (furan), alkoxy group-substituted poly (furan) [poly (3-methoxyfuran), poly (3-ethoxyfuran), poly (3-butoxyfuran), poly (3 -Hexyloxyfuran), poly (3-methyl-4-hexyloxyfuran), poly (3-methyl-4-hexyloxyfuran) and the like], alkyl group-substituted poly (furan) s [poly (3-methylfuran) Poly (3-ethylfuran), poly (3-n-propylfuran), poly (3-butylfuran), poly (3-octylfuran), poly (3-decylfuran), poly (3-dodecylfuran), Poly (3,4-dimethylfuran), poly (3,4-dibutylfuran, etc.)], carboxyl group-substituted poly (furan) s [poly (3-carboxyfuran), poly (3- Til-4-carboxyfuran), poly (3-methyl-4-carboxyethylfuran), poly (3-methyl-4-carboxybutylfuran), etc.], hydroxy-substituted poly (furan) s [poly (3-hydroxy Franc) etc.].

Examples of polyanilines include poly (aniline), poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid), and the like.

The component (a1) and other π-conjugated conductive polymers can be obtained by a known chemical oxidative polymerization method or electrolytic polymerization method. In the former case, a method of synthesizing a conductive polymer in a solution containing a precursor monomer, a dopant and an oxidizing agent is mentioned. In the latter case, a supporting electrode is included in the electrolytic solution containing the precursor monomer and the dopant. And a method of forming a conductive polymer thereon. In the polymerization, water or a component (D) described later may be used as a solvent.

As oxidizing agents, metal salt oxidizing agents (ferric chloride, ferric sulfate, ferric nitrate, cupric chloride, aluminum chloride, etc.), non-metal salt oxidizing agents (ammonium peroxodisulfate, peroxo) Sodium disulfate, potassium peroxodisulfate, boron trifluoride, ozone, benzoyl peroxide, oxygen, etc.).

The sulfoan anion group-containing polymer as the component (a2) is a doping component for the component (a1), and specifically, a homopolymer of a sulfonic acid polymerizable monomer, a sulfonic acid polymerizable monomer and a sulfo anion group. Various known materials such as a copolymer with a polymerizable monomer having no benzene can be used without particular limitation. The “sulfoanion group” means a sulfo group or a monosubstituted sulfoester group which is an anionic functional group. The “monosubstituted sulfoester group” refers to a group in which hydrogen on a hydroxyl group in the sulfoester group is substituted with an alkyl group (having about 1 to 20 carbon atoms).

Examples of sulfonic acid-based polymerizable monomers include vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, α-methyl styrene sulfonic acid, methallyloxybenzene sulfonic acid, allyloxybenzene sulfonic acid, 1,3-butadiene- 1-sulfonic acid, 1-methyl-1,3-butadiene-2-sulfonic acid, 1-methyl-1,3-butadiene-4-sulfonic acid, isoprenesulfonic acid, ethyl (meth) acrylate sulfonic acid (CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) ₂ —SO ₃ H), (meth) acrylic acid propylsulfonic acid (CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) ₃ —SO ₃ H) (Meth) acrylic acid-t-butylsulfonic acid (CH ₂ ═C (CH ₃ ) —COO—C (CH ₃ ) ₂ CH ₂ —SO ₃ H), A) Acrylic acid-n-butylsulfonic acid (CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) ₄ —SO ₃ H), (meth) acrylic acid phenylene sulfonic acid (CH ₂ ═C (CH ₃ )) —COO—C ₆ H ₄ —SO ₃ H), (meth) acrylic acid naphthalenesulfonic acid (CH ₂ ═C (CH ₃ ) —COO—C ₁₀ H ₈ —SO ₃ H), ethyl allyl sulfonic acid (CH ₂ = CHCH ₂ —COO— (CH ₂ ) ₂ —SO ₃ H), allyl acid-t-butylsulfonic acid (CH ₂ ═CHCH ₂ —COO—C (CH ₃ ) ₂ CH ₂ —SO ₃ H), 4 -Pentenoic acid ethylsulfonic acid (CH ₂ ═CH (CH ₂ ) ₂ —COO— (CH ₂ ) ₂ —SO ₃ H), 4-pentenoic acid propyl sulfonic acid (CH ₂ ═CH (CH ₂ ) ₂ —COO— (CH ₂ ) _3- SO ₃ H), 4-pentenoic acid-n-butylsulfonic acid (CH ₂ ═CH (CH ₂ ) ₂ —COO— (CH ₂ ) ₄ —SO ₃ H), 4-pentenoic acid-t— Butylsulfonic acid (CH ₂ ═CH (CH ₂ ) ₂ —COO—C (CH ₃ ) ₂ CH ₂ —SO ₃ H), 4-pentenoic acid phenylene sulfonic acid (CH ₂ ═CH (CH ₂ ) ₂ —COO— C ₆ H ₄ —SO ₃ H), 4-pentenoic acid naphthalenesulfonic acid (CH ₂ ═CH (CH ₂ ) ₂ —COO—C ₁₀ H ₈ —SO ₃ H), acrylamide-t-butylsulfonic acid, 2- Examples include acrylamide-2-methylpropanesulfonic acid, cyclobutene-3-sulfonic acid, and salts thereof (sodium salt and the like).

Examples of the polymerizable monomer having no sulfoanionic group include aromatic monomers [styrene, p-methylstyrene, p-ethylstyrene, p-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, α-methylstyrene, vinylphenol, 2-vinylnaphthalene, 6-methyl-2-vinylnaphthalene, etc.], non-alicyclic dienes [1,3-butadiene, 1-methyl-1,3-butadiene, 2-methyl- 1,3-butadiene, 1,4-dimethyl-1,3-butadiene, 1,2-dimethyl-1,3-butadiene, 1,3-dimethyl-1,3-butadiene, 1-octyl-1,3- Butadiene, 2-octyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1-hydroxy- , 3-butadiene, etc.], non-alicyclic monoenes [2-hydroxy-1,3-butadiene, ethylene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2 -Hexene, etc.], alicyclic monoenes (cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 2-methylcyclohexene, etc.), imidazole monomers (1-vinylimidazole, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, N-vinyl-2-pyrrolidone, N-vinylacetamide, N-vinylformamide, N-vinylimidazole, etc.], acrylamides ((meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N vinylform Muamide, 3-acrylamidophenylboronic acid, etc.], amine monomers [acryloylmorpholine, vinylamine, N, N-dimethylvinylamine, N, N-diethylvinylamine, N, N-dibutylvinylamine, N, N-di- t-butyl vinylamine, N, N-diphenylvinylamine, N-vinylcarbazole, etc.], other monomers [vinyl acetate, acrolein, methacrolein, acrylonitrile, vinyl alcohol, vinyl chloride, vinyl fluoride, methyl vinyl ether, ethyl vinyl ether Etc.].

As the component (a2), polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, and polyacrylic are preferable because they have good doping performance and contribute to the stability of the organic solvent dispersion of the component (A) described later. Acid ethyl sulfonic acid, polybutyl acrylate, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacrylic acid At least one selected from the group consisting of carboxylic acid, poly-2-acrylamido-2-methylpropanecarboxylic acid, polyisoprene carboxylic acid, polyacrylic acid, and salts thereof, in particular polystyrene sulfonic acid and / or its salt (Especially Nat Umushio) (hereinafter sometimes collectively referred to as PSS.) Are preferred.

The method of doping the component (a1) with the component (a2) is not particularly limited. For example, the component (a2) is added to the component (a1) and mixed by stirring by various known means, or the production of the component (a1) And a method of coexisting the component (a2) in the reaction system. The amount of component (a1) and component (a2) used is not particularly limited, but is usually about 0.5 to 5 parts by weight of component (a2) with respect to 1 part by weight of component (a1).

When the component (A) is prepared as an aqueous solution or aqueous dispersion, various known methods (Japanese Patent Application Laid-Open Nos. 2008-045116, 2008-156442, 2008-222850, and 2011) are used. -2081616 etc.) to obtain an organic solvent dispersion. Specifically, for example, when an aqueous solution or aqueous dispersion of PEDOT / PSS is used as the component (A), the PEDOT / PSS blue color is obtained by drying it with various known drying means (spray dryer or the like). A solid can be obtained and can be used as component (A).

As component (A), PEDOT and PSS are particularly preferable from the viewpoints of chemical stability as a conductive polymer / dopant complex, conductivity, and hue and transparency of a film made of the conductive composition of the present invention. A complex consisting of (hereinafter referred to as PEDOT / PSS) is preferred. As PEDOT / PSS, for example, commercially available products such as “Clevios P” (trade name; manufactured by Heraeus) and “Orgacon” (trade name; manufactured by Agfa Gebalto, Japan) can be used.

The component (B) is a compound represented by the following general formula (2) and acts as a dispersant for the component (A). By using the component (B), the storage stability of the organic solvent dispersion of the present invention is improved, and the storage stability is improved without impairing the conductivity of the conductive composition containing the component. You can also.

Examples of the compound represented by the general formula (2) include N, N-poly (oxyethylene) -hexylamine, N, N-poly (oxypropylene) -hexylamine, N, N-poly (oxyethylene Oxypropylene) -hexylamine, N, N-poly (oxyethylene) -decylamine, N, N-poly (oxypropylene) -decylamine, N, N-poly (oxyethylene oxypropylene) -decylamine, N, N- Poly (oxyethylene) -decylamine, N, N-poly (oxypropylene) -decylamine, N, N-poly (oxyethylene oxypropylene) -decylamine, N, N-poly (oxyethylene) -pentadecylamine, N , N-poly (oxypropylene) -pentadecylamine, N, N-poly (oxyethylene o Cypropylene) -pentadecylamine, N, N-poly (oxyethylene) -icosylamine, N, N-poly (oxypropylene) -icosylamine, N, N-poly (oxyethylene oxypropylene) -icosylamine, N, N -Poly (oxyethylene) -hexacosylamine, N, N-poly (oxypropylene) -hexacosylamine, N, N-poly (oxyethylene oxypropylene) -hexacosylamine, N, N-poly (oxyethylene) N, N-poly (oxyalkylene) -alkylamines such as N) N-poly (oxypropylene) -triacontylamine, N, N-poly (oxyethylene oxypropylene) -triacontylamine These may include two or more of them.

If necessary, amine-based dispersants other than component (B) such as secondary polyoxyalkyleneamines such as polyoxyethylene stearylamine and polyoxyethylene laurylamine, polyoxyethylene alkyl ether, polyoxyethylene styrylphenyl Non-amine nonionic surfactants such as ether and polyoxyethylene sorbitan fatty acid ester can be used in combination, and these may be used in combination of two or more.

Component (C) is an alcohol-soluble compound represented by the following general formula (3). Due to the action of the component (C), the conductivity of the film obtained from the conductive composition of the present invention is improved, and the decrease width with time is reduced.

In addition, examples of the alkoxy group in the formula (3) include those having an alkyl group such as a methoxy group, an ethoxy group, and a propoxy group having about 1 to 5 carbon atoms (the same applies hereinafter).

Further, as the component (C), from the viewpoint of the conductivity of the conductive film of the present invention, those in which 3 to 5 of X ₁ to X ₇ are hydroxyl groups are more preferable, and in particular, the following general formula (3-1) ) Is preferred. The latter compound is considered to capture transition metal ions (iron, copper, magnesium, etc.) derived from the component (A) in the organic solvent dispersion of the present invention, and as a result, the organic solvent dispersion was used. The temporal decrease in the conductivity of the film obtained from the conductive composition is reduced.

(In the formula (3-1), the broken line portion represents a carbon-carbon single bond or a carbon-carbon double bond. X ₁ represents a hydroxyl group or an alkoxy group. Further, X ₃ , X ₄ and X ₅ (One of them is a hydroxyl group, and the remaining two are hydrogen or a hydroxyl group, respectively, and Y represents a methylene group or a carbonyl group.)

Further, among the compounds represented by the formula (3-1), the compounds represented by the following formulas (3-2) to (3-4), particularly those represented by the following formula (3-2) are used. For example, the conductive coating film according to the present invention is preferable because the decrease in conductivity over time is further reduced.

(In formula (3-2), X ₁ represents a hydroxyl group or an alkoxy group.)

(In formula (3-3), X ₁ represents a hydroxyl group or an alkoxy group.)

(In the formula (3-4), X ₁ represents a hydroxyl group or an alkoxy group.)

In addition, among the compounds represented by the formula (3), an alcohol-soluble compound was used as the component (C) because the organic solvent dispersion of the present invention contains an alcohol ((d1) component) ((D This is because component) is used as a dispersion medium. Therefore, even if it is a compound represented by Formula (3) or a compound structurally similar to this, what is not alcohol-soluble is not included in (C) component. As such, for example, any one or two or more of X ₁ to X _{7 in} the formula (3) is a glycoside group (for example, —ORha (Rha represents a rhamnosyl residue), —ORu (Ru Is a group represented by a rutinosyl (β-lutinose) residue), but this has a strong hydrophilicity at the glycoside group and is difficult to dissolve in the component (D). It is difficult to achieve the desired effect.

In the present specification, “alcohol-soluble” means that the alcohol is soluble in an alcohol solvent (particularly ethanol) at room temperature, but is hardly soluble or insoluble in water. Specifically, when the compound is a 1% solution (25 ° C.) of a mixed solvent in which ethanol / water = 9/1 (weight ratio), the solution exhibits a transparent appearance without turbidity. When a 1% solution (25 ° C.) of a mixed solvent in which / water = 8/2 (weight ratio) is used, it means that insoluble matter or turbidity occurs in the solution.

Examples of the component (d1) constituting the component (D) include non-ether monoalcohol [methanol, ethanol, propanol, butanol, isopropyl alcohol, etc.], non-ether diol [ethylene glycol, neopentyl glycol, propylene glycol, 1 , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol, etc.], ether alcohols (dioxane, diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, propylene glycol monomethyl) Ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.), and the like. It may be combined. Among these, when a non-ether diol, particularly ethylene glycol is used, the conductivity of the conductive coating of the present invention is improved. The amount of the component (d1) in the component (D) is not particularly limited, but is usually about 95 to 99.5% by weight, preferably about 97 to 100% by weight, and more preferably 100% by weight.

Examples of the component (D) include solvents other than the component (d1) (hereinafter referred to as the component (d2)) such as ketones, alicyclic hydrocarbons, nitrogen-containing compound solvents, sulfur-containing compound solvents, and the like. Can be included. Specifically, acetone, methyl ethyl ketone, etc. as the ketones, benzene, toluene, xylene, etc. as the aromatic hydrocarbons, cyclohexane, methylcyclohexane, etc. as the alicyclic hydrocarbons, the ester Examples include ethyl formate and ethyl acetate, nitriles include acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, and the like, and nitrogen-containing compounds include N-methyl-2-pyrrolidone and 3 -Methyl-2-oxazolidinone, N, N-dimethylformamide, N, N-dimethylacetamide and the like, and examples of the sulfur-containing compound solvent include dimethyl sulfoxide, hexamethylene phosphortriamide, and the like. May be combined.

The organic solvent dispersion of the present invention is obtained by blending (A) component, (B) component and (C) component with (D) component, and dispersing and mixing them by various known means. In addition, the addition order of each component is not specifically limited. As the dispersing / mixing means, various known dispersing devices (emulsification dispersing device, ultrasonic dispersing device, etc.) can be used.

Further, the content of the component (A), the component (B), the component (C) and the component (D) in the organic solvent dispersion of the present invention is not particularly limited, but the storage stability of the organic solvent dispersion, In consideration of the storage stability of the conductive composition obtained using the organic solvent dispersion, the conductivity of the film obtained from the conductive composition and its stability over time, etc., the following is usually as follows: . (However, components other than the component (D) are in terms of solid content.)
Component (A): about 0.01 to 2% by weight, preferably 0.02 to 1% by weight
Component (B): about 0.01 to 2% by weight, preferably 0.02 to 1% by weight
Component (C): about 0.01 to 5% by weight, preferably 0.01 to 1% by weight
Component (D): about 95 to 99.5% by weight, preferably 97 to 99.95% by weight

The solid content concentration of the organic solvent dispersion of the present invention is not particularly limited, and may be appropriately determined according to its use. Usually, it is about 0.5 to 10% by weight, preferably about 3 to 8% by weight. is there.

The organic solvent dispersion is a non-aqueous composition using the organic solvent as a solvent. However, for example, when a commercially available PEDOT / PSS aqueous solution or aqueous dispersion is used as the component (A), water derived from this may be inevitably mixed. In this case, the water content in the organic solvent dispersion is usually in the range of 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, and substantially 0% by weight. %.

Further, the particle size of the component (A) in the organic solvent dispersion is not particularly limited, but usually the average primary particle size is about 10 to 500 nm, and considering the storage stability of the organic solvent dispersion, The thickness is preferably about 10 to 50 nm.

The conductive composition of the present invention comprises the component (A), the component (B), the component (C), the component (D), the active energy ray radical polymerization compound (α) (hereinafter referred to as the component (α). 1) selected from the group consisting of epoxy resin (β) (hereinafter referred to as (β) component) and inactive energy ray radical polymerization type acrylic copolymer (γ) (hereinafter referred to as (γ) component). It is a composition containing a seed binder component.

(In Formula (2), X ¹ represents any of an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 3 to 40 carbon atoms, and an aralkyl group having 3 to 40 carbon atoms. Y represents oxyethylene, respectively. Represents any one of a group, an oxypropylene group, and an oxyethylene-oxypropylene group, and m represents an integer of 1 to 20.)

(In the formula (3), the broken line portion represents a carbon-carbon single bond or a carbon-carbon double bond. X ₁ to X ₇ are all selected from the group consisting of hydrogen, hydroxyl group and alkoxy group. (However, at least two of X ₁ to X ₇ are hydroxyl groups.) Y represents a methylene group or a carbonyl group.)

The conductive composition according to the first aspect of the present invention uses the component (α) as a binder component. In addition, the (A) component, (B) component, and (C) component (D) component which are contained in the said composition are respectively the same as what was mentioned above.

As the (α) component, various known compounds can be used without particular limitation as long as they are radically polymerized by active energy rays such as ultraviolet rays and electron beams to form a cured film. Specifically, a bifunctional to hexafunctional (meth) acrylate compound (α1) (hereinafter referred to as (α1) component) and / or (meth) acrylic polymerization having a free (meth) acryloyl group in the molecule. The product (α2) (hereinafter referred to as the (α2) component) is preferable.

Examples of the (α1) component include bifunctional (meth) acrylate compounds [hexamethylene glycol diacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol] Di (meth) acrylate, hexaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-f Sundiol di (meth) acrylate, 2,2′-bis (4-acryloxydiethoxyphenyl) propane, 1,9-nonanediol di (meth) acrylate, bisphenol A tetraethylene glycol diacrylate, etc.], trifunctional (meth) Acrylate compounds (trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, ethylene oxide modified glycerol triacrylate, propylene oxide modified glycerol triacrylate, epsilon caprolactone modified trimethylolpropane triacrylate, pentaerythritol triacrylate, etc.), Tetrafunctional (meth) acrylate compounds [ditrimethylolpropane tetraacrylate, pentaerythritol ethoxytetraacrylate, Taerythritol tetraacrylate], (meth) acrylate compounds having five or more functional groups (dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polypentaerythritol polyacrylate, etc.) and the like. These may be used alone or in combination. A combination of more than one species can be used. *

In addition, as the (α1) component, various modified polyfunctional (meth) acrylate compounds such as polyurethane polyacrylate, polyester polyacrylate, epoxy polyacrylate, and the like can be used.

As the polyurethane acrylate, an isocyanate group-terminated prepolymer obtained by urethanation reaction of various known polyols and polyisocyanates, and further an acrylate oligomer obtained by urethanation of a hydroxyl group-containing (meth) acrylate, a polyol, Examples include acrylate oligomers obtained by reacting isocyanate group-terminated prepolymers.

Examples of the polyol include high molecular weight polyols such as polyester polyol, polyalkylene glycol, and polycarbonate polyol, and these may be used in combination of two or more.

Examples of the polyester polyol include polycondensates (polyester diols) of various known dicarboxylic acids and low molecular diols. Examples of the dicarboxylic acids include succinic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and itacone. Examples include acids, mesaconic acid, citraconic acid, muconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and acid anhydrides thereof. Examples of the low-molecular diol include ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, , 5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1,4-cyclohexanediol, 2-ethyl-2-butylpropanediol, etc. It is done. Two or more of these may be combined.

In addition, examples of the polyester polyol include polyaddition products (polyester diol) obtained by ring-opening reaction of various known lactones using the low molecular diol as an initiator. Examples of the lactones include γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Two or more of these may be combined.

Examples of the polyalkylene glycol include polyalkylene diols such as various known polyethylene glycols, polypropylene glycols, and poly (ethylene / propylene) glycols, and these may be used in combination of two or more.

Examples of the polycarbonate polyol include a condensation reaction product of one low molecular weight carbonate compound selected from the group consisting of dimethyl carbonate, diphenyl carbonate, ethylene carbonate and the like and the low molecular diol.

Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, diphenylmethane-4,4-diisocyanate, 3-methyl-diphenylmethane diisocyanate, or 1,5-naphthalene diisocyanate. Aromatic diisocyanate compounds such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and the like; and dimers and hexamers thereof. These may be used in combination of two or more.

Examples of the hydroxyl group-containing mono (meth) acrylate compound include 1-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy (meth) acrylate. Butyl, 4-hydroxybutyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl 2-hydroxypropionate, (meta ) Hydroxyphenyl acrylate and the like, and two or more of these may be combined.

Examples of the isocyanate group-containing mono (meth) acrylate compound include 2-isocyanatoethyl (meth) acrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, and these may be used in combination of two or more. .

As the polyester polyacrylate, a hydroxyl-terminated polyester obtained by esterifying the dicarboxylic acid and a low molecular diol, and an acrylate oligomer obtained by esterifying a carboxyl group-containing mono (meth) acrylate compound, Examples include acrylate oligomers obtained by esterifying the hydroxyl group-containing mono (meth) acrylate compound with a carboxyl group-terminated polyester obtained by reacting the dicarboxylic acid with a diol compound.

Examples of the carboxyl group-containing mono (meth) acrylate compound include acrylic acid, methacrylic acid, itaconic acid, (anhydrous) maleic acid, fumaric acid, and crotonic acid. These may be used in combination of two or more. .

Examples of the epoxy polyacrylate include acrylate oligomers obtained by addition reaction of the carboxyl group-containing mono (meth) acrylate compound to an epoxy resin (compound) having at least two epoxy groups in one molecule.

Examples of the epoxy resin (compound) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolac type epoxy resin, and naphthalenediol. Type epoxy resin, phenol dicyclopentadiene novolak type epoxy resin and hydrides thereof; 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-epoxy-vinylcyclohexene, bis (3 4-epoxycyclohexylmethyl) adipate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2: 8,9 diepoxy limonene, 3,4-epoxycyclohexylme 1,2-epoxy-4- (2-oxiranyl) cyclosexane adduct of diol, dicyclopentadiene diepoxide, 2,2-bis (hydroxymethyl) -1-butanol (manufactured by Daicel Chemical Industries, Ltd., trade name) And an alicyclic epoxy resin such as “EHPE-3150”), which may be used in combination of two or more. Among the alicyclic epoxy resins, those of the oligomer type include, for example, epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-caprolactone (for example, trade name “manufactured by Daicel Chemical Industries, Ltd.”) Examples include epoxy resins obtained by epoxidizing alicyclic olefins such as Epolide GT401 ").

The (α2) component is not particularly limited as long as it is a (meth) acrylic polymer having a free (meth) acryloyl group in the molecule (hereinafter referred to as a (meth) acrylic polymer). Can be used. The “(meth) acrylic polymer” means a (meth) acrylic homopolymer and / or a (meth) acrylic copolymer. Specific examples of the component (α2) include at least one selected from the group consisting of the following components (α2-1) to (α2-4).

(Α2-1) component: (meth) acrylic polymer having an alkyl ester group and an epoxy group in the side chain and / or (meth) acrylic polymer having an epoxy group in the side chain and no alkyl ester group (Hereinafter referred to as (α2-1 ′) component) and the above-mentioned carboxyl group-containing mono (meth) acrylate compound, an acrylic polymer having a free (meth) acryloyl group and a hydroxyl group in the molecule .

(Α2-2) component: (meth) acrylic polymer having an alkyl ester group and a carboxyl group in the side chain and / or (meth) acrylic polymer having a carboxyl group in the side chain and no alkyl ester group (Hereinafter referred to as the (α2-2 ′) component) and the epoxy group-containing mono (meth) acrylate compound, which is an esterification reaction product, an acrylic polymerization having a free (meth) acryloyl group and a hydroxyl group in the molecule object.

(Α2-3) component: (meth) acrylic polymer having an alkyl ester group and an isocyanate group in the side chain and / or (meth) acrylic polymer having an isocyanate group in the side chain and no alkyl ester group (Meth) acrylic having a urethane bond and a free (meth) acryloyl group in the molecule, which is a urethanization reaction product of the hydroxyl group-containing mono (meth) acrylate (hereinafter referred to as (α2-3 ′) component) Polymer.

(Α2-4) component: (meth) acrylic polymer having an alkyl ester group and a hydroxyl group and a carboxyl group in the side chain, and / or (meth) acrylic having a hydroxyl group in the side chain and no alkyl ester group This is a urethanization reaction product of a polymer (hereinafter referred to as (α2-4 ′) component) and the above-mentioned isocyanate group-containing mono (meth) acrylate, and has a urethane bond and a free (meth) acryloyl group in the molecule. (Meth) acrylic polymer.

Examples of the (α2-1 ′) component that is a precursor polymer of the (α2-1) component include, for example, a homopolymer obtained only from the epoxy group-containing mono (meth) acrylate compound, and the epoxy group-containing mono ( A binary copolymer obtained from a (meth) acrylate compound and an alkyl ester group-containing mono (meth) acrylate compound, a ternary copolymer further comprising another monomer in the homopolymer or binary copolymer Etc.

Examples of the alkyl ester group-containing mono (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylic. A rate, isobonyl (meth) acrylate, etc. are mentioned, These may combine 2 or more types.

Examples of the other monomers include the hydroxyl group-containing mono (meth) acrylate compounds, amide monomers [(meth) acrylamide, N-methylol (meth) acrylamide, N, N′-dimethyl (meth) acrylamide, N-vinyl]. Formamide, etc.], succinimide monomers [N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide], ultraviolet absorption unit Containing mono (meth) acrylate [2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methacrylic) Roxyethylfe ) -2H-benzotriazole, 2- [2 ′-(meth) acryloyloxy-5′-methylphenyl] benzotriazole, 2- [2 ′-(meth) acryloyloxy-5′-t-octylphenyl] benzo Triazole, 2- [2 ′-(meth) acryloyloxy-3 ′, 5′-di-t-butylphenyl] benzotriazole, 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone, 2-hydroxy-4- ( Acryloyloxyethoxy) benzophenone, 2-hydroxy-4-methacryloyloxymethylaminobenzophenone, 2-hydroxy-4- (methacryloyloxymethoxy) benzophenone, 2-hydroxy-4-methacryloyloxymethylthiobenzophenone, 2- (meth) acryloyloxy 4-methoxybenzophenone, 2- (meth) acryloyloxy-2'-hydroxy-4-methoxybenzophenone, 2,2'-di (meth) acryloyloxy-4-methoxybenzophenone, 2,2'-di (meth) acryloyl Oxy-4,4′-dimethoxybenzophenone, 2- (meth) acryloyloxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, Benzophenone compounds such as 2,2′-dihydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone; 2- (4,6-diphenyl-1,2,5-triazin-2-yl) -5- (methacryloyloxyethoxy) -phenol, etc. ], Vinyl acetate, N-vinylpyrrolidone, N-vinylcarboxylic amides, styrene, N-vinylcaprolactam, (meth) acrylonitrile and the like.

In the binary copolymer, the weight ratio of the alkyl ester group-containing mono (meth) acrylate compound and the epoxy group-containing mono (meth) acrylate compound, or the weight weight of the epoxy group-containing mono (meth) acrylate compound and other monomers The ratio is not particularly limited, but is usually in the range of about 1:99 to 95: 5 in order. In the case of the terpolymer, the amount of the other monomer used is usually 1 to the total weight of the alkyl ester group-containing mono (meth) acrylate compound and the epoxy group-containing mono (meth) acrylate compound. The range is about 95%.

The production conditions for the (α2-1 ′) component are not particularly limited, and various known polymerization reactions can be employed. Specifically, it can be obtained, for example, by subjecting the raw material monomer to a (co) polymerization reaction at a temperature of usually about 40 to 150 ° C. for about 2 to 12 hours in the presence of various known radical polymerization initiators. In the polymerization reaction, hydrogen peroxide, ammonium persulfate, potassium persulfate, benzoyl peroxide, dicumyl peroxide, lauryl peroxide 2,2′-azobisisobutyronitrile, dimethyl-2,2′-azo Radical polymerization initiators such as bisisobutyrate, chain transfer agents such as lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane, and the component (D) (organic solvent) can be used.

The addition reaction between the obtained (α2-1 ′) component and the carboxyl group-containing mono (meth) acrylate compound is usually performed at a temperature of about 80 to 120 ° C. in the absence of a solvent or in the presence of an organic solvent that does not react with both components. Just do it. The amount of both components used is not particularly limited, but usually the amount of the carboxyl group-containing mono (meth) acrylate compound used is 1.0 to 1.1 mol per mol of the epoxy group in the (α2-1 ′) component. It is a range which becomes a grade. In addition, a polymerization inhibitor such as methoquinone, hydroquinone, trimethylhydroquinone, N-nitrosophenylhydroxylamine or the like can be used in the addition reaction, or the reaction system can be bubbled with air.

The physical properties of the (α2-1) component thus obtained are not particularly limited, but the weight average molecular weight (referred to polystyrene conversion by gel permeation chromatography, hereinafter the same) is usually about 3,000 to 50,000. .

Examples of the (α2-2 ′) component which is a precursor polymer of the (α2-2) component include, for example, a homopolymer obtained only from the carboxyl group-containing mono (meth) acrylate compound, and the carboxyl group-containing mono ( A ternary copolymer obtained from a (meth) acrylate compound and the above-mentioned mono (meth) acrylate compound containing an alkyl ester group, a ternary having the other monomer as a further constituent component in the homopolymer or binary copolymer A copolymer etc. are mentioned.

In the binary copolymer, the weight ratio of the alkyl ester group-containing mono (meth) acrylate compound to the carboxyl group-containing mono (meth) acrylate compound, or the use of the carboxyl group-containing mono (meth) acrylate compound and other monomers. The weight ratio is not particularly limited, but is usually in the range of about 1:99 to 95: 5 in order. In the case of the terpolymer, the amount of the other monomer used is usually 1 to the total weight of the alkyl ester group-containing mono (meth) acrylate compound and the carboxyl group-containing mono (meth) acrylate compound. The range is about 95%.

The production conditions of the (α2-2 ′) component are not particularly limited, and may be the same as those of the (α2-1 ′) component. The conditions for the addition reaction of the obtained (α2-2 ′) component and the epoxy group-containing mono (meth) acrylate compound were the reaction of the aforementioned (α2-1 ′) component and the carboxyl group-containing mono (meth) acrylate compound. It is the same as conditions. Further, the amount of the epoxy group-containing mono (meth) acrylate compound used per mole of the carboxyl group in the component (α2-2 ′) is not particularly limited, but is usually in the range of about 0.9 to 1.0 mole. The physical properties of the (α2-2) component thus obtained are not particularly limited, and the weight average molecular weight is usually about 3,000 to 50,000.

Examples of the (α2-3 ′) component, which is a precursor polymer of the (α2-3) component, include homopolymers obtained only from the isocyanate group-containing mono (meth) acrylate compound, and the isocyanate group-containing mono ( Binary copolymers obtained from a meth) acrylate compound and an alkyl ester group-containing mono (meth) acrylate compound, and other monomers in the homopolymer or binary copolymer (provided that the hydroxyl group-containing mono (meth) acrylate) And terpolymers, etc., whose constituents are excluded.

In the binary copolymer, the weight ratio of the alkyl ester group-containing mono (meth) acrylate compound and the isocyanate group-containing mono (meth) acrylate compound, or the weight of the isocyanate group-containing mono (meth) acrylate compound and other monomers. The ratio is not particularly limited, but is usually in the range of about 1:99 to 95: 5 in order. In the case of the terpolymer, the amount of the other monomer used is usually 1 to the total weight of the alkyl ester group-containing mono (meth) acrylate compound and the isocyanate group-containing mono (meth) acrylate compound. The range is about 95%.

The reaction (urethane reaction) of the (α2-3 ′) component and the hydroxyl group-containing mono (meth) acrylate is usually carried out at about 60 to 120 ° C. in the absence of a solvent or in the presence of an organic solvent that does not react with both components. do it. Also, the amount of both components used is not particularly limited, but the amount of the hydroxyl group-containing mono (meth) acrylate compound is usually about 1.0 to 1.1 moles per mole of the isocyanate group in the (α2-3 ′) component. This is the range. In the urethanization reaction, various well-known urethanization catalysts such as organometallic catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, and bismuth octylate, and amine catalysts such as organic amines such as triethylamine and triethylenediamine and their salts, etc. Can be used together.

The physical properties of the (α2-3) component thus obtained are not particularly limited, but the weight average molecular weight is usually about 3,000 to 50,000.

Examples of the (α2-4 ′) component which is a precursor polymer of the (α2-4) component include, for example, a homopolymer obtained only from the hydroxyl group-containing mono (meth) acrylate compound, and the hydroxyl group-containing mono (meth) A binary copolymer obtained from an acrylate compound and an alkyl ester group-containing mono (meth) acrylate compound, a homopolymer or a binary copolymer, and other monomers (however, the isocyanate group-containing mono (meth) acrylate compound) And the like, and terpolymers having the above-mentioned carboxyl group-containing mono (meth) acrylate compound and epoxy group-containing mono (meth) acrylate compound) as constituent components.

In the binary copolymer, the weight ratio of the alkyl ester group-containing mono (meth) acrylate compound and the hydroxyl group-containing mono (meth) acrylate compound, or the weight ratio of the hydroxyl group-containing mono (meth) acrylate compound and the other monomer is Although not particularly limited, it is usually in the range of about 1:99 to 90:10 in order. In the case of the terpolymer, the amount of the other monomer used is usually 1 with respect to a total of 100 mol% of the alkyl ester group-containing mono (meth) acrylate compound and the hydroxyl group-containing mono (meth) acrylate compound. It is in the range of about ~ 95 mol%.

The reaction (urethanization reaction) between the (α2-4 ′) component and the isocyanate-containing mono (meth) acrylate is the same as the reaction between the (α2-3 ′) component and the hydroxyl group-containing mono (meth) acrylate. Further, the amount of the epoxy group-containing mono (meth) acrylate compound used per 1 mol of the hydroxyl group in the (α2-4 ′) component is not particularly limited, but is usually in the range of about 0.9 to 1.0 mol. The physical properties of the (α2-4) component thus obtained are not particularly limited, but the weight average molecular weight is usually about 3,000 to 50,000.

Note that the conductive composition of the present invention containing the component (α) can further contain a photopolymerization initiator. Specifically, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphos Fin oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, etc. These may be used alone or in combination of two or more, of them.

The method for preparing the conductive composition of the first aspect is not particularly limited, and the organic solvent dispersion of the present invention and the component (α) may be dispersed and mixed by various known means. In addition, the component (A), the component (B), the component (C) and the component (α) and the photopolymerization initiator used as necessary are blended in the component (D), and dispersed and mixed by various known means. It may be made. In the latter case, the order of adding the solute components is not particularly limited. Moreover, it can be said that the electroconductive composition obtained by the latter method contains the organic-solvent dispersion of this invention as a result.

The content of the component (A), the component (B), the component (C), the component (α) and the photopolymerization initiator in the conductive composition is not particularly limited, and may be set as appropriate according to the application. Usually it is as follows. (However, the total of all components does not exceed 100% by weight. In addition, components other than the component (D) are in terms of solid content.))

Component (A): about 0.01 to 2% by weight, preferably 0.02 to 1.5% by weight
Component (B): about 0.01 to 2% by weight, preferably 0.02 to 1.5% by weight
Component (C): about 0.01 to 10% by weight, preferably 0.01 to 5% by weight
Component (D): about 70 to 99.95% by weight, preferably 80 to 99.5% by weight
Component (α): about 0.01 to 29.95% by weight, preferably 0.02 to 29% by weight
Photopolymerization initiator: about 0.01 to 3% by weight, preferably 0.02 to 2% by weight

The conductive composition according to the second aspect of the present invention uses the (β) component as a binder component. In addition, the (A) component, (B) component, and (C) component (D) component which are contained in the said composition are respectively the same as what was mentioned above.

As the (β) component, various known ones can be used without particular limitation as long as they are epoxy resins (compounds) having at least two epoxy groups in the molecule. Specific examples include at least one selected from the group consisting of an aromatic epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin. Among these, alicyclic epoxy resins are preferable because they are excellent in both hardness and transparency of the cured film.

Examples of the aromatic epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin; Triphenolalkane type epoxy resins such as epoxy resins and triphenolpropane type epoxy resins; phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, stilbene type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, cyclopentadiene type epoxy resins Etc., and two or more of them may be combined.

As the alicyclic epoxy resin, specifically, for example, an epoxy resin and / or a hydrogenated epoxy resin obtained by epoxidizing an alicyclic olefin is preferable. Examples of the former include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-epoxy-vinylcyclohexene, bis (3,4-epoxycyclohexylmethyl) adipate, 1-epoxyethyl 1,3,4 of 1,4-epoxycyclohexane, 1,2: 8,9 diepoxy limonene, 3,4-epoxycyclohexyl methanol, dicyclopentadiene diepoxide, 2,2-bis (hydroxymethyl) -1-butanol -Epoxy-4- (2-oxiranyl) cyclosexane adduct (for example, “EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.), oligomeric alicyclic epoxy resin (epoxidized butanetetracarboxylic acid tetrakis- ( 3-cyclohexenylmethyl) -modified ε-cap Lactone (for example, trade name “Epolide GT401” manufactured by Daicel Chemical Industries, Ltd.) may be used, or a combination of two or more types may be used, and as the hydrogenated epoxy resin, the aromatic epoxy resin may be hydrotreated. Similarly, two or more of them may be combined.

Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols. Examples of the polyhydric alcohols include 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, cyclohexane. Examples include dimethanol, hydrogenated bisphenol, and polyalkylene glycols having an alkylene glycol structure. Examples of the polyalkylene glycols include polyethylene glycol, polypropylene glycol, polybutylene glycol and the like. Other aliphatic epoxy resins include polybutadiene diglycidyl ether, epoxidized oil (for example, “Adeka Sizer O-130P” (epoxidized soybean oil), “Adeka Sizer O-180A” (epoxidized linseed oil) ), Dimer acid glycidyl ester (“Epototo YD-171”, “Epototo YD-172”, both manufactured by Toto Kasei Co., Ltd.) and the like.

The conductive composition of the second aspect may further contain an epoxy group reactive crosslinking agent. This is a component used for imparting hardness to the resulting conductive film when the conductive composition is thermally cured, and various known ones as long as it is a crosslinking agent that easily reacts with an epoxy group, for example, Examples of the acid anhydride crosslinking agent, imidazole crosslinking agent, amine crosslinking agent, and polymercaptan crosslinking agent.

The acid anhydride crosslinking agent is not particularly limited as long as it is an anhydride of a carboxylic acid having at least two carboxyl groups in one molecule, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride Aromatic carboxylic anhydrides such as, maleic anhydride, aliphatic carboxylic anhydrides such as glutaric anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Examples thereof include alicyclic carboxylic acid anhydrides such as methyl nadic acid and anhydrous nadic acid. Moreover, you may combine these 2 or more types. Of these, hexahydrophthalic anhydride and / or methylhexahydrophthalic anhydride are preferred because the cured coating is unlikely to turn yellow.

Examples of the imidazole-based crosslinking agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, epoxy imidazole adduct, and the like. Can be combined.

Examples of the amine-based crosslinking agent include polyamines such as diethyleneamine, triethylenetetramine, dipropylenediamine, diethylaminopropylamine, N-aminoethylpiverazine, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Two or more types can be combined.

The conductive composition may further contain a neutralizing agent. By including the neutralizing agent, the cross-linking agent is hardly consumed by the component (a2) which is a strong acid substance, and a high-hardness film can be obtained. Specific examples of the neutralizing agent include ammonia, primary alkyl monoamines [methylamine, ethylamine, propylamine, butylamine, oleylamine, cyclohexylamine, etc.], secondary alkyl monoamines [dimethylamine, Diethylamine, dipropylamine, dibutylamine, dicyclohexylamine, etc.), tertiary alkyl monoamines [trimethylamine, triethylamine, tripropylamine, tributylamine, tricyclohexylamine, etc.] and the like. Also good. Among these, tertiary alkyl monoamines and / or ammonia are preferable.

In addition, when the conductive composition is cured with active energy rays, a cationic polymerization catalyst may be further included. Specifically, for example, specifically, for example, diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, iodonium tetrakis (pentafluorophenyl) borate, boron tetrafluoride phenyldiazonium salt, arsenic hexafluoride tri- Examples include 4-methylphenylsulfonium salt, antimony tetrafluoride tri-4-methylphenylsulfonium salt, diphenyliodonium salt of phosphorus hexafluoride, and antimony diphenyliodonium salt of hexafluoride. it can.

The method for preparing the conductive composition is not particularly limited, and examples thereof include a method of mixing and dispersing the organic solvent dispersion of the present invention and the component (β) by various known means. In addition, the (A) component, the (B) component, the (C) component, the (β) component, and the optional components (crosslinking agent, neutralizing agent, cationic polymerization catalyst) are used as the (D) component in various known means. Can be mixed and dispersed. The order of adding each solute component is not particularly limited. Moreover, it can be said that the electroconductive composition obtained by the latter method contains the organic-solvent dispersion of this invention as a result.

The content of each component in the conductive composition of the present invention is not particularly limited, and may be appropriately set according to the use, but is usually as follows. (However, the total of all components does not exceed 100% by weight. In addition, components other than the component (D) are converted to solid content.)

<When thermosetting the conductive composition>
Component (A): about 0.01 to 2% by weight, preferably 0.02 to 1% by weight
Component (B): about 0.01 to 2% by weight, preferably 0.02 to 1% by weight
Component (C): about 0.01 to 5% by weight, preferably 0.01 to 1% by weight
Component (D): about 95 to 99.5% by weight, preferably 97 to 99.95% by weight
(Β) component: about 0.01 to 2% by weight, preferably 0.05 to 0.5% by weight
Epoxy group-reactive crosslinking agent: about 0 to 2% by weight, preferably 0.01 to 1.0% by weight
Neutralizing agent: 0 to 0.1% by weight, preferably 0.005 to 0.03% by weight

<When curing the conductive composition with active energy rays>
Component (A): about 0.01 to 2% by weight, preferably 0.02 to 1% by weight
Component (B): about 0.01 to 2% by weight, preferably 0.02 to 1% by weight
Component (C): about 0.01 to 5% by weight, preferably 0.01 to 1% by weight
Component (D): about 95 to 99.5% by weight, preferably 97 to 99.95% by weight
(Β) component: about 0.01 to 2% by weight, preferably 0.05 to 0.5% by weight
Neutralizing agent: 0 to 0.1% by weight, preferably 0.005 to 0.03% by weight
Cationic polymerization catalyst: about 0.005 to 0.25% by weight, preferably 0.05 to 0.2% by weight

The conductive composition according to the third aspect of the present invention uses the (γ) component as a binder component. In addition, the (A) component, (B) component, and (C) component (D) component which are contained in the said composition are respectively the same as what was mentioned above.

The (γ) component is called α, β unsaturated carboxylic acid (γ1) (hereinafter referred to as (γ1) component) and (meth) acrylic acid alkyl ester (γ2) (hereinafter referred to as (γ2) component, (γ3) And a copolymer obtained by reacting (meth) acrylic acid hydroxyalkyl ester (γ3) (hereinafter referred to as (γ3) component), if necessary (γ) The component (A) improves the dispersibility of the component (A) in the conductive composition, and a film having excellent smoothness can be obtained.

Examples of the component (γ1) include α, β unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and α, β-unsaturated materials such as maleic acid, maleic anhydride, fumaric acid, and itaconic acid. A dicarboxylic acid is mentioned, These may combine 2 or more types. Of these, α and β unsaturated monocarboxylic acids are preferable from the viewpoint of reactivity, and acrylic acid and / or methacrylic acid are particularly preferable. *

Examples of the component (γ2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and acrylic acid. t-butyl, isooctyl (meth) acrylate, isononylbutyl (meth) acrylate, lauryl (meth) acrylate, allyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, (meth ) Cyclohexyl acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, (meth) acrylic acid Ethoxyethyl, methoxybutyl (meth) acrylate, and these It may be a combination of two or more. Further, as the (γ2) component, those having an alkyl group having about 1 to 20 carbon atoms (but not including a hydroxyl group) are particularly preferred.

(Γ3) component includes 1-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) 4-hydroxybutyl acrylate, hydroxycyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl 2-hydroxypropionate, hydroxyphenyl (meth) acrylate Etc., and two or more of these may be combined.

The (γ) component can be obtained by various known methods. Specifically, for example, the (γ1) component and the (γ2) component and, if necessary, the (γ3) component are usually subjected to radical polymerization reaction (aqueous solution polymerization, solution at about 60 to 180 ° C. for about 1 to 20 hours. Polymerization, bulk polymerization, etc.). The amount of the (γ1) component, the (γ2) component, and the (γ3) component is not particularly limited, but is usually about 5 to 90% by weight, about 10 to 90% by weight, and about 0 to 50% by weight. They are preferably about 10 to 70% by weight, about 10 to 70% by weight, and about 0 to 30% by weight. As the reaction solvent, water such as deionized water or the component (D) (propylene glycol monomethyl ether or the like) can be used.

In the radical polymerization, as an initiator, inorganic peroxides such as hydrogen peroxide, ammonium persulfate and potassium persulfate, and organic peroxides such as t-butyl peroxybenzoate, dicumyl peroxide, and lauryl peroxide are used. Oxides, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, azo compounds such as dimethyl-2,2′-azobisisobutyrate are used it can. The amount used is not particularly limited, but is usually about 0.01 to 10% by weight when the total of the (γ1) component, (γ2) component and (γ3) component is 100% by weight.

Also, a chain transfer agent such as dodecyl mercaptan, 2-mercaptobenzothiazole or bromotrichloromethane can be used for the purpose of adjusting the molecular weight of the component (γ). The amount used is not particularly limited, but is usually about 0.01 to 10% by weight when the total of the (γ1), (γ2) and (γ3) components is 100% by weight.

The physical properties of the component (γ) thus obtained are not particularly limited. Usually, the glass transition temperature (JIS-K-7121-1987) is about 20 to 300 ° C. (preferably about 40 to 250 ° C.), and the acid value (JIS- K2501-2003) is about 1 to 150 mgKOH / g (preferably 5 to 120 mgKOH / g), and the number average molecular weight (polystyrene conversion value by gel permeation chromatography) is about 1,000 to 500,000 (preferably 3,000). ~ About 25,000).

In addition, a carboxyl group-reactive crosslinking agent can be included in the conductive composition of the third aspect as necessary for the purpose of increasing the hardness of the film obtained from the composition. Specifically, for example, an oxazoline crosslinking agent, an aziridine crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, an isocyanate crosslinking agent, and the like can be given.

Examples of the oxazoline-based crosslinking agent include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, A component containing a vinyl monomer containing an oxazoline group such as 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline alone, or a vinyl monomer containing an oxazoline group and others And vinyl resins or acrylic resins copolymerized with these monomers. As commercially available products, EPOCROSS WS-300, WS-500, WS-700, EPOCROSS K-2010, K-2020, K-2030 and the like manufactured by Nippon Shokubai Co., Ltd. can be used.

Examples of the aziridine-based crosslinking agent include glycerol-tris (1-aziridinylpropionate), glycerol-tris [2-methyl- (1-aziridinyl)] propionate, glycerol-tris [2-ethyl- ( 1-aziridinyl)] propionate, glycerol-tris [2-butyl- (1-aziridinyl)] propionate), glycerol-tris [2-propyl- (1-aziridinyl)] propionate, glycerol-tris [ 2-pentyl- (1-aziridinyl)] propionate, glycerol-tris [2-hexyl- (1-aziridinyl)] propionate, glycerol-tris [2,3-dimethyl- (1-aziridinyl)] propionate Glycerol-Tris [2,3-diethyl- (1-aziridinini )] Propionate, glycerol-tris [2,3-dibutyl- (1-aziridinyl)] propionate), glycerol-tris [2,3-dipropyl- (1-aziridinyl)] propionate, glycerol-tris [2,3-dipentyl- (1-aziridinyl)] propionate, glycerol-tris [2,3-dihexyl- (1-aziridinyl)] propionate, trimethylolpropane-tris (1-aziridinylpropionate) -To), trimethylolpropane-tris [2-methyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2-ethyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [ 2-butyl- (1-aziridinyl)] propionate), trimethy Propane-tris [2-propyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2-pentyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2-hexyl- (1 -Aziridinyl)] propionate, trimethylolpropane-tris [2,3-dimethyl- (1-aziridinyl)] propionate, trimethylolpropane-tris [2,3-diethyl- (1-aziridinyl)] propionone Trimethylolpropane-tris [2,3-dibutyl- (1-aziridinyl)] propionate), trimethylolpropane-tris [2,3-dipropyl- (1-aziridinyl)] propionate, trimethylolpropane Tris [2,3-dipentyl- (1-aziridinini Propionate, trimethylolpropane-tris [2,3-dihexyl- (1-aziridinyl)] propionate tetramethylolmethane-tris (1-aziridinylpropionate), tetramethylolmethane-tris [2-Methyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2-ethyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2-butyl- (1-aziridinyl) ] Propionate), tetramethylolmethane-tris [2-propyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2-pentyl- (1-aziridinyl)] propionate, tetramethylolmethane- Tris [2-hexyl- (1-aziridinyl)] propi Neato, tetramethylolmethane-tris [2,3-dimethyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2,3-diethyl- (1-aziridinyl)] propionate, tetramethylol Methane-tris [2,3-dibutyl- (1-aziridinyl)] propionate), tetramethylolmethane-tris [2,3-dipropyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2 , 3-dipentyl- (1-aziridinyl)] propionate, tetramethylolmethane-tris [2,3-dihexyl- (1-aziridinyl)] propionate, pentaerythritol-tetra (1-aziridinylpropionate) G), pentaerythritol-tetra [2-methyl- (1-aziridy) )] Propionate, pentaerythritol-tetra [2-ethyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2-butyl- (1-aziridinyl)] propionate), pentaerythritol-tetra [2-propyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2-pentyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2-hexyl- (1-aziridinyl)] propione -Pentaerythritol-tetra [2,3-dimethyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2,3-diethyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [ 2,3-dibutyl- (1-aziridinyl )] Propionate), pentaerythritol-tetra [2,3-dipropyl- (1-aziridinyl)] propionate, pentaerythritol-tetra [2,3-dipentyl- (1-aziridinyl)] propionate, Pentaerythritol-tetra [2,3-dihexyl- (1-aziridinyl)] propionate, tetraaziridinylmetaxylenediamine, tetraaziridinylmethylparaxylenediamine, tetramethylpropanetetraaziridinylpropionate, Neopentyl glycol di (β-aziridinylpropionate), 4,4′-isopropylidenediphenol di (β-aziridinylpropionate), 4,4′-methylenediphenoldi (β- Aziridinylpropionate), 4,4'-bis (ethyleneiminocarbo Arylamino) diphenylmethane, compounds and the like described in JP 2003-104970.

As the epoxy-based cross-linking agent, various known ones can be used without particular limitation as long as they are epoxy resins (compounds) having at least two epoxy groups in the molecule, and examples thereof include the same as the component (β). Specifically, aromatic epoxy compounds such as bisphenol A type epoxy compounds, bisphenol S type epoxy resins, bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds; Hydrogenated epoxy compounds in which an aromatic ring is hydrogenated to have an alicyclic structure, vinylcyclohexene dioxide, dicyclopentadiene oxide, 3,4-epoxy-1- [8,9-epoxy-2,4-dioxaspiro [5 .5] Epoxy- [epoxy-oxaspiro C8-15 alkyl] -cyclo-12alkane, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate such as undecan-3-yl] -cyclohexane , 5-epoxy Epoxy C5-12 cycloalkyl C1-3 alkyl-epoxy C5-12 cycloalkane carboxylate such as looctylmethyl-4 ', 5'-epoxycyclooctanecarboxylate, bis (2-methyl-3,4-epoxycyclohexylmethyl) ) An alicyclic epoxy compound such as adipate; a nitrogen-containing ring epoxy resin such as a hydantoin epoxy resin; an aliphatic epoxy resin, a glycidyl ether type epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, etc .; One species can be used alone, or two or more species can be used in combination. *

As the melamine-based crosslinking agent, for example, a methylol melamine derivative obtained by condensing melamine and formaldehyde and a compound obtained by etherification by reacting methyl alcohol, ethyl alcohol, isopropyl alcohol or the like as a lower alcohol are preferable. Examples of the methylol melamine derivative include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, and melamine compounds described in JP2012-97132A.

It can be used when the (γ3) component (hydroxyl group-containing monomer) is used as the constituent monomer of the (γ) component as the isocyanate-based crosslinking agent. For example, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates and these Examples thereof include nurate or adduct bodies of diisocyanate compounds, and block bodies thereof. Examples of the aromatic diisocyanate include tolylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and the like. Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of alicyclic diisocyanates include dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate (HYDI), and hydrogenated tolylene diisocyanate.

In addition, the conductive composition of the third aspect can include the neutralizing agent in consideration of the possibility that the carboxyl group-reactive crosslinking agent is consumed by the component (a2) which is a strong acid substance. As the neutralizing agent, tertiary alkylamines and / or ammonia are particularly preferable.

The method for preparing the conductive composition is not particularly limited, and examples thereof include a method of mixing and dispersing the organic solvent dispersion of the present invention and the (γ) component by various known methods. In addition, a method of mixing and dispersing the component (A), the component (B), the component (C) and the optional component (carboxyl group-reactive crosslinking agent, neutralizing agent) in the component (D) can be mentioned. . In the latter case, the order of adding the solute components is not particularly limited. Moreover, it can be said that the electroconductive composition obtained by the latter method contains the organic-solvent dispersion of this invention as a result.

The content of each component in the conductive composition is not particularly limited, and may be appropriately set according to the use, but is usually as follows. (However, the total of all components does not exceed 100% by weight. In addition, components other than the component (D) are converted to solid content.)

Component (A): about 0.01 to 2% by weight, preferably 0.02 to 1% by weight
Component (B): about 0.01 to 2% by weight, preferably 0.02 to 1% by weight
Component (C): about 0.01 to 5% by weight, preferably 0.01 to 1% by weight
Component (D): about 95 to 99.5% by weight, preferably 97 to 99.95% by weight
Component (γ): about 0.01 to 2% by weight, preferably 0.05 to 0.5% by weight
Carboxyl group-reactive crosslinking agent: about 0 to 2% by weight, preferably 0.01 to 0.5% by weight
Neutralizing agent: 0 to 0.1% by weight, preferably 0.005 to 0.02% by weight

The conductive compositions of the first aspect, the second aspect, and the third aspect include various pigments, colorants, photosensitizers, antioxidants other than the component (C), light stabilizers, leveling agents, and conductive materials. Additives such as property-improving substances (such as dimethyl sulfoxide) may be included. Moreover, you may mix | blend various well-known inactive energy ray hardening-type resins, such as a polyurethane resin, a polyester resin, an epoxy resin, an acrylic resin, a polypropylene resin, as needed. In addition, when the (α2-1) component and / or the (α2-2) component having a hydroxyl group in the molecule is used as the (α) component, the polyisocyanate compound or other isocyanate is used for the purpose of crosslinking reaction with the hydroxyl group. A system cross-linking agent can also be blended.

<About conductive film>
The conductive film of the present invention is obtained by applying the conductive composition of the first aspect, the second aspect, or the third aspect of the present invention to a substrate and performing various curing treatments.

In the case of the conductive composition of the first aspect, the target conductive film can be obtained by applying the conductive composition to a substrate and irradiating active energy rays. In addition, you may provide the drying process which evaporates (D) component before irradiating an active energy ray.

Examples of the active energy rays include ultraviolet rays and electron beams. Examples of the ultraviolet light source include a high-pressure mercury lamp and a metal halide lamp, and the irradiation amount is usually about 100 to 2,000 mJ / cm ² . Examples of the electron beam supply method include scanning electron beam irradiation and curtain electron beam irradiation method, and the irradiation energy is usually about 10 to 200 kGy.

In the case of the conductive composition of the second embodiment, the target conductive film is applied depending on whether the conductive composition is applied to a substrate and cured by heating or by irradiation with active energy rays. Is obtained. In addition, you may provide the drying process which evaporates (D) component prior to these hardening processes.

The temperature of thermosetting is not particularly limited and may be appropriately set depending on the type of the substrate, but is usually room temperature or higher, and when the epoxy group-reactive crosslinking agent is used, the crosslinking reaction proceeds under heating. Since it is necessary, the temperature of thermosetting is usually about 40 to 180 ° C. On the other hand, the conditions for curing by irradiation with active energy rays are the same as in the case of the conductive composition of the first embodiment.

In the case of the conductive composition of the third aspect, it is obtained by applying the conductive composition to a substrate and evaporating the component (D). In addition, the temperature at which component (D) is evaporated may be appropriately set depending on the type of substrate, and is usually room temperature or higher. However, when a carboxyl group-reactive crosslinking agent is used, the crosslinking reaction is performed under heating. Since it is necessary to proceed, it is usually about 40 to 180 ° C.

The substrate is not particularly limited, and examples thereof include triacetyl cellulose resin, polyester resin, polyolefin resin, polycarbonate resin, polymethyl methacrylate resin, polystyrene resin, epoxy resin, melamine resin, ABS resin, AS resin, and norbornene resin. It is done. Further, the form of the substrate is not particularly limited, and may be a structure or a film. Examples of the film include triacetyl cellulose film, polyester film, polyolefin film, polycarbonate film, polymethyl methacrylate film, polystyrene film, epoxy film, melamine film, ABS film, AS film, norbornene resin film, etc., optical characteristics From the viewpoint of the above, a triacetyl cellulose film is particularly preferable.

The coating method is not particularly limited, and examples thereof include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Preparation of component (A)>
Preparation Example 1
1000 g of a commercially available aqueous dispersion of PEDOT / PSS (trade name “Orgacon”, solid content concentration 1.2% by weight) using a spray dryer (product name “GA-32”, manufactured by Yamato Scientific Co., Ltd.) Processing (spray pressure 0.6 MPa, drying temperature (intake) 150 ° C.) gave 9.0 g of a blue solid. Further, the same operation was repeated to prepare an amount of blue solid necessary for the preparation of the conductive composition.

<Synthesis of (α2) component>
Synthesis example 1
In a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 37.5 g of glycidyl methacrylate, 37.5 g of methyl methacrylate, 247.5 g of methyl isobutyl ketone and 2,2′-azobisisobutyro After charging 3 g of nitrile, the temperature in the system was increased to about 85 ° C. over about 1 hour under a nitrogen stream, and the temperature was kept for 1 hour. Next, from a dropping funnel previously charged with a mixed liquid consisting of 112.5 g of glycidyl methacrylate, 112.5 g of methyl methacrylate and 9 g of 2,2′-azobisisobutyronitrile, the mixed liquid was subjected to about 2 in a nitrogen stream. It took time to drop into the system and kept at the same temperature for 3 hours. Then, 3 g of 2,2′-azobisisobutyronitrile was added and kept for 1 hour. Then, it heated up to 115 degreeC and heat-retained for 2 hours. Next, after cooling the reaction system to 60 ° C., the nitrogen introduction tube was replaced with an air introduction tube, 76 g of acrylic acid, 0.6 g of methoquinone and 1.5 g of triphenylphosphine were added and mixed, and then under air bubbling, The temperature was raised to 110 ° C. After incubating at the same temperature for 8 hours, the mixture was cooled and methyl isobutyl ketone was added so that the solid content was 56% to obtain a polymer solution. The copolymer had a hydroxyl value of 76 mgKOH / g (solution) and a weight average molecular weight of 17,600. The weight average molecular weight was measured using a commercially available GPC apparatus (product name “HLC-8220”, manufactured by Tosoh Corporation) and a commercially available column (trade name “TSK-GEL SUPERHZM-M”, manufactured by Tosoh Corporation). It is the measured value obtained.

<Preparation of conductive composition of first aspect>
Example 1
In a beaker, 7.87 g of the solid component (A) obtained in Preparation Example 1 (hereinafter abbreviated as P / P) and 733.97 g of ethanol were placed, and as the component (B), an amine alkylene oxide adduct (trade name) : Esopropomin C18 / 18, manufactured by Lion Akzo Co., Ltd. (hereinafter abbreviated as EPA) 7.87 g was added, and then an emulsifying disperser (product name: Claremix, manufactured by M Technique Co., Ltd., the same applies hereinafter). ) Using a ultrasonic disperser (19.6 kHz, manufactured by Ginsen Co., Ltd., the same shall apply hereinafter) for 10 minutes at an output of 400 W for 10 minutes. A composition having a partial concentration of 2.1% by weight was obtained. Next, 1.97 g of 3,4 ′, 5,5 ′, 7-pentahydroxyflavone (hereinafter abbreviated as QT) is used as the component (C), and 24. 143.86 g of 28 g and 25.00 g of ethylene glycol, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name “M400”, manufactured by Toagosei Co., Ltd.) as the (α1) component, and the above (α2 ) Component (45.33 g) and a commercially available photopolymerization initiator (product name “Irgacure 184”, manufactured by Ciba Japan Co., Ltd.) 9.84 g are added and the mixture is stirred well to obtain a conductive composition (solid content concentration of about 19.7% by weight). QT is known to be insoluble in water, and a 1% solution (25 ° C.) using a mixed solvent of ethanol / water = 9/1 shows a transparent appearance without turbidity, but ethanol / water A 1% solution (25 ° C.) using a mixed solvent of 8/2 exhibits turbidity.

(Structural formula of QT)

Example 2
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, 4.92 g of QT, 24.63 g of ethanol, 25 g of ethylene glycol, 9.84 g of Irgacure 184, 141.35 g of M400, and 44.54 g of the above (α2) component were added to the composition. By stirring, a conductive composition (solid content concentration of about 19.7% by weight) was obtained. In addition, content of QT in the said composition was 2.5 weight% (solid content conversion).

Example 3
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, 9.84 g of QT, 25.21 g of ethanol, 25.00 g of ethylene glycol, 131.17 g of M400, 43.23 g of the (α2) component and 9.84 g of Irgacure 184 were added to the composition, By thoroughly stirring, a conductive composition (solid content concentration of about 19.7% by weight) was obtained.

Example 4
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, instead of QT, the composition was replaced with (2R, 3S) -2- (3,4-dihydroxyphenyl) chroman-3,5,7-triol (hereinafter referred to as CQ) 4.92 g and ethanol. 24.63 g, ethylene glycol 25.00 g, M400 131.17 g, the above (α2) component 43.23 g and Irgacure 184 9.84 g were added and stirred well to obtain a conductive composition (solid content concentration of about 19.7% by weight).

(CQ structure)

Comparative Example 1
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, instead of QT, octyl gallate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the composition, 4.92 g, ethanol 24.64 g, ethylene glycol 25 g, M400 141.35 g, and the component (α2) 44.54 g and 9.84 g of Irgacure 184 were added and stirred well to obtain a conductive composition (solid content concentration of about 19.7% by weight).

Comparative Example 2
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, in place of QT, benzophenone-based ultraviolet absorber (trade name “3HBR”, manufactured by Iwate Chemical Co., Ltd.) was used instead of QT, 4.92 g, ethanol was 24.64 g, and ethylene glycol was 25.00 g, Irgacure. 9.84 g of 184, 141.35 g of M400, and 44.54 g of the component (α2) were added and stirred well to obtain a conductive composition (solid content concentration of about 19.7% by weight).

Comparative Example 3
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, in place of QT, propyl gallate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the composition, 4.92 g, ethanol 24.64 g, ethylene glycol 25.00 g, Irgacure 184 9.84 g, and M400. 141.35 g and 44.54 g of the component (α2) were added and stirred well to obtain a conductive composition (solid content concentration of about 19.7% by weight).

Comparative Example 4
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, instead of QT, the composition was changed to 4.92 g of dodecyl gallate (manufactured by Tokyo Chemical Industry Co., Ltd.), 24.64 g of ethanol, 25.00 g of ethylene glycol, 141.35 g of M400, and the (α2) component. And 4.84 g of Irgacure 184 were added and stirred well to obtain a conductive composition (solid content concentration of about 19.7% by weight).

Comparative Example 5
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, 24.05 g of ethanol, 25.00 g of ethylene glycol, 9.84 g of Irgacure 184, 145.53 g of M400, and 45.86 g of the above (α2) component were added to the composition and stirred well. An electrically conductive composition containing no antioxidant (solid content concentration of about 19.7% by weight) was obtained.

Comparative Example 6
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, 0.98 g of a commercially available aminocarboxylic acid chelating agent (trade name “Kyrest EA”, manufactured by Kirest Co., Ltd.) instead of QT, 24.05 g of ethanol, and 25. of ethylene glycol were added to the composition. 00 g, Irgacure 184 9.84 g, M400 145.53 g, and 45.86 g of the component (α2) were added and stirred well to obtain a conductive composition (solid content concentration of about 19.7 wt%). Obtained.

Comparative Example 7
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, 0.98 g of a commercially available carboxylic acid chelating agent (trade name “Kyrest MZ-8”, manufactured by Kirest Co., Ltd.) instead of QT, 24.05 g of ethanol, and 25.00 g of ethylene glycol were added to the composition. , Irgacure 184 (9.84 g), M400 (145.53 g), and (α2) component (45.86 g) were added and stirred well to obtain a conductive composition (solid content concentration of about 19.7 wt%). It was.

Comparative Example 8
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, 0.98 g of a commercially available carboxylic acid chelating agent (trade name “Kyrest MZ-2”, manufactured by Kirest Co., Ltd.) instead of QT, 24.05 g of ethanol, and 25.00 g of ethylene glycol were added to the composition. , Irgacure 184 (9.84 g), M400 (145.53 g), and (α2) component (45.86 g) were added and stirred well to obtain a conductive composition (solid content concentration of about 19.7 wt%). It was.

Comparative Example 9
In a beaker, 7.87 g of P / P and 733.97 g of ethanol were added, and 7.87 g of EPA was added, and then treated by using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 1. A composition having a partial concentration of 2.1% by weight was obtained. Next, 0.98 g of a commercially available hindered phenol light stabilizer (trade name “ADEKA LA-81”, manufactured by ADEKA Corporation) instead of QT, 24.05 g of ethanol, and 25 of ethylene glycol were added to the composition. 0.000 g, Irgacure 184 9.84 g, M400 145.53 g, and the above (α2) component 45.86 g were added and stirred well to obtain a conductive composition (solid content concentration of about 19.7 wt%). Got.

<Preparation of conductive film>
The conductive composition of Example 1 was applied onto a triacetyl cellulose film using a # 4 bar coater (calculated value: film thickness: 1.0 μm) and dried at 80 ° C. for 1 minute. Next, this was passed through an ultraviolet irradiation device (manufactured by Multiply Co., Ltd., light quantity: 300 mJ / cm ² , distance from the coating to the light source: 10 cm, pass speed: 6.1 m / min) to produce a conductive coating. The same applies to the conductive compositions according to Examples 2 to 4 and Comparative Examples 1 to 9.

<Evaluation of conductivity: initial surface resistivity>
For the test film according to Example 1, the surface resistivity (Ω / □) of the conductive film immediately after the production was measured using a commercially available surface resistivity meter (product name “Loresta EP MCP-T360”, manufactured by Mitsubishi Chemical Corporation). And measured at room temperature. The initial surface resistivity was also measured in the same manner for the test films of Examples 2 to 4 and Comparative Examples 1 to 9. The results are shown in Table 1.

<Evaluation of conductivity: surface resistivity over time (ultraviolet irradiation test)>
After testing the test film according to Example 1 with a super accelerated weathering tester (product name “U48AU”, manufactured by Suga Test Instruments Co., Ltd.) (irradiance 500 W / m ² near ultraviolet wavelength 388 nm × 96 hours), The surface resistivity was measured at room temperature, and the rate of increase (= surface resistivity after UV irradiation test / initial surface resistivity × 100) was determined. The initial surface resistivity was also measured in the same manner for the test films of Examples 2 to 4 and Comparative Examples 1 to 9. The results are shown in Table 1.

<Preparation of conductive composition of second aspect>
Example 5
In a beaker, 4.2 g of P / P obtained in Preparation Example 1 and 458.27 g of ethanol were added, and 4.2 g of EPA was added. Then, the emulsion was dispersed for 10 minutes at 18,000 rpm using the above emulsifying disperser. A composition having a solid content concentration of 1.8% by weight was obtained by carrying out treatment for 10 minutes at an output of 400 W using an ultrasonic disperser. Next, 0.36 g of QT, 129.73 g of ethanol, 300 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, and 3,4-epoxycyclohexylmethyl-3 ′, 4 as (β) component were added to the composition. Add 3.24 g of '-epoxycyclohexanecarboxylate (trade name “Celoxide 2021P”, manufactured by Daicel Chemical Industries, Ltd.) and stir well to obtain a conductive composition (solid content concentration of about 1.2% by weight). It was.

Example 6
In a beaker, 4.2 g of P / P and 458.27 g of ethanol were added, and 4.2 g of EPA was added. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.36 g of QT, 129.54 g of ethanol, 300 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, 3.24 g of celoxide 2021P, and 0.19 g of TEA are added to the composition, and stirred well. As a result, a conductive composition (solid content concentration of about 1.2% by weight) was obtained.

Example 7
In a beaker, 4.2 g of P / P and 458.27 g of ethanol were added, and 4.2 g of EPA was added, and then the mixture was treated with an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 5 to obtain a solid. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.6 g of QT, 129.73 g of ethanol, 300 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, and 3.0 g of celoxide 2021P are added to the composition, and the conductive composition is stirred well. (Solid content concentration of about 1.2% by weight) was obtained.

Example 8
In a beaker, 4.2 g of P / P and 458.27 g of ethanol were added, and 4.2 g of EPA was added, and then the mixture was treated with an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 5 to obtain a solid. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.6 g of QT, 129.54 g of ethanol, 300 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, 3.0 g of celoxide 2021P, and 0.19 g of TEA were added to the composition and stirred well. As a result, a conductive composition (solid content concentration of about 1.2% by weight) was obtained.

Comparative Example 10
In a beaker, 4.2 g of P / P and 458.27 g of ethanol were added, and 4.2 g of EPA was added, and then the mixture was treated with an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 5 to obtain a solid. A composition having a partial concentration of 1.8% by weight was obtained. Next, 129.73 g of ethanol, 300 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, and 3.6 g of celoxide 2021P were added to the composition, and the mixture was thoroughly stirred to obtain a conductive composition containing no QT (solid A partial concentration of about 1.2% by weight).

Comparative Example 11
In a beaker, 4.2 g of P / P and 458.27 g of ethanol were added, and 4.2 g of EPA was added, and then the mixture was treated with an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 5 to obtain a solid. A composition having a partial concentration of 1.8% by weight was obtained. Next, 129.54 g of ethanol, 300 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, 3.6 g of ceroxide 2021P, and 0.19 g of TEA were added to the composition, and the mixture was thoroughly stirred to contain QT. A conductive composition (solid content concentration of about 1.2% by weight) was obtained.

<Preparation of conductive film>
The conductive composition according to Example 5 was applied on a PET film using a # 20 bar coater (calculated value: film thickness: 0.25 μm) and dried at 120 ° C. for 5 minutes to form a conductive film. A prepared test film was obtained. In addition, test films were obtained in the same manner for the conductive compositions according to Examples 6 to 8 and Comparative Examples 10 to 11.

<Evaluation of conductivity: initial surface resistivity>
For the test film according to Example 5, the surface resistivity (Ω / □) of the conductive film immediately after the production was measured using a commercially available surface resistivity meter (product name “Loresta EP MCP-T360”, manufactured by Mitsubishi Chemical Corporation). And measured at room temperature. The surface resistivity of the test films of Examples 6 to 8 and Comparative Examples 10 to 11 was measured in the same manner. The results are shown in Table 2.

<Evaluation of conductivity: surface resistivity over time (ultraviolet irradiation test)>
After testing the test film according to Example 5 with a super accelerated weathering tester (product name “U48AU”, manufactured by Suga Test Instruments Co., Ltd.) (irradiance 500 W / m ² near ultraviolet wavelength 388 nm × 96 hours), The surface resistivity was measured at room temperature, and the rate of increase (= surface resistivity after UV irradiation test / initial surface resistivity × 100) was determined. The rate of increase (unit:%) was similarly determined for the test films of Examples 6 to 8 and Comparative Examples 10 to 11. The results are shown in Table 2.

<Evaluation of conductivity: surface resistivity over time (heating test)>
The test film according to Example 5 was put in an incubator at 80 ° C., and the surface resistivity after being allowed to stand for 96 hours was measured at room temperature, and the rate of increase (= surface resistivity after heating test / initial surface resistivity × 100). Asked. Further, the rate of increase (unit:%) was similarly determined for the test films of Examples 6 to 8 and Comparative Examples 10 to 11. The results are shown in Table 2.

<Synthesis of (γ) component>
Synthesis example 2
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 50.0 g of acrylic acid (hereinafter abbreviated as AA) and methyl methacrylate (hereinafter abbreviated as MMA) were added. 49.5 g, 0.5 g of normal butyl acrylate (hereinafter abbreviated as BA), 5.0 g of 2,2′-azobis (2-methylbutyronitrile), and 40.0 g of propylene glycol monomethyl ether were added. It hold | maintained at 85 degreeC under nitrogen gas stream for 5 hours. Thus, an acrylic copolymer solution having a solid concentration of 20% by weight was obtained. Table 3 shows the glass transition temperature (Tg), acid value (AV), and weight average molecular weight (Mw) of the acrylic copolymer.

Synthesis example 3
In a reaction vessel similar to Synthesis Example 2, AA 50.0 g, MMA 24.5 g, BA 25.0 g, 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) 0.5 g, and 2, By adding 5.0 g of 2′-azobis (2-methylbutyronitrile) and 420.0 g of propylene glycol monomethyl ether, and maintaining at 85 ° C. for 5 hours under a nitrogen gas stream, the solid content concentration is 20% by weight. A solution of the acrylic copolymer (C2) was obtained. Table 3 shows the glass transition temperature (Tg), acid value (AV), and weight average molecular weight (Mw) of the acrylic copolymer.

The glass transition temperature is a measured value obtained with a commercially available measuring device (product name “DSC6200”, manufactured by Seiko Instruments Inc.). The acid value is a measured value obtained according to the method of JIS-K2501-2003. Mw was obtained using a commercially available GPC device (product name “HLC-8220”, manufactured by Tosoh Corporation) and a commercially available column (trade name “TSK-GEL SUPERHZM-M”, manufactured by Tosoh Corporation). It is a measured value.

<Preparation of conductive composition of third aspect>
Example 9
In a beaker, 2.1 g of P / P obtained in Preparation Example 1 and 229.13 g of ethanol were added, and 2.1 g of EPA was added. Then, using the above emulsifying disperser, the mixture was processed at 18,000 rpm for 10 minutes, A composition having a solid content concentration of 1.8% by weight was obtained by performing a treatment for 10 minutes at an output of 400 W using the ultrasonic disperser. Next, 0.18 g of QT, 164.87 g of ethanol, 495.75 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, 3.38 g of the acrylic copolymer solution obtained in Synthesis Example 2, and oxazoline-based cross-linking 2.4 g of the agent (trade name “Epocross WS-500”, manufactured by Nippon Shokubai Co., Ltd., solid content concentration: 39.3%, hereinafter abbreviated as “OXZ”) and 0.095 g of TEA were added and stirred well. As a result, a conductive composition (solid content concentration of about 0.6% by weight) was obtained.

Comparative Example 12
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of a commercially available phosphorous antioxidant (trade name “SIPOME PAM 4000”, manufactured by Rhodia Nikka Co., Ltd., hereinafter referred to as PAM 4000) is added to the composition, 164.87 g of ethanol, and propylene glycol. By adding 495.75 g of monomethyl ether, 100.00 g of ethylene glycol, 3.38 g of the acrylic copolymer solution obtained in Synthesis Example 2 above, 2.4 g of OXZ, and 0.095 g of TEA, and stirring well A conductive composition (solid content concentration of about 0.6% by weight) was obtained.

Comparative Example 13
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of a commercially available phosphorus-based antioxidant (trade name “ADEKA C”, manufactured by ADEKA Corporation), 164.87 g of ethanol, 495.75 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, 3.38 g of the acrylic copolymer aqueous solution obtained in Synthesis Example 2 above, 2.4 g of OXZ, and 0.095 g of TEA were added, and the mixture was stirred well to obtain a conductive composition (solid content concentration of about 0.6% by weight). )

Comparative Example 14
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of a commercially available phosphorous antioxidant (trade name “ADEKA 3010”, manufactured by ADEKA Corporation), ethanol of 164.87 g, propylene glycol monomethyl ether of 495.75 g, and ethylene glycol of 100.00 g Then, 3.38 g of the acrylic copolymer aqueous solution obtained in Synthesis Example 2 above, 2.4 g of OXZ and 0.095 g of TEA were charged and stirred well to obtain a conductive composition (solid content concentration of about 0.6% by weight) )

Comparative Example 15
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of a commercially available phenolic antioxidant (trade name “AO-80”, manufactured by ADEKA Corporation), 164.87 g of ethanol, 495.75 g of propylene glycol monomethyl ether, ethylene Add 100.00 g of glycol, 3.38 g of the acrylic copolymer aqueous solution obtained in Synthesis Example 2 above, 2.4 g of OXZ, and 0.095 g of TEA, and stir well to obtain a conductive composition (solid content concentration). About 0.6% by weight).

Comparative Example 16
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of a commercially available sulfur-based antioxidant (trade name “AO-503”, manufactured by ADEKA Corporation), 164.87 g of ethanol, 495.75 g of propylene glycol monomethyl ether, ethylene Add 100.00 g of glycol, 3.38 g of the acrylic copolymer aqueous solution obtained in Synthesis Example 2 above, 2.4 g of OXZ, and 0.095 g of TEA, and stir well to obtain a conductive composition (solid content concentration). About 0.6% by weight).

Comparative Example 17
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of a commercially available benzophenone ultraviolet absorber (trade name “DAINSORB P-6”, manufactured by Daiwa Kasei Co., Ltd., hereinafter referred to as P-6), 164.87 g of ethanol and propylene were added to the composition. By adding 495.75 g of glycol monomethyl ether, 100.00 g of ethylene glycol, 3.38 g of the acrylic copolymer aqueous solution obtained in Synthesis Example 2 above, 2.4 g of OXZ and 0.095 g of TEA, and stirring well A conductive composition (solid content concentration of about 0.6% by weight) was obtained.

Comparative Example 18
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of a commercially available benzotriazole-based ultraviolet absorber (trade name “DAINSORB T-0”, manufactured by Daiwa Kasei Co., Ltd., hereinafter referred to as T-0) and 164.87 g of ethanol were added to the composition. Add 495.75 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, 3.38 g of the acrylic copolymer aqueous solution obtained in Synthesis Example 2, 2.4 g of OXZ and 0.095 g of TEA, and stir well. As a result, a conductive composition (solid content concentration of about 0.6% by weight) was obtained.

Comparative Example 19
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 164.87 g of ethanol, 495.28 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, 3.75 g of the acrylic copolymer aqueous solution obtained in Synthesis Example 2 and 2.67 g of OXZ were added to the composition. And 0.095 g of TEA were added and stirred well to obtain a conductive composition containing no antioxidant (solid content concentration: about 0.6% by weight).

<Preparation of conductive film>
The conductive composition according to Example 9 was applied on a PET film using a # 20 bar coater (calculated value: film thickness 0.2 μm) and dried at 120 ° C. for 5 minutes to form a conductive film. A prepared test film was obtained. In addition, test films were obtained in the same manner for the conductive compositions according to Comparative Examples 12 to 19.

<Evaluation of conductivity: initial surface resistivity>
For the test film according to Example 9, the surface resistivity (Ω / □) of the conductive film immediately after production was measured using a commercially available surface resistivity meter (product name “Loresta EP MCP-T360”, manufactured by Mitsubishi Chemical Corporation). And measured at room temperature. Further, the surface resistivity of the test films according to Comparative Examples 12 to 19 was measured in the same manner. The results are shown in Table 4.

<Evaluation of conductivity: surface resistivity over time (ultraviolet irradiation test)>
After testing the test film according to Example 9 with a super accelerated weathering tester (product name “U48AU”, manufactured by Suga Test Instruments Co., Ltd.) (irradiance 500 W / m ² near ultraviolet wavelength 388 nm × 96 hours), The surface resistivity was measured at room temperature, and the rate of increase (= surface resistivity after UV irradiation test / initial surface resistivity × 100) was determined. The rate of increase (unit:%) was similarly determined for the test films of Comparative Examples 12-19. The results are shown in Table 4.

<Evaluation of conductivity: surface resistivity over time (heating test)>
The test film according to Example 9 was put in a thermostat at 80 ° C., and the surface resistivity after being allowed to stand for 96 hours was measured at room temperature, and the rate of increase (= surface resistivity after heating test / initial surface resistivity × 100). Asked. Further, the rate of increase (unit:%) was similarly obtained for the test films according to Comparative Examples 12 to 19. The results are shown in Table 4.

Example 10
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of QT, 164.87 g of ethanol, 495.75 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, and 3.38 g of the acrylic copolymer solution obtained in Synthesis Example 3 were added to the composition. Then, 2.40 g of OXZ and 0.095 g of TEA were added and stirred well to obtain a conductive composition (solid content concentration of about 0.6% by weight).

Example 11
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of CQ, 164.87 g of ethanol, 495.75 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, and the acrylic copolymer obtained in Synthesis Example 3 as the component (C) in the composition. 3.38 g of the solution, 2.40 g of OXZ, and 0.095 g of TEA were added and stirred well to obtain a conductive composition (solid content concentration of about 0.6% by weight). CQ is known to be hardly soluble in water and ethanol.

Comparative Example 20
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of AO-80, 164.87 g of ethanol, 495.75 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, and 3% of the acrylic copolymer solution obtained in Synthesis Example 3 were added to the composition. .38 g, 2.4 g of OXZ and 0.095 g of TEA were added and stirred well to obtain a conductive composition (solid content concentration of about 0.6% by weight).

Comparative Example 21
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Then, the composition was ethanol (164.87 g), propylene glycol monomethyl ether (495.28 g), ethylene glycol (100.00 g), the acrylic copolymer solution obtained in Synthesis Example 3 (3.75 g), and OXZ (2.67 g). Then, 0.095 g of TEA and TEA were added and stirred well to obtain a conductive composition containing no antioxidant (solid content concentration: about 0.6% by weight).

Comparative Example 22
In a beaker, 2.1 g of P / P and 229.13 g of ethanol were added, and 2.1 g of EPA was added, followed by treatment using an emulsifying disperser and an ultrasonic disperser under the same conditions as in Example 9. A composition having a partial concentration of 1.8% by weight was obtained. Next, 0.18 g of a compound (hereinafter referred to as QT-Ru) in which a β-lutinose residue is bonded to the 7th position of QT and a methoxy group is bonded to the 3rd position (hereinafter referred to as QT-Ru) as component (C) is added to the composition. .87 g, 495.75 g of propylene glycol monomethyl ether, 100.00 g of ethylene glycol, 3.38 g of the acrylic copolymer solution obtained in Synthesis Example 3 above, 2.40 g of OXZ, and 0.095 g of TEA were added, By thoroughly stirring, a conductive composition (solid content concentration of about 0.6% by weight) was obtained. QT-Ru is known to be hardly soluble in both water and ethanol.

(Structure of QT-Ru)

Using each conductive composition of Examples 10 to 11 and Comparative Examples 20 to 22, test films were prepared in the same manner as described above, and the conductivity of the coating was evaluated. The results are shown in Table 5.

Claims

Conductive polymer / polyanion complex (A) comprising polythiophene (a1) and sulfoanion group-containing polymer (a2) having a structure represented by the following general formula (1), amine represented by the following general formula (2) An organic solvent dispersion containing the compound (B), an alcohol-soluble compound (C) among the compounds represented by the following general formula (3), and an organic solvent (D) containing the alcohol (d1).

(In the formula (1), A represents an alkylene group having 1 to 12 carbon atoms.)

(In Formula (2), X 1 represents any of an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 3 to 40 carbon atoms, and an aralkyl group having 3 to 40 carbon atoms. Y represents oxyethylene, respectively. Represents any one of a group, an oxypropylene group, and an oxyethylene-oxypropylene group, and m represents an integer of 1 to 20.)

(In formula (3), the broken line portion represents a carbon-carbon single bond or a carbon-carbon double bond. X 1 to X 7 are all selected from the group consisting of hydrogen, a hydroxyl group and an alkoxy group. (However, at least two of X 1 to X 7 are hydroxyl groups.) Y represents a methylene group or a carbonyl group.)
The organic solvent dispersion according to claim 1, wherein the component (C) is a compound represented by the following general formula (3-1).

(In the formula (3-1), a broken line part represents a carbon-carbon single bond or a carbon-carbon double bond, X 1 represents a hydroxyl group or an alkoxy group, and any one of X 3 , X 4 and X 5 represents (One is a hydroxyl group, and the other two are hydrogen or a hydroxyl group, respectively, and Y represents a methylene group or a carbonyl group.)
Conductive polymer / polyanion complex (A) comprising polythiophene (a1) and sulfoanion group-containing polymer (a2) having a structure represented by the following general formula (1), amine represented by the following general formula (2) Compound (B), and an alcohol-soluble compound (C) among the compounds represented by the following general formula (3),
An organic solvent (D) containing an alcohol (d1);
An active energy ray radical polymerization type compound (α), an epoxy resin (β) and a binder component selected from the group consisting of an inactive energy ray radical polymerization type acrylic copolymer (γ),
Conductive composition.

(In the formula (1), A represents an alkylene group having 1 to 12 carbon atoms.)

(In Formula (2), X 1 represents any of an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 3 to 40 carbon atoms, and an aralkyl group having 3 to 40 carbon atoms. Y represents oxyethylene, respectively. Represents any one of a group, an oxypropylene group, and an oxyethylene-oxypropylene group, and m represents an integer of 1 to 20.)

(In formula (3), the broken line portion represents a carbon-carbon single bond or a carbon-carbon double bond. X 1 to X 7 are all selected from the group consisting of hydrogen, a hydroxyl group and an alkoxy group. (However, at least two of X 1 to X 7 are hydroxyl groups.) Y represents a methylene group or a carbonyl group.)
The conductive composition according to claim 3, wherein the component (C) is a compound represented by the following general formula (3-1).

(In the formula (3-1), a broken line part represents a carbon-carbon single bond or a carbon-carbon double bond, X 1 represents a hydroxyl group or an alkoxy group, and any one of X 3 , X 4 and X 5 represents One is a hydroxyl group and the remaining two are hydrogen or a hydroxyl group, respectively, and Y represents a methylene group or a carbonyl group.)
The (α) component is a bifunctional to hexafunctional (meth) acrylate compound (α1) and / or a (meth) acrylic polymer (α2) having a free (meth) acryloyl group in the molecule. 3 or 4 conductive compositions.
The conductive composition according to any one of claims 3 to 5, further comprising a photopolymerization initiator.
A conductive film obtained by applying the conductive composition according to any one of claims 3 to 6 to a substrate and irradiating with active energy rays.
The conductive composition according to claim 3 or 4, wherein the component (β) is at least one selected from the group consisting of an aromatic epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin.
The conductive composition according to any one of claims 3, 4, and 8, wherein the alicyclic epoxy resin is an epoxy resin and / or a hydrogenated epoxy resin obtained by epoxidizing an alicyclic olefin.
Furthermore, the electrically conductive composition of any one of Claim 3, 4, 8, 9 containing an epoxy-group reactive crosslinking agent.
The conductive composition according to any one of claims 3, 4, 8 to 10, further comprising a neutralizing agent.
The conductive composition according to claim 3, further comprising a cationic polymerization catalyst.
A conductive film obtained by applying the conductive composition according to any one of claims 3, 4, and 8 to 12 to a base material and curing it by heating.
A conductive film obtained by applying the conductive composition according to any one of claims 3, 4, and 8 to 13 to a substrate and irradiating and curing the active energy ray.
The (γ) component is obtained by reacting an α, β unsaturated carboxylic acid (γ1), a (meth) acrylic acid alkyl ester (γ2) and, if necessary, a (meth) acrylic acid hydroxyalkyl ester (γ3). The conductive composition according to claim 3 or 4, which is an acrylic copolymer.
Furthermore, the electrically conductive composition of any one of Claim 3, 4, 15 containing a carboxyl group reactive crosslinking agent.
Furthermore, the electrically conductive composition of any one of Claim 3, 4, 15, 16 containing a neutralizing agent.
A conductive film obtained by applying the conductive composition according to any one of claims 3, 4, 15 to 17 to a substrate.