JP7225879B2 - Compositions, cured products and articles - Google Patents

Description

The present disclosure relates to compositions, cured products and articles.

A conductive polymer/polyanion complex composed of polythiophene and a sulfonion group-containing polymer is used in an antistatic coating agent because of its good transparency when formed into a thin film. In antistatic coating agents containing such conductive polymer/polyanion complexes, various additives have been studied in order to maintain antistatic properties (Patent Document 1).

WO2014/065314

Recently, when the additive (quercetin) described in Patent Document 1 is used, the antistatic property is maintained under heating conditions, but the additive is oxidized to produce colored matter, which impairs the appearance of the coating film. was found.

Accordingly, the problem to be solved by the present invention is to provide a composition that does not produce colored matter while maintaining antistatic properties even under heating conditions.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a specific composition.

（式（１）中、Ａはアルキレン基である。）
で表されるポリチオフェン（ａ１）及びスルホアニオン基含有ポリマー（ａ２）からなる導電性高分子／ポリアニオン錯体（Ａ）、
式（２）

（式（２）中、Ｘ^１はアルキル基、アルケニル基、又はアリールアルキル基であり、Ｙ^１及びＹ^２はそれぞれ独立に、ポリオキシアルキレン基である。）
で表されるアミン（Ｂ）、
式（３）

（式（３）中、Ｒはアルキル基、アルケニル基、アリール基、又はアリールアルキル基を表す。）
で表されるガレート化合物（Ｃ）、並びに有機溶媒（Ｄ）を含む、組成物。
（項目２）
重合性不飽和炭素結合含有化合物（Ｅ）を含む、上記項目に記載の組成物。
（項目３）
上記項目のいずれか１項に記載の組成物の硬化物。
（項目４）
上記項目に記載の硬化物を含む物品。 The following items are provided by this disclosure.
(Item 1) Formula (1)

(In formula (1), A is an alkylene group.)
A conductive polymer/polyanion complex (A) consisting of a polythiophene (a1) and a sulfonion group-containing polymer (a2) represented by
formula (2)

(In formula (2), X ¹ is an alkyl group, an alkenyl group, or an arylalkyl group, and Y ¹ and Y ² are each independently a polyoxyalkylene group.)
Amine (B) represented by
Formula (3)

(In Formula (3), R represents an alkyl group, an alkenyl group, an aryl group, or an arylalkyl group.)
A composition comprising a gallate compound (C) represented by and an organic solvent (D).
(Item 2)
The composition according to the above items, comprising a polymerizable unsaturated carbon bond-containing compound (E).
(Item 3)
A cured product of the composition according to any one of the above items.
(Item 4)
An article containing the cured product according to the above items.

In the present disclosure, one or more of the features described above may be provided in further combinations in addition to the explicit combinations.

The composition of the present embodiment maintains its antistatic properties even under heating conditions, but does not generate colored matter. Therefore, the composition of this embodiment can be used as an antistatic coating agent or a conductive coating agent.

Throughout the present disclosure, the range of numerical values for each physical property value, content, etc. can be set as appropriate (for example, by selecting from the upper and lower limit values described in each item below). Specifically, for the numerical value α, when A1, A2, A3, A4 (with A1>A2>A3>A4), etc. are exemplified as the upper and lower limits of the numerical value α, the range of the numerical value α is A1 or less, Examples include A2 or less, A3 or less, A2 or more, A3 or more, A4 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, A3 to A4.

[Description of various groups]
Alkyl groups are exemplified by linear alkyl groups, branched alkyl groups, cycloalkyl groups and the like.

A linear alkyl group is represented by the general formula: -C _n H _2n+1 (n is an integer of 1 or more). A straight-chain alkyl group includes a methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decamethyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group (stearyl group), n-nonadecyl group, n -icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, n -Triacontyl group and the like are exemplified.

Branched alkyl groups are groups in which one or more hydrogen atoms of a straight chain alkyl group have been replaced by an alkyl group. Examples of branched alkyl groups include i-propyl, i-butyl, s-butyl, t-butyl, i-pentyl, neopentyl, t-pentyl and i-hexyl groups.

A cycloalkyl group is an alkyl group having a ring structure. The cycloalkyl group is exemplified by a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, a condensed ring cycloalkyl group and the like. A cycloalkyl group may also have one or more hydrogen atoms replaced by a straight or branched chain alkyl group.

In the present disclosure, monocyclic means a cyclic structure formed by covalent carbon bonds and having no internal bridging structure. A condensed ring means a cyclic structure in which two or more single rings share two atoms (that is, each ring shares (condenses) only one edge with each other). Bridged ring means a cyclic structure in which two or more single rings share three or more atoms.

Monocyclic cycloalkyl groups are exemplified by cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl and 3,5,5-trimethylcyclohexyl groups.

The bridging ring cycloalkyl group is exemplified by a tricyclodecyl group, an adamantyl group, a norbornyl group and the like.

The condensed ring cycloalkyl group is exemplified by a bicyclodecyl group and the like.

Alkenyl groups are exemplified by linear alkenyl groups, branched alkenyl groups, cycloalkenyl groups and the like.

A linear alkenyl group is represented by the general formula: -C _n H _2n-1 (n is an integer of 2 or more). Linear alkyl groups are exemplified by vinyl, allyl, n-butenyl, n-pentenyl, n-hexenyl, n-heptenyl, n-octenyl, n-nonenyl and n-decamethenyl groups. be.

Branched alkenyl groups are groups in which one or more hydrogen atoms of a straight-chain alkenyl group have been replaced by an alkyl group. The branched alkenyl group is exemplified by 1-methylvinyl group, 1-methylallyl group and the like.

A cycloalkenyl group is an alkenyl group having a ring structure. The cycloalkenyl group is exemplified by a monocyclic cycloalkenyl group, a bridged ring cycloalkenyl group, a condensed ring cycloalkenyl group and the like. A cycloalkenyl group may also have one or more hydrogen atoms replaced by a straight or branched alkyl group.

A monocyclic cycloalkenyl group is exemplified by a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and the like.

The bridging ring cycloalkenyl group is exemplified by a norbornenyl group and the like.

The condensed ring cycloalkenyl group is exemplified by a bicyclodecenyl group and the like.

The arylalkyl group is a group represented by -R ^alkylene -R ^aryl (R ^alkylene means an alkylene group and R ^aryl means an aryl group).

The aryl group is exemplified by a monocyclic aryl group, a condensed ring aryl group, and the like. An aryl group may have one or more hydrogen atoms replaced by a straight or branched alkyl group.

The monocyclic aryl group is exemplified by a phenyl group and the like.

A naphthyl group etc. are illustrated as a condensed ring aryl group.

The arylalkyl group is exemplified by a benzyl group and the like.

The alkylene group is exemplified by a linear alkylene group, a branched alkylene group, a cycloalkylene group and the like.

A linear alkylene group is represented by the general formula: —(CH ₂ ) _n — (n is an integer of 1 or more). Straight-chain alkylene group includes methylene group, ethylene group, propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decamethylene group, etc. are exemplified.

A branched alkylene group is one in which one or more hydrogen atoms of a linear alkylene group have been replaced by an alkyl group. The branched alkylene group is exemplified by a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, a trimethylhexylene group and the like.

The cycloalkylene group is exemplified by a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, a condensed ring cycloalkylene group and the like. A cycloalkylene group may also have one or more hydrogen atoms replaced by a straight or branched alkyl group.

The monocyclic cycloalkylene group is exemplified by a cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclodecylene group, 3,5,5-trimethylcyclohexylene group and the like.

The bridging ring cycloalkylene group is exemplified by a tricyclodecylene group, an adamantylene group, a norbornylene group and the like.

The condensed ring cycloalkylene group is exemplified by a bicyclodecylene group and the like.

The number of carbon atoms in the alkyl group, alkylene group, alkenyl group, alkenylene group, aryl group, and arylalkyl group described above is not particularly limited, but the upper and lower limits are 40, 35, 30, 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. are exemplified.

The polyoxyalkylene group is a group represented by -[R ^alkylene -O-] _n - (R ^alkylene means an alkylene group and n means an integer of 1 or more).

The polyoxyalkylene group is exemplified by an oxyethylene group, an oxypropylene group, an oxyethylene-oxypropylene group, and the like.

（式（１）中、Ａはアルキレン基である。）
で表されるポリチオフェン（ａ１）及びスルホアニオン基含有ポリマー（ａ２）からなる導電性高分子／ポリアニオン錯体（Ａ）、
式（２）

（式（２）中、Ｘ^１はアルキル基、アルケニル基、又はアリールアルキル基であり、Ｙ^１及びＹ^２はそれぞれ独立に、ポリオキシアルキレン基である。）
で表されるアミン（Ｂ）、
式（３）

（式（３）中、Ｒはアルキル基、アルケニル基、アリール基、又はアリールアルキル基を表す。）
で表されるガレート化合物（Ｃ）、並びに有機溶媒（Ｄ）を含む、組成物を提供する。 [Composition]
The present disclosure provides formula (1)

(In formula (1), A is an alkylene group.)
A conductive polymer/polyanion complex (A) consisting of a polythiophene (a1) and a sulfonion group-containing polymer (a2) represented by
formula (2)

(In formula (2), X ¹ is an alkyl group, an alkenyl group, or an arylalkyl group, and Y ¹ and Y ² are each independently a polyoxyalkylene group.)
Amine (B) represented by
Formula (3)

(In Formula (3), R represents an alkyl group, an alkenyl group, an aryl group, or an arylalkyl group.)
Provided is a composition comprising a gallate compound (C) represented by and an organic solvent (D).

<Conductive polymer/polyanion complex (A): Also referred to as component (A). ＞
The component (A) is composed of a conductive polymer, polythiophene (a1), and a dopant, a sulfonion group-containing polymer (a2). (A) A component can be used individually or in 2 or more types.

（式（１）中、Ａはアルキレン基である。Ａは炭素数１～１２のアルキレン基が好ましい。）
で表される。（ａ１）成分は、単独又は２種以上で使用され得る。 (Polythiophene (a1): Also referred to as component (a1).)
(a1) component is represented by formula (1)

(In formula (1), A is an alkylene group. A is preferably an alkylene group having 1 to 12 carbon atoms.)
is represented by The component (a1) may be used singly or in combination of two or more.

Component (a1) is exemplified by poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butenedioxythiophene) and the like. Among these, poly(3,4-ethylenedioxythiophene) (hereinafter referred to as PEDOT) is particularly preferable in terms of conductivity.

The component (a1) can be obtained by a known chemical oxidation 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 can be mentioned. is immersed, and a conductive polymer is formed thereon. In the polymerization, water or an organic solvent (D) component described later may be used as a solvent.

Oxidizing agents include metal salt-based oxidizing agents [ferric chloride, ferric sulfate, ferric nitrate, cupric chloride, aluminum chloride, etc.], non-metallic salt-based oxidizing agents [ammonium peroxodisulfate, peroxodisulfate, sodium sulfate, potassium peroxodisulfate, boron trifluoride, ozone, benzoyl peroxide, oxygen, etc.] and the like.

(Sulfonion group-containing polymer (a2): Also referred to as component (a2).)
The sulfonion group-containing polymer is a doping component for component (a1). Component (a2) may be a homopolymer of a sulfonic acid-based polymerizable monomer, a copolymer of a sulfonic acid-based polymerizable monomer and a polymerizable monomer having no sulfanion group, or any other known component without particular limitation. can be (a2) component can be used individually or in 2 or more types.

In addition, the "sulfonion group" means a sulfo group or a monosubstituted sulfoester group which is an anionic functional group. The "monosubstituted sulfoester group" refers to a sulfoester group in which the hydrogen on the hydroxyl group is substituted with an alkyl group (having about 1 to 20 carbon atoms).

Sulfonic acid-based polymerizable monomers include vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, methallyloxybenzenesulfonic acid, allyloxybenzenesulfonic acid, and 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)acrylatesulfonic acid (CH ₂ = C(CH ₃ )—COO—(CH ₂ ) ₂ —SO ₃ H), propyl (meth)acrylate sulfonate (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 ) _{2CH 2} —SO ₃ H), (meth)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 allylic acid sulfonic acid (CH ₂ ═CHCH ₂ —COO—(CH ₂ ) ₂ —SO ₃ H), t-butyl allylic acid (CH ₂ ═CHCH ₂ —COO—C(CH ₃ ) ₂ CH ₂ —SO ₃ H), ethyl 4-pentenoate (CH ₂ ═CH( CH ₂ ) ₂ -COO-(CH ₂ ) ₂ -SO ₃ H), 4-pentenoic acid propylsulfonic 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( _CH3 ) _{2CH2 -SO3H} ), 4-pentenoic _acid phenylenesulfonic acid ( _CH2 =CH( _CH2 ) _2- COO- _{C6H4 -} SO3H ₎ , 4-pentenoic acid naphthalenesulfonic acid (CH ₂ ═CH(CH ₂ ) ₂ —COO—C ₁₀ H ₈ —SO ₃ H), acrylamide -t-butylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, cyclobutene-3-sulfonic acid, salts thereof (sodium salt, etc.), and the like.

Polymerizable monomers having no sulfonion group include aromatic monomers [styrene, p-methylstyrene, p-ethylstyrene, p-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, α-methyl styrene, 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-1,3-butadiene, etc.], non-alicyclic monoene [2-hydroxy -1,3-butadiene, ethylene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, etc.], alicyclic monoene [cyclopropene, cyclobutene, cyclopentene , cyclohexene, cycloheptene, cyclooctene, 2-methylcyclohexene, etc.], imidazole-based monomers [1-vinylimidazole, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, N-vinyl-2-pyrrolidone, N-vinyl Acetamide, N-vinylformamide, N-vinylimidazole, etc.], acrylamides [(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-vinylformamide, 3-acrylamidephenyl boronic acid, etc.], amine-based monomers [acryloylmorpholine, vinylamine, N,N-dimethylvinylamine, N,N-diethylvinylamine, N,N-dibutylvinylamine, N,N-di-t-butylvinylamine, 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.]. be.

Component (a2) has good doping performance and contributes to the stability of the organic solvent dispersion of component (A), which will be described later. Ethyl sulfonic acid, polybutyl acrylate sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic carboxylic acid, poly methacrylic carboxylic acid Acid, poly-2-acrylamido-2-methylpropanecarboxylic acid, and polyisoprenecarboxylic acid, polyacrylic acid, and at least one selected from the group consisting of salts thereof, particularly polystyrene sulfonic acid and / or salts thereof ( In particular, sodium salt) (hereinafter sometimes collectively referred to as PSS) is preferred.

The method of doping the component (a1) with the component (a2) is not particularly limited. At the time (during the polymerization of the precursor monomer), a method of allowing the component (a2) to coexist in the reaction system is exemplified.

(A) When the component is prepared as an aqueous solution or aqueous dispersion, various known methods (JP 2008-045116, JP 2008-156452, JP 2008-222850, JP 2011 -208016, etc.). Specifically, for example, when an aqueous solution or aqueous dispersion of PEDOT/PSS is used as the component (A), it is dried by various known drying means (such as a spray dryer) to obtain a blue color of PEDOT/PSS. A solid can be obtained, which can be used as component (A).

The component (A) is particularly selected from PEDOT and PSS in terms of chemical stability as a conductive polymer / dopant complex, conductivity, hue and transparency of the coating made of the conductive composition of the present invention, etc. A complex (hereinafter referred to as PEDOT/PSS) is preferred. Examples of commercially available PEDOT/PSS products include "Clevios P" (trade name; manufactured by Heraeus) and "Orgacon" (trade name; manufactured by Agfa-Gewalt Japan Ltd.).

The upper and lower limits of the content of component (A) in 100% by mass of the composition are 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, Examples include 0.5, 0.1, 0.09, 0.05, 0.04, 0.01, 0.005, 0.002% by mass. In one embodiment, the content of component (A) in 100% by mass of the composition is preferably 0.002 to 5% by mass.

［式（２）中、Ｘ^１はアルキル基（例えば炭素数１～４０のアルキル基）、アルケニル基（例えば炭素数２～４０のアルケニル基）、又はアリールアルキル基（例えば炭素数７～４０のアリールアルキル基）であり、Ｙ^１及びＹ^２はそれぞれ独立に、ポリオキシアルキレン基である。］
で表される。（Ｂ）成分は、単独又は２種以上で使用され得る。 <Amine (B): Also referred to as component (B). ＞
(B) component is the formula (2)

[In formula (2), X ¹ is an alkyl group (eg, an alkyl group having 1 to 40 carbon atoms), an alkenyl group (eg, an alkenyl group having 2 to 40 carbon atoms), or an arylalkyl group (eg, a arylalkyl group), and Y ¹ and Y ² are each independently a polyoxyalkylene group. ]
is represented by (B) A component can be used individually or in 2 or more types.

Component (B) is 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/oxypropylene)-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)-triacontylamine, N,N-poly(oxypropylene)-triacontylamine, N,N-poly(oxyethylene/oxypropylene)-triacontylamine, etc. are exemplified.

The upper and lower limits of the content of component (B) in 100% by mass of the composition are 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.5, 0.1, 0.09, 0.05, 0.04, 0.01, 0.005, 0.002, 0.001% by mass and the like are exemplified. In one embodiment, the content of component (B) in 100% by mass of the composition is preferably 0.001 to 10% by mass.

（式（３）中、Ｒはアルキル基、アルケニル基、アリール基、又はアリールアルキル基を表す。）
で表される。（Ｃ）成分は、単独又は２種以上で使用され得る。 <Gallate compound (C): Also referred to as component (C). ＞
(C) component is the formula (3)

(In Formula (3), R represents an alkyl group, an alkenyl group, an aryl group, or an arylalkyl group.)
is represented by (C) A component can be used individually or in 2 or more types.

Examples of component (C) include gallic acid alkyl esters, gallic acid alkenyl esters, gallic acid aryl esters, and gallic acid arylalkyl esters.

Examples of gallic acid alkyl esters include gallic acid linear alkyl esters, gallic acid branched alkyl esters, gallic acid cycloalkyl esters, and the like.

Gallic acid linear alkyl esters include methyl gallate, ethyl gallate, propyl gallate, n-butyl gallate, n-pentyl gallate, n-hexyl gallate, n-heptyl gallate, n-octyl gallate, n-nonyl gallate, n-decamethyl gallate, n-undecyl gallate, n-dodecyl gallate, n-tridecyl gallate, n-tetradecyl gallate, n-pentadecyl gallate, n-hexadecyl gallate, gallic acid n-heptadecyl, n-octadecyl gallate (stearyl gallate), n-nonadecyl, n-icosyl gallate, n-heneicosyl gallate, n-docosyl gallate, n-tricosyl gallate, n-tetracosyl gallate, gallic acid Examples include n-pentacosyl gallate, n-hexacosyl gallate, n-heptacosyl gallate, n-octacosyl gallate, n-nonacosyl gallate, and n-triacontyl gallate.

Gallic acid branched alkyl esters include i-propyl gallate, i-butyl gallate, s-butyl gallate, t-butyl gallate, i-pentyl gallate, neopentyl gallate, t-pentyl gallate, gallic acid i-hexyl and the like are exemplified.

Gallic acid cycloalkyl esters include cyclopentyl gallate, cyclohexyl gallate, cycloheptyl, cyclodecyl gallate, 3,5,5-trimethylcyclohexyl gallate, tricyclodecyl gallate, adamantyl gallate, norbornyl gallate, and bicyclo gallate. Decyl and the like are exemplified.

Gallic acid alkenyl esters are exemplified by vinyl gallate and allyl gallate.

Gallic acid aryl esters are exemplified by phenyl gallate and the like.

Gallic acid arylalkyl esters are exemplified by benzyl gallate and the like.

The upper and lower limits of the content of component (C) in 100% by mass of the composition are 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, Examples include 0.5, 0.1, 0.09, 0.05, 0.04, 0.01, 0.005, 0.002, 0.001% by mass. In one embodiment, the content of component (C) in 100% by mass of the composition is preferably 0.001 to 5% by mass.

The upper and lower limits of the content of component (C) with respect to 100% by mass of component (A) are 5000, 4000, 2500, 1000, 900, 750, 500, 400, 300, 250, 100, 90, 75, 73, 50. , 30, 25, 10, 5, 2, 1, 0.1, 0.01, 0.002% by mass, and the like. In one embodiment, the content of component (C) is preferably 0.002 to 5000% by mass with respect to 100% by mass of component (A).

<Organic solvent (D): Also referred to as component (D). ＞
(D) A component can be used individually or in 2 or more types. Component (D) is exemplified by non-ether monoalcohol solvents, non-ether diol solvents, ether solvents, ketone solvents, alicyclic hydrocarbon solvents, ester solvents, nitrile solvents, nitrogen-containing compound solvents, sulfur-containing compound solvents, and the like. .

Non-ether monoalcoholic solvents are exemplified by methanol, ethanol, propanol, butanol, isopropyl alcohol and the like.

Examples of non-ether diol solvents include ethylene glycol, neopentyl glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol.

Examples of ether solvents include dioxane, diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, propylene glycol monomethyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether and the like.

Ketone solvents are exemplified by acetone, methyl ethyl ketone, methyl isobutyl ketone and the like.

Aromatic hydrocarbon solvents are exemplified by benzene, toluene, xylene and the like.

The alicyclic hydrocarbon solvent is exemplified by cyclohexane, methylcyclohexane and the like.

Ester solvents are exemplified by ethyl formate, ethyl acetate and the like.

Nitrile solvents are exemplified by acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile and the like.

Nitrogen-containing compound solvents are exemplified by N-methyl-2-pyrrolidone, 3-methyl-2-oxazolidinone, N,N-dimethylformamide, N,N-dimethylacetamide and the like. the

Examples of sulfur-containing compound solvents include dimethylsulfoxide and hexamethylene phosphortriamide.

The upper and lower limits of the content of component (D) in 100% by mass of the composition are 45, 40, 35, 30, 25, 20% by mass and the like are exemplified. In one embodiment, the content of component (D) in 100% by mass of the composition is preferably 20 to 99.996% by mass.

<Polymerizable unsaturated carbon bond-containing compound (E): Also referred to as component (E). ＞
In one embodiment, the composition may contain a polymerizable unsaturated carbon bond-containing compound (E). (E) A component can be used individually or in 2 or more types.

Component (E) is exemplified by polymer poly(meth)acrylates, oligomer poly(meth)acrylates, and the like.

In the present disclosure, "(meth)acryl" means "at least one selected from the group consisting of acryl and methacryl." Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". "(Meth)acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl".

(polymer poly(meth)acrylate)
In the present disclosure, "polymer poly(meth)acrylate" means a polymer having two or more (meth)acryloyl groups.

Polymer poly(meth)acrylates can be produced by known techniques. Examples of the method for producing the polymer poly(meth)acrylate include a method of reacting an epoxy group-containing (meth)acrylic copolymer with an α,β-unsaturated carboxylic acid. An epoxy group-containing (meth)acrylic copolymer can be produced by a known method using an epoxy group-containing (meth)acrylate.

α,β-unsaturated carboxylic acids are exemplified by (meth)acrylic acid and the like.

The epoxy group-containing (meth)acrylate is exemplified by glycidyl (meth)acrylate and the like.

Examples of monomers other than those described above that can be used in the production of polymer poly(meth)acrylates include non-hydroxyl-containing alkyl(meth)acrylates and hydroxyl-containing alkyl(meth)acrylates.

Examples of hydroxyl-free alkyl (meth)acrylates include hydroxyl-free linear alkyl (meth)acrylates, hydroxyl-free branched alkyl (meth)acrylates, and hydroxyl-free cycloalkyl (meth)acrylates.

Linear alkyl (meth)acrylates not containing hydroxyl groups include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and hexyl (meth)acrylate. , heptyl (meth)acrylate, octyl (meth)acrylate, hexadecyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, icosyl (meth)acrylate, docosyl (meth)acrylate, etc. are exemplified.

Hydroxyl group-free branched alkyl (meth)acrylates include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-(meth)acrylate. Ethylhexyl and the like are exemplified.

Examples of hydroxyl-free cycloalkyl (meth)acrylates include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate.

Examples of hydroxyl-containing alkyl (meth)acrylates include hydroxyl-containing linear alkyl (meth)acrylates, hydroxyl-containing branched alkyl (meth)acrylates, and hydroxyl-containing cycloalkyl (meth)acrylates. From the viewpoint of the pot life of the undercoating agent, it is preferable that the hydroxyalkyl group has about 1 to 4 carbon atoms.

Examples of hydroxyl group-containing linear alkyl (meth)acrylates include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

Examples of hydroxyl group-containing branched alkyl (meth)acrylates include 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate.

Examples of hydroxyl group-containing cycloalkyl (meth)acrylates include hydroxycyclohexyl (meth)acrylate and 4-(hydroxymethyl)cyclohexylmethyl (meth)acrylate.

(oligomer poly(meth)acrylate)
Examples of oligomer poly(meth)acrylates include (poly)pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, and hydroxyl group-containing glycerin di(meth)acrylate.

（式中、ｍは０以上の整数であり、Ｒ^ｐ１～Ｒ^ｐ６は、それぞれ独立に水素原子、又は（メタ）アクリロイル基であり、Ｒ^ｐ１～Ｒ^ｐ６の少なくとも１つが（メタ）アクリロイル基である。なお、Ｒ^ｐ３及びＲ^ｐ５は、各構成単位ごとに基が異なっていてもよい。）
により示される化合物である。 ((poly)pentaerythritol poly(meth)acrylate)
(Poly)pentaerythritol poly(meth)acrylate has the structural formula (E1)

(Wherein, m is an integer of 0 or more, R ^p1 to R ^p6 are each independently a hydrogen atom or a (meth)acryloyl group, and at least one of R ^p1 to R ^p6 is a (meth)acryloyl group. Note that R ^p3 and R ^p5 may have different groups for each structural unit.)
It is a compound represented by

In the present disclosure, "(poly)pentaerythritol poly(meth)acrylate" means "at least one selected from the group consisting of pentaerythritol poly(meth)acrylate and polypentaerythritol poly(meth)acrylate".

Ｒ^ｐ３ＡとＲ^ｐ３Ｂとは異なる基であってよく、Ｒ^ｐ５ＡとＲ^ｐ５Ｂとは異なる基であってよいことを意味する（以下同様）。 Further, "each structural unit may have a different group" means, for example, when m is 2 in Structural Formula (E1),

It means that R ^p3A and R ^p3B may be different groups, and R ^p5A and R ^p5B may be different groups (the same shall apply hereinafter).

Examples of pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

Polypentaerythritol poly(meth)acrylate is dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa (meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, Examples include tripentaerythritol hepta(meth)acrylate and tripentaerythritol octa(meth)acrylate.

（式中、ｐは０以上の整数であり、Ｒ^ｐ７～Ｒ^ｐ１０は水素原子、又は（メタ）アクリロイル基であり、Ｒ^ｐ７～Ｒ^ｐ１０の少なくとも１つが（メタ）アクリロイル基である。なお、Ｒ^ｐ９は、各構成単位ごとに基が異なっていてもよい。）
により示される化合物である。 ((poly)trimethylolpropane poly(meth)acrylate)
(Poly)trimethylolpropane poly(meth)acrylate has the structural formula (E2)

(In the formula, p is an integer of 0 or more, R ^p7 to R ^p10 are hydrogen atoms or (meth)acryloyl groups, and at least one of R ^p7 to R ^p10 is a (meth)acryloyl group. R ^p9 may have different groups for each structural unit.)
It is a compound represented by

In the present disclosure, "(poly)trimethylolpropane poly(meth)acrylate" means "at least one selected from the group consisting of trimethylolpropane poly(meth)acrylate and polytrimethylolpropane poly(meth)acrylate". means.

Examples of trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate and trimethylolpropane tri(meth)acrylate.

Examples of polytrimethylolpoly(meth)acrylate include ditrimethyloldi(meth)acrylate, ditrimethyloltri(meth)acrylate, ditrimethyloltetra(meth)acrylate and the like.

（式中、Ｒ^ｐ１１～Ｒ^ｐ１３が、（メタ）アクリロイル基又は水素原子であり、Ｒ^ｐ１１～Ｒ^ｐ１３の少なくとも１つが、（メタ）アクリロイル基である。）
により示される化合物である。 (glycerin (poly) (meth) acrylate)
Glycerin (poly)(meth)acrylate has the structural formula (E3)

(In the formula, R ^p11 to R ^p13 are (meth)acryloyl groups or hydrogen atoms, and at least one of R ^p11 to R ^p13 is a (meth)acryloyl group.)
It is a compound represented by

In the present disclosure, "glycerin (poly)(meth)acrylate" means "at least one selected from the group consisting of glycerin poly(meth)acrylate and glycerin (meth)acrylate".

Glycerin poly(meth)acrylate is exemplified by glycerin di(meth)acrylate, glycerin tri(meth)acrylate and the like.

The upper and lower limits of the content of component (E) in 100% by mass of the composition are 5, 3, 1, 0.5, 0.1, 0% by mass and the like are exemplified. In one embodiment, the content of component (E) in 100% by mass of the composition is preferably 0 to 75% by mass.

<Photoinitiator (F): Also referred to as component (F). ＞
In one embodiment, the active energy ray-curable resin composition contains a photopolymerization initiator. Two or more photopolymerization initiators may be used in combination. Photoinitiators include 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-cyclohexylphenylketone, 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, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone and the like. A photopolymerization initiator is used when ultraviolet curing is performed, but is not necessarily required when electron beam curing is performed.

The upper and lower limits of the content of component (F) in 100% by mass of the composition are exemplified by 10, 9, 5, 3, 1, 0.5, 0.1 and 0% by mass. In one embodiment, the content of component (F) in 100% by mass of the composition is preferably 0 to 10% by mass.

<Additive>
The above composition may contain, as an additive, an agent that does not fall under any of the above components (A) to (F).

Additives include conductive polymers other than component (A), such as polythiophene vinylenes, polypyrroles, polyfurans, and polyanilines, amine-based surfactants other than component (B), non-amine-based nonionic surfactants, and the like. exemplified.

In one embodiment, the content of the additive is exemplified by less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, and 0 part by mass with respect to 100 parts by mass of the solid content of the composition. be. Further, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc. are exemplified with respect to 100 parts by mass of any one of components (A) to (F).

The above composition can be produced by dispersing and mixing components (A) to (D), and optionally components (E) to (F) and additives by various known means. In addition, the addition order of each component is not specifically limited. Further, various known devices (emulsification disperser, ultrasonic dispersion device, etc.) can be used as the dispersing/mixing means.

In one embodiment, the composition is an active energy ray-curable composition. Also, in one embodiment, the composition can be used as a coating agent, an antistatic coating agent, a conductive coating agent.

[Hardened material]
The present disclosure provides a cured product of the above composition. In one embodiment, the cured product is obtained by irradiating the composition with active energy rays such as ultraviolet rays, electron beams, and radiation.

The active energy rays used for the curing reaction are exemplified by ultraviolet rays and electron beams. As the ultraviolet light source, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp can be used. In addition, the amount of light, the arrangement of the light source, the transport speed, etc. can be adjusted as necessary. / min. On the other hand, in the case of electron beams, curing is preferably carried out at an electron beam accelerator having an acceleration voltage of approximately 10 to 300 kV at a conveying speed of approximately 5 to 50 m/min.

[Goods]
The present disclosure provides an article containing the cured product.

The articles described above can be manufactured by various known methods. Examples of the method for producing the article include a method of applying the above composition to at least one surface of a base film (substrate), drying if necessary, and then irradiating active energy rays. In addition, the non-coated surface of the obtained base film is coated with the composition according to the present embodiment, another base film is laminated thereon, and then active energy rays are irradiated to produce a laminated article. You can also

As the base film (substrate), various known ones can be adopted. Base films include polycarbonate films, acrylic films (polymethyl methacrylate films, etc.), polystyrene films, polyester films, polyolefin films, epoxy resin films, melamine resin films, triacetylcellulose films, ABS films, AS films, norbornene resin films, A cyclic olefin film, a polyvinyl alcohol film, etc. are illustrated. Although the thickness of the base film is not particularly limited, it is preferably about 15 to 100 μm.

Examples of the coating method include bar coater coating, wire bar coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing and the like.

The coating amount is not particularly limited, but the weight after drying is preferably about 0.1 to 30 g/m ² , more preferably 1 to 20 g/m ² .

Hereinafter, the present invention will be described in detail through examples and comparative examples. However, the above description of preferred embodiments and the following examples are provided for illustrative purposes only and not for the purpose of limiting the invention. Accordingly, the scope of the present invention is not limited to the embodiments or examples specifically described herein, but only by the claims. Further, in each example and comparative example, numerical values such as parts and % are based on mass unless otherwise specified.

<Preparation of component (A)>
Preparation example 1
1000 g of a commercially available PEDOT/PSS aqueous dispersion (trade name “Orgacon”, solid content concentration 1.2% by weight) was dried using a spray dryer (product name “GA-32”, manufactured by Yamato Scientific Co., Ltd.). Treatment (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 preparing the conductive composition.

Example 1
Into a beaker, 1.20 g of the solid component (A) obtained in Preparation Example 1 (hereinafter abbreviated as P/P) and 96.4 g of ethanol are added. : After adding 2.40 g of Liponol C/18-18, manufactured by Lion Specialty Chemicals Co., Ltd., an emulsifying disperser (product name: Clearmix, manufactured by M Technique Co., Ltd., hereinafter the same). After treatment at a rotation speed of 18000 rpm for 10 minutes, an ultrasonic disperser (19.6 kHz, manufactured by Ginsen Co., Ltd.; hereinafter the same) is used to treat for 10 minutes at an output of 400 W, thereby solid content A composition with a concentration of 3.6% by weight was obtained. Next, the composition was added with 0.87 g of stearyl gallate as component (C), 123.89 g of ethanol and 40.59 g of ethylene glycol as component (D), and dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. 160.95 g of a mixture (trade name "Aronix M-400", manufactured by Toagosei Co., Ltd.) and 8.70 g of a photopolymerization initiator (trade name "OMNIRAD 2959", manufactured by IGM Resins B.V.) were added. , to obtain a composition (solid concentration: about 40% by weight).

Examples other than Example 1 and Comparative Examples were carried out in the same manner as in Example 1 except that the components were changed as shown in Table 1.

(Production of film)
Each active energy ray-curable resin composition was coated on a 100 μm-thick PET film (Lumirror 100U483 manufactured by Toray Industries, Inc.) with a bar coater (model number “No. 24 ”, manufactured by Daiichi Rika Co., Ltd.) and dried for 1 minute in a drier at 80° C. to prepare a film. Then, the obtained film was treated with an ultraviolet curing device (product name: UBT-080-7A/BM, manufactured by Multiply Co., Ltd., high pressure mercury lamp 300 mJ/cm ² ) to obtain a film having a cured coating. Table 1 shows the following evaluation results for the produced films.

<Antistatic property test>
The surface resistance of the film immediately after production was measured using a commercially available resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., product name "Hiresta MCP-HT-450") according to JIS K 6911 at an applied voltage of 500V.
1×10 ¹³ Ω/sq≧・・・〇1×10 ¹³ Ω/sq<・・・×

<Heat resistance test>
The produced film was heated in a dryer at 170° C. for 30 minutes. The surface resistance of the film after the test was measured in the same manner as described above. In addition, the film after the test was measured by the transmission method with a color difference meter (trade name: ZE 6000, manufactured by Nippon Denshoku Industries Co., Ltd.), and if the yellow index value (YI value) after heating was less than 4, it was evaluated as "○". , 4 or more were classified as "x".

ＢＨＴ：２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール
アデカスタブＡＯ－６０：ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］
ライトエステルＰ－１Ｍ：リン酸エステルアクリレート

BHT: 2,6-di-tert-butyl-p-cresol adekastab AO-60: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
Light ester P-1M: Phosphate ester acrylate

Claims (4)

formula (1)

(In formula (1), A is an alkylene group.)
A conductive polymer/polyanion complex (A) consisting of a polythiophene (a1) and a sulfonion group-containing polymer (a2) represented by
formula (2)

(In formula (2), X ¹ is an alkyl group, an alkenyl group, or an arylalkyl group, and Y ¹ and Y ² are each independently a polyoxyalkylene group.)
Amine (B) represented by
Formula (3)

(In formula (3), R is n-hexadecyl group, n-heptadecyl group, n-octadecyl group (stearyl group), n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n- tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, or n-triacontyl group.)
A composition comprising a gallate compound (C) represented by and an organic solvent (D). The composition according to claim 1, comprising a polymerizable unsaturated carbon bond-containing compound (E). A cured product of the composition according to claim 1 or 2. An article comprising the cured product of claim 3.