JP2019131768A - Conductive polymer dispersion liquid and method for producing the same, and method for producing conductive film - Google Patents

Abstract

To provide a conductive polymer dispersion liquid that can easily form a conductive layer having sufficiently excellent conductivity and soil resistance, and provide a method for producing a conductive film that can easily produce a conductive film having a conductive layer having sufficiently excellent conductivity and soil resistance.SOLUTION: A conductive polymer dispersion liquid contains a conductive complex containing a π-conjugated conductive polymer and a polyanion, a specific acrylate compound having a perfluoropolyether group, and a dispersion medium. A method for producing a conductive film includes applying a conductive polymer dispersion liquid to a film substrate, and optionally irradiating it with an active energy ray.SELECTED DRAWING: None

Description

  The present invention relates to a conductive polymer dispersion containing a π-conjugated conductive polymer, a method for producing the same, and a method for producing a conductive film.

A conductive film having a conductive layer formed on the surface of a plastic substrate is used in applications requiring antistatic properties, such as packaging or containers for electronic parts, packaging or containers for foods, and the like.
As the conductive material contained in the conductive layer, a π-conjugated conductive polymer may be used because it is excellent in conductivity and transparency and is stable without depending on humidity. .
As a method for producing a conductive film, for example, a conductive polymer dispersion in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is dispersed in water is applied to a film substrate and dried. A method of forming a conductive layer and obtaining a conductive film is known (Patent Document 1).
The conductive layer of the conductive film may be required to have antifouling properties. As a method for improving the antifouling property, it is known that in a conductive polymer dispersion, a silicone-modified acrylic resin is blended in addition to a conductive complex containing a π-conjugated conductive polymer and a polyanion (patent) Reference 2).

International Publication No. 2015/108001 JP 2008-156452 A

However, the conductive polymer dispersion described in Patent Document 2 could not form a conductive layer having both excellent conductivity and antifouling property. That is, in the conductive polymer dispersion described in Patent Document 2, when the amount of the silicone-modified acrylic resin is increased in order to increase the antifouling property, the conductivity tends to decrease. When the amount of the acrylic resin was reduced, the antifouling property tended to decrease.
An object of this invention is to provide the electroconductive polymer dispersion which can form easily the electroconductive layer which was excellent in both electroconductivity and antifouling property, and its manufacturing method. Moreover, an object of this invention is to provide the manufacturing method of the electroconductive film which can manufacture an electroconductive film provided with the electroconductive layer excellent in both electroconductivity and antifouling property easily.

The present invention includes the following aspects.
[1] Conductivity containing a π-conjugated conductive polymer and a conductive complex containing a polyanion, an acrylate compound having a perfluoropolyether group represented by the following formula (1), and a dispersion medium Polymer dispersion.

[In the formula (1), Rf is a difluoro perfluoropolyether group having a molecular weight of 500 or more and 30000 or less and may contain a branch in the middle,
X ¹ is independently of each other a group represented by the following formula (2):

(In the formula (2), a and c are each independently 0 or more and 4 or less, b is an integer of 1 or more and 4 or less, provided that a + b + c is 2, 3 or 4, and R ¹ is independently of each other the following formula ( 3) a group represented by

(In the formula (3), d, e, f and g are integers of 0 or more and 20 or less independently of each other within the range where the molecular weight of R ¹ is 30 or more and 600 or less, and the arrangement of each repeating unit is random. R ³ is a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms.
R ² is an acrylic group or α-substituted acrylic group-containing group represented by the following formula (4),

(In Formula (4), R ⁴ is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and R ⁵ is at least one of an ether bond and an ester bond having 1 to 18 carbon atoms. A divalent or trivalent linking group optionally containing n. N is an integer of 1 or 2.)
Q ¹ and Q ² are divalent linking groups that may contain an ether bond, an ester bond, an amide bond, or a urethane bond having 3 to 20 carbon atoms, each independently containing a cyclic structure or a branch. They may be the same or different. )
X ² is independently a group represented by the following formula (5),

(In Formula (5), R ¹ , R ² , Q ¹ and Q ² are the same as in Formula (2), h, i and j are each independently an integer of 0 or more and 3 or less, and h + i + j is 1 Any one of the values above and below 3, and the arrangement of the repeating units may be random.)
Z is a divalent organic group, may contain an oxygen atom, a nitrogen atom, or a fluorine atom, or may be a group having a cyclic structure or an unsaturated bond, and v is an integer of 0 or more and 5 or less. It is. ]

[2] The conductive polymer dispersion according to [1], wherein Rf in the formula (1) of the acrylate compound includes 1 to 500 repeating units represented by the following formula (6).
-C _i F _2i O- (6)
(I is an integer of 1 to 6 independently for each unit.)
[3] The conductive polymer dispersion according to [1] or [2], wherein Rf in the formula (1) of the acrylate compound is selected from groups represented by any of the following formulas (7) to (9): .

(In Formula (7), Y is independently F or CF ₃ group, r is an integer of 2 or more and 6 or less, m and n are each independently an integer of 0 or more and 200 or less, provided that m + n is 2 or more and 200 or less. S is an integer of 0 to 6, and each repeating unit may be bonded at random.)

(In formula (8), j is an integer from 1 to 3, and k is an integer from 1 to 200.)

(In Formula (9), Y is F or CF ₃ group, j is an integer of 1 or more and 3 or less, m and n are each independently an integer of 0 or more and 200 or less, provided that m + n is 2 or more and 200 or less. (Repeating units may be combined randomly.)

[4] The conductive polymer dispersion according to any one of [1] to [3], wherein Z in the formula (1) of the acrylate compound is any group of the following formulas (10) to (14): liquid.

[5] Any of [1] to [4], wherein Q ¹ and Q ² in the formula (2) of the acrylate compound are each independently any group of the following formulas (15) to (20) A conductive polymer dispersion according to any one of the above.

[6] The conductive polymer according to any one of [1] to [5], wherein R ² in Formula (2) of the acrylate compound is any group of Formulas (21) to (24) below: Dispersion.

[7] The conductive polymer dispersion according to any one of [1] to [6], wherein R ¹ in the formula (2) of the acrylate compound is a group represented by the following formula (25).

(P and q in the formula (25) are each independently an integer of 0 or more and 20 or less, p + q is 1 or more and 40 or less, the propylene group in the formula may be branched, and each repeating unit is randomly selected. May be combined.)

[8] The conductive polymer dispersion according to any one of [1] to [7], wherein the dispersion medium is an organic solvent.
[9] The conductive polymer dispersion according to any one of [1] to [8], wherein an amine compound is bonded to a part of the anion group of the polyanion.
[10] The conductive polymer dispersion according to any one of [1] to [8], wherein an epoxy compound is bonded to a part of the anion group of the polyanion.

[11] A method for producing a conductive polymer dispersion for producing the conductive polymer dispersion according to [9], wherein an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion Adding an amine compound, precipitating the conductive composite to form a precipitate, recovering the precipitate, and adding the acrylate compound and an organic solvent to the recovered precipitate; A process for producing a conductive polymer dispersion.
[12] A method for producing a conductive polymer dispersion for producing the conductive polymer dispersion according to [9], wherein an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion A method for producing a conductive polymer dispersion, comprising: a step of freeze-drying to obtain a freeze-dried product; and a step of adding an amine compound, the acrylate compound and an organic solvent to the freeze-dried product.
[13] A method for producing a conductive polymer dispersion for producing the conductive polymer dispersion according to [10], wherein an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion An epoxy compound is added to the conductive composite to form a precipitate, a step of collecting the precipitate, and a step of adding the acrylate compound and the organic solvent to the collected precipitate. A process for producing a conductive polymer dispersion.
[14] A method for producing a conductive film, comprising applying the conductive polymer dispersion according to any one of [1] to [10] to a film substrate.
[15] The method for producing a conductive film according to [14], wherein the conductive polymer dispersion is applied to a film substrate, then dried and irradiated with active energy rays.

According to the conductive polymer dispersion of the present invention, a conductive layer excellent in both conductivity and antifouling property can be easily formed.
According to the method for producing a conductive polymer dispersion of the present invention, the conductive polymer dispersion can be easily produced.
According to the method for producing a conductive film of the present invention, it is possible to easily produce a conductive film including a conductive layer having both excellent conductivity and antifouling property.

<Conductive polymer dispersion>
One embodiment of the conductive polymer dispersion of the present invention will be described.
The conductive polymer dispersion of this embodiment contains a conductive composite, an acrylate compound represented by the formula (1) (hereinafter referred to as “acrylate compound (A)”), and a dispersion medium.

(Conductive composite)
The conductive composite in this embodiment includes a π-conjugated conductive polymer and a polyanion.
In this embodiment, the polyanion is coordinated to the π-conjugated conductive polymer, and the anion group of the polyanion is doped into the π-conjugated conductive polymer, so that a conductive composite having conductivity is formed.
In the polyanion, all the anion groups are not doped into the π-conjugated conductive polymer and have an excess anion group. In this embodiment, it is preferable that at least one of the amine compound and the epoxy compound is bonded to at least a part of the surplus anion group. If at least one of the amine compound and the epoxy compound is bonded to the surplus anion group, the conductive composite can be hydrophobized. The hydrophobic conductive composite is excellent in affinity with the acrylate compound (A).

[Π-conjugated conductive polymer]
The π-conjugated conductive polymer is not particularly limited as long as it has the effect of the present invention as long as the main chain is an organic polymer composed of π-conjugated system. For example, polypyrrole-based conductive polymer, polythiophene-based polymer Conductive polymer, polyacetylene conductive polymer, polyphenylene conductive polymer, polyphenylene vinylene conductive polymer, polyaniline conductive polymer, polyacene conductive polymer, polythiophene vinylene conductive polymer, and These copolymers are exemplified. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-hexylthiophene). , Poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene) , Poly (3-hydroxythiophene), poly (3-methoxythiophene), poly ( -Ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly ( 3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyl) Oxythiophene), poly (3,4-didecyloxythiophene), poly (3, -Didodecyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4 -Methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), Poly (3-methyl-4-carboxybutylthiophene) is mentioned.
Examples of the polypyrrole conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and poly (3-butyl Pyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3 -Carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole) , Poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyl) Oxy pyrrole), poly (3-methyl-4-hexyloxy-pyrrole) and the like.
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), and poly (3-anilinesulfonic acid).
Among the π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity, transparency, and heat resistance.
The π-conjugated conductive polymer contained in the conductive composite may be one type or two or more types.

[Polyanion]
The polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anion group of the polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene sulfone. Polymers having a sulfonic acid group such as acid, polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzenesulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid , Polymers having a carboxylic acid group such as polymethacrylcarboxylic acid, poly (2-acrylamido-2-methylpropanecarboxylic acid), polyisoprene carboxylic acid, polyacrylic acid and the like. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
Among these polyanions, a polymer having a sulfonic acid group is preferable, and polystyrene sulfonic acid is more preferable because conductivity can be further increased.
The said polyanion may be used individually by 1 type, and may use 2 or more types together.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight of the polyanion was determined by measuring the elution time using gel permeation chromatography (GPC), and obtained based on a calibration curve of elution time versus molecular weight in advance from a polystyrene standard having a known molecular weight. That is.

When at least one of an amine compound and an epoxy compound is bonded to a part of the anion group of the polyanion, a hydrophobic substituent can be formed. By forming a hydrophobic substituent on the polyanion with at least one of an amine compound and an epoxy compound, the hydrophobicity of the conductive composite increases. The bond may be a covalent bond, an ionic bond, a coordination bond, or a hydrogen bond.
Although detailed analysis of the conductive complex is not always easy, it is assumed that a hydrophobic substituent represented by -HNR ¹ R ² R ³ is formed by the reaction between the anion group of the polyanion and the amine compound. The R ¹ , R ² and R ³ are substituents derived from an amine compound described later. For example, at least one of R ¹ , R ² , and R ³ is a hydrocarbon group (provided that at least one hydrogen atom of the hydrocarbon group may be substituted with an alkyl group, an aryl group, a hydroxy group, etc.). It is. Of R ¹ , R ² and R ³ , those which are not hydrocarbon groups are hydrogen atoms.
By reaction of the anionic group and the epoxy compound of polyanion, it is presumed that the hydrophobic substituent represented by -CH ₂ CHOHR ⁴ is formed. R ⁴ is a substituent derived from an epoxy compound described later. For example, R ⁴ is a hydrocarbon group (provided that at least one hydrogen atom of the hydrocarbon group may be substituted with an alkyl group, an aryl group, a hydroxy group, etc.).
The hydrophobic substituent is bonded to the oxygen atom of the anionic group.

The amine compound is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. An amine compound may be used individually by 1 type, and may use 2 or more types together.
Examples of the primary amine include aniline, toluidine, benzylamine, and ethanolamine.
Examples of secondary amines include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, and dinaphthylamine.
Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, trinaphthylamine and the like.
Of the amine compounds, a tertiary amine is preferable, and at least one of tributylamine and trioctylamine is more preferable because the conductive polymer dispersion of this embodiment can be easily produced.

An epoxy compound is a compound having one or more epoxy groups in one molecule. In terms of preventing aggregation or gelation, the epoxy compound is preferably a compound having one epoxy group in one molecule.
An epoxy compound may be used individually by 1 type, and may use 2 or more types together.

  Examples of the monofunctional epoxy compound having one epoxy group in one molecule include propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, 1,2- Epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monooxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2-epoxyoctadecane, 1,2-epoxyhexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2- (chloromethyl) -1,2-epoxypropane, glycidol, epichlorohydrin, epibromohy Phosphorus, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2- (chloromethyl) -1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2-epoxy-1H , 1H, 2H, 2H, 3H, 3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-methyl -1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H, 1H, 2H, 2H, 3H, 3H-hepta Decafluorobutane, 3,4-epoxytetrahi Lofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxy succinic acid, glycidyl phenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzyl glycidyl ether, diethoxy (3-glycidyloxypropyl) Methylsilane, 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl-3- (3-glycidyloxypropyl) trisiloxane, 9,10-epoxy-1,5-cyclododecadiene, glycidyl 4-tert-butylbenzoate, 2,2-bis (4-glycidyloxyphenyl) propane, 2-tert-butyl-2- [2- (4 -Chlorophenyl)] ethyloxirane Styrene oxide, glycidyl trityl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α, 6α-epoxide, stilbene oxide, glycidyl p-toluenesulfonate, 3-methyl -3-ethyl phenylglycidate, N-propyl-N- (2,3-epoxypropyl) perfluoro-n-octylsulfonamide, (2S, 3S) -1,2-epoxy-3- (tert-butoxycarbonyl) Amino) -4-phenylbutane, 3-nitrobenzenesulfonic acid (R) -glycidyl, 3-nitrobenzenesulfonic acid-glycidyl, parthenolide, N-glycidylphthalimide, endrin, dieldrin, 4-glycidyloxycarbazole, 7, - dimethyl octanoic acid [oxiranylmethyl], 1,2-epoxy-4-vinyl cyclohexane, C12, C13 mixed higher alcohol glycidyl ether.

  Examples of the polyfunctional epoxy compound having two or more epoxy groups in one molecule include 1,6-hexanediol diglycidyl ether, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, and 4-butanediol. Diglycidyl ether, 1,2: 3,4-diepoxybutane, 1,2-cyclohexanedicarboxylic acid diglycidyl, isocyanuric acid triglycidyl neopentyl glycol diglycidyl ether, 1,2: 3,4-diepoxybutane, polyethylene glycol Diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol di Ricidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin Examples include polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol-based polyglycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, and triglycidyl tris (2-hydroxyethyl) isocyanate.

  The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass to 1000 parts by mass with respect to 100 parts by mass of the π-conjugated conductive polymer, and 10 parts by mass to 700 parts by mass. It is more preferable that it is in the range of 100 parts by mass or more and 500 parts by mass or less. If the content ratio of the polyanion is not less than the lower limit, the doping effect on the π-conjugated conductive polymer tends to become strong, and the conductivity becomes higher. On the other hand, if the content of the polyanion is not more than the above upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

(Acrylate compound (A))
The acrylate compound (A) in this embodiment is an acrylate compound having a perfluoropolyether group represented by the formula (1).
In the formula (1), Rf is a difluoro perfluoropolyether group having a molecular weight of 500 or more and 30000 or less, and may contain a branch in the middle.
Rf is preferably a divalent perfluoropolyether residue containing 1 to 500 repeating units represented by the following formula (6).
-C _i F _2i O- (6)
I in Formula (6) is an integer of 1 or more and 6 or less independently for each unit.
More preferably, Rf is a perfluoropolyether residue represented by any one of formulas (7) to (9).
In formula (7), each Y is independently F or CF ₃ group. r is an integer of 2 or more and 6 or less, m and n are each independently an integer of 0 or more and 200 or less, provided that m + n is 2 or more and 200 or less. s is an integer of 0 or more and 6 or less. Each repeating unit may be bonded at random.
In Formula (8), j is an integer of 1 to 3, and k is an integer of 1 to 200.
In formula (9), Y is an F or CF ₃ group. j is an integer of 1 to 3, m and n are each independently an integer of 0 to 200, provided that m + n is 2 to 200. Each repeating unit may be bonded at random.

In the formula (1), X ¹ is a group represented by the formula (2) independently of each other.
In the formula (2), a and c are each independently 0 or more and 4 or less, b is an integer of 1 or more and 4 or less, provided that a + b + c is 2, 3, or 4.

In Formula (2), Q ¹ and Q ² are each independently a divalent linking group that may contain an ether bond, an ester bond, an amide bond, or a urethane bond having 3 to 20 carbon atoms, A ring structure or a branch may be included, and each may be the same or different.
Q ¹ and Q ² are preferably groups of any one of formulas (15) to (20), independently of each other.

R ¹ is independently a group represented by the formula (3).
In the formula (3), d, e, f, and g are independently 0 to 20 and preferably 1 to 10 in a range where the molecular weight of R ¹ is 30 to 600, preferably 60 to 300. Is an integer. The arrangement of each repeating unit may be random.
R ³ in the formula (3) is a saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 10 carbon atoms.
Examples of the saturated hydrocarbon group or unsaturated hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, Examples include an allyl group, a butenyl group, and a styryl group. Among these, a methyl group or an ethyl group is preferable.

Of the R ^1, the group represented by the formula (25) is preferable.
In formula (25), p and q are each independently an integer of 0 to 20, and p + q is 1 to 40. The propylene group in formula (25) may be branched. Each repeating unit may be bonded at random.

R ² is a monovalent organic group having 1 to 20 carbon atoms and having either an acrylic group represented by the formula (4) or an α-substituted acrylic group.
In the formula (4), R ⁴ is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and among them, a hydrogen atom or a methyl group is preferable.
R ⁵ in Formula (4) is a divalent or trivalent linking group having 1 to 18 carbon atoms, and may contain at least one of an ether bond and an ester bond.
N in Formula (4) is an integer of 1 or 2.
R ² is preferably a group of any one of the above formulas (21) to (24), and among them, a group having an ethylene group is preferable.

In Formula (2), when a> 1, a preferable combination of R ¹ and Q ¹ is as follows. A combination in which R ¹ is any ^one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group and Q ¹ is any ^one of a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group is preferable.
In the formula (2), when b> 1, a preferable combination of R ² and Q ² is as follows. A combination in which R ² is any one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group and Q ² is any one of a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group is preferable.
In the formula (2), when c> 1, preferable Q ² is any one of a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.
In the formula (2), in the case of a> 1, b> 1, a compound obtained by further combining the preferable combination of R ¹ and Q ¹ and the preferable combination of R ² and Q ² is preferable.
In the formula (2), when a> 1, c> 1, a compound obtained by further combining the preferable combination of R ¹ and Q ¹ with the preferable Q ² is preferable.
In the formula (2), when b> 1 and c> 1, a compound in which the combination of the preferable R ² and Q ² and the preferable Q ² are further combined is preferable.
In the formula (2), when a> 1, b> 1, c> 1, the preferred combination of R ¹ and Q ¹ , the preferred combination of R ² and Q ^2, and the preferred Q ² The compound which combined these further is preferable.

In Formula (1), X ² is a group represented by Formula (5), independently of each other.
In the formula (5), R ¹ , R ² , Q ¹ and Q ² are the same as in the formula (2).
In the formula (5), h, i, and j are each independently an integer of 0 or more and 3 or less, and h + i + j is any one of 1, 2, and 3. The arrangement of repeating units may be random. )

In formula (1), Z is a divalent organic group and may contain an oxygen atom, a nitrogen atom, or a fluorine atom. Z may be a cyclic structure or a group having an unsaturated bond, and v is an integer of 0 or more and 5 or less.
The structure of Z is not particularly limited as long as it does not inhibit the polymerization of acrylic groups. Preferable Z includes any group of the formulas (10) to (14).
More preferable examples of Z include groups represented by any of the following formulas (26) to (33). More preferable Z includes a group represented by the following formula (28) or formula (29).

An acrylate compound may be used individually by 1 type, and may use 2 or more types together.
A method for synthesizing the acrylate compound (A) is described in, for example, JP 2010-285501 A.

  In the conductive polymer dispersion of this embodiment, the content of the acrylate compound (A) is preferably 0.01 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the conductive complex. The amount is more preferably no less than 500 parts by mass and even more preferably no less than 0.1 parts by mass and no greater than 100 parts by mass. If content of an acrylate compound (A) is more than the said lower limit, antifouling property of a conductive layer can be improved more, and if it is more than the said lower limit, sufficient electroconductivity can be ensured.

(Other acrylate compounds)
The conductive polymer dispersion of this embodiment may contain an acrylate compound other than the acrylate compound (A) (hereinafter referred to as “acrylate compound (B)”). The acrylate compound (B) may be an acrylate compound containing a fluorine atom or an acrylate compound not containing fluorine. An acrylate compound that does not contain fluorine is preferable because it is easily available and the conductivity hardness can be easily increased.

Examples of the acrylate compound (B) that does not contain fluorine include urethane acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and isocyanuric acid ethylene oxide modified. Di (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, Hydrogen phthalate- (2,2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meta Bifunctional to hexafunctional (meth) acrylic compounds such as acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, etc. Can be mentioned.
In addition, the acrylate compound (B) containing no fluorine is an epoxy acrylate obtained by reacting the (meth) acrylic compound with an epoxy compound, a copolymer in which a (meth) acryloyl group is introduced into the side chain of the acrylic ester copolymer. It may be a polymer or the like.
An acrylate compound (B) may be used individually by 1 type, and may use 2 or more types together.

Among the acrylate compounds (B), urethane acrylate is preferable because it has excellent reactivity with the acrylate compound (A) and can easily increase the hardness of the conductive layer.
Urethane acrylate is a compound obtained by reacting a polyisocyanate having two or more isocyanate groups with a (meth) acrylate having a hydroxy group, a polyisocyanate and a polyester of a terminal diol reacting with a (meth) acrylate having a hydroxy group. And compounds obtained by reacting a polyisocyanate obtained by reacting an excess of a diisocyanate with a polyol, a (meth) acrylate having a hydroxy group, and the like.
Among urethane acrylates, (hydroxy) (meth) acrylate having a hydroxy group selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate, hexamethylene diisocyanate, A urethane acrylate obtained by reacting a polyisocyanate selected from isophorone diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate is preferred.

  When the conductive polymer dispersion of this embodiment contains the acrylate compound (B), the content of the acrylate compound (B) is 0.1 parts by mass or more and 10,000 parts by mass with respect to 100 parts by mass of the acrylate compound (A). Part or less, preferably 0.5 part by weight or more and 5000 parts by weight or less, and more preferably 1.0 part by weight or more and 1000 parts by weight or less. If content of an acrylate compound (B) is more than the said lower limit, it can fully react with an acrylate compound (A), and can raise the hardness of a conductive layer. If content of an acrylate compound (B) is below the said upper limit, the electroconductivity of a conductive layer is securable.

(Dispersion medium)
In the conductive polymer dispersion of this embodiment, when the conductive composite is hydrophobized, it is preferable to use an organic solvent as the main component of the dispersion medium. However, the dispersion medium is not limited to the organic solvent, and may contain water.
As the organic solvent, it is preferable to use an alcohol solvent, a ketone solvent, or an ester solvent, and more preferably at least one of a ketone solvent and an alcohol solvent since the dispersibility of the conductive composite can be increased. . The organic solvent is preferably a solvent that does not contain fluorine.
Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol (also referred to as isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and allyl. Examples include alcohol, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether.
Examples of the ketone solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate and the like.

Specifically, the content of the organic solvent in the conductive polymer dispersion is preferably 50% by mass or more and less than 100% by mass when the conductive polymer dispersion is 100% by mass, and 80% by mass. The content is more preferably less than 100% by mass, and still more preferably 90% by mass or more and less than 100% by mass. The conductive polymer dispersion may not contain any water.
In the conductive polymer dispersion of this embodiment, the content of the conductive composite with respect to the total mass of the conductive polymer dispersion is preferably, for example, from 0.1% by mass to 20% by mass, More preferably, the content is greater than or equal to 10% by weight and less than or equal to 10% by weight, more preferably greater than or equal to 1.0% and less than or equal to 5.0% by weight.

(High conductivity agent)
The conductive polymer dispersion may contain a high conductivity agent in order to further improve the conductivity of the conductive layer. Here, the above-described π-conjugated conductive polymer, polyanion, amine compound, epoxy compound, acrylate compound (A), acrylate compound (B) and organic solvent are not classified as highly conductive agents.
The highly conductive agent is a saccharide, a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxy groups, a compound having one or more hydroxy groups and one or more carboxy groups, a compound having an amide group, It is preferably at least one compound selected from the group consisting of a compound having an imide group and a lactam compound.
The highly conductive agent contained in the conductive polymer dispersion may be one type or two or more types.
The content ratio of the highly conductive agent is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, with respect to 100 parts by mass of the conductive composite. More preferably, it is at least 2,500 parts by mass. If the content ratio of the high conductive agent is equal to or higher than the lower limit value, the effect of improving the conductivity due to the addition of the high conductive agent is sufficiently exerted, and if it is equal to or lower than the upper limit value, the concentration of the π-conjugated conductive polymer is decreased. It is possible to prevent a decrease in conductivity due to the above.

(Additive)
The conductive polymer dispersion may contain other known additives.
The additive is not particularly limited as long as the effects of the present invention can be obtained. For example, a polymerization initiator, a surfactant, an inorganic conductive agent, an antifoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber, or the like is used. it can. However, the additive is composed of a compound other than the above-described π-conjugated conductive polymer, polyanion, amine compound, epoxy compound, acrylate compound (A), acrylate compound (B), organic solvent and high conductivity agent.
Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. The acrylate compound (A) and the acrylate compound (B) can be cured by radical polymerization when irradiated with active energy rays in the presence of a photopolymerization initiator.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferred from the viewpoint of storage stability. Further, a polymer surfactant such as polyvinyl pyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving a metal salt in water.
Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone oil.
Examples of the coupling agent include a silane coupling agent having a vinyl group or an amino group.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and saccharides.
Examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. Is mentioned.
When the conductive polymer dispersion contains the additive, the content ratio is appropriately determined according to the type of the additive. For example, the content is 0. 10 parts by mass with respect to 100 parts by mass of the solid content of the conductive composite. The range can be 001 parts by mass or more and 5 parts by mass or less.

(Method for producing conductive polymer dispersion)
The conductive polymer dispersion used in this embodiment can be produced by the following method (a) or (b).
(A) A step of adding at least one of an amine compound and an epoxy compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, and depositing the conductive complex to form a precipitate. And a step of recovering the precipitate, and a step of adding the acrylate compound (A) and an organic solvent to the recovered precipitate.
(B) a step of lyophilizing an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion to obtain a lyophilized product, and at least one of an amine compound and an epoxy compound in the lyophilized product, Adding an acrylate compound (A) and an organic solvent.

  The aqueous dispersion of the conductive composite used in the methods (a) and (b) is an aqueous dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, and water. . The aqueous dispersion may contain an organic solvent, but since the conductive composite is not hydrophobized at this point, it is preferable that the content of the organic solvent is small from the viewpoint of enhancing the dispersibility of the conductive composite. . Specifically, the content of the organic solvent in the aqueous dispersion is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more and 30% by mass or less, and 0% by mass. More preferably, it is 10 mass% or less.

Examples of a method for producing an aqueous dispersion of a conductive composite include a method in which a monomer that forms a π-conjugated conductive polymer is chemically oxidatively polymerized in an aqueous solution of a polyanion.
In addition, as the aqueous dispersion of the conductive composite, a commercially available aqueous dispersion containing a conductive composite of a π-conjugated conductive polymer and a polyanion may be used.
A known catalyst may be applied to the chemical oxidative polymerization. For example, a catalyst and an oxidizing agent can be used. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidizing agent can return the reduced catalyst to its original oxidation state.
The solid content concentration of the conductive composite contained in the aqueous dispersion of the conductive composite is preferably 0.1% by mass or more and 10% by mass or less with respect to the total mass of the aqueous dispersion. More preferably, it is at least 5% by mass.

In the method (a), when at least one of an amine compound and an epoxy compound is added to the aqueous dispersion, a part of an anion group of the polyanion constituting the conductive composite, specifically a π-conjugated system At least one of an amine compound and an epoxy compound is added to an anionic group that does not participate in doping the conductive polymer, and the anionic group disappears. Thereby, the conductive composite is hydrophobized.
However, at least one of the amine compound and the epoxy compound may not be added to all the anionic groups not participating in the doping to the π-conjugated conductive polymer, and a part of the anionic groups not participating in the doping may remain. .
Since the hydrophobic conductive composite cannot be dispersed in the aqueous dispersion medium, it precipitates into a precipitate.

  When adding an amine compound, the addition amount of the amine compound is preferably 1 part by mass or more and 100000 parts by mass or less, and preferably 10 parts by mass or more and 50000 parts by mass or less with respect to 100 parts by mass of the conductive composite. Is more preferable, and more preferably 50 parts by mass or more and 10,000 parts by mass or less. If the addition amount of the amine compound is not less than the lower limit, the hydrophobicity of the conductive composite can be sufficiently improved, and if it is not more than the upper limit, it is possible to prevent the conductivity of the conductive layer from being lowered.

  When adding an epoxy compound, it is preferable that the addition amount of an epoxy compound is 10 to 10,000 mass parts with respect to 100 mass parts of conductive composites, and is 100 to 5000 mass parts. Is more preferably 200 parts by mass or more and 500 parts by mass or less. If the addition amount of the epoxy compound is not less than the above lower limit value, the hydrophobicity of the conductive composite can be sufficiently improved, and if it is not more than the above upper limit value, it is possible to prevent the conductivity of the conductive layer from being lowered.

  When depositing the conductive composite, an organic solvent may be added. Examples of the organic solvent added at the time of precipitation include alcohol solvents, ketone solvents, and ester solvents. The organic solvent added in the case of precipitation may be used individually by 1 type, and may use 2 or more types together.

  Before adding at least one of the amine compound and the epoxy compound to the conductive polymer aqueous dispersion, during the addition, or after the addition, the conductive polymer aqueous dispersion may be heated to promote the reaction.

  In the step of collecting the precipitate in the method (a), for example, a well-known sorting method such as filtration, precipitation, or extraction can be applied. Among these fractionation methods, filtration is preferable, and it is preferable to perform filtration using a coarse filter so that the polyanion used for forming the conductive complex passes along with the filtrate. According to this filtration method, the precipitate can be separated and the excess polyanion not forming the conductive complex can be left on the filtrate side to separate the precipitate from the excess polyanion. By removing the excess polyanion, the conductivity of the precipitate can be increased.

  As the filter used for filtration, filter paper used in the chemical analysis field is preferable. Examples of the filter paper include a filter paper manufactured by Advantech, and a reserved particle diameter of 7 μm. Here, the retained particle diameter of the filter paper is a measure of the roughness of the eyes, and is obtained from the leaked particle diameter when barium sulfate or the like specified by JIS P 3801 [filter paper (for chemical analysis)] is naturally filtered. The retained particle diameter of the filter paper can be, for example, 2 μm or more and 20 μm or less. The retained particle diameter is preferably 5 μm or more and 10 μm or less because it can be easily separated by permeating excess polyanions.

In the step of adding the acrylate compound (A) and the organic solvent to the precipitate in the method of (a), after adding the acrylate compound (A) and the organic solvent to the precipitate, the precipitate and the acrylate compound (A) are included. It is preferable to disperse the organic solvent.
In the dispersion process, it is preferable to use a disperser. Examples of the disperser include a homogenizer, a high-pressure homogenizer, and a bead mill. Among the dispersers, a high-pressure homogenizer is preferable in that the dispersibility of the precipitate in the organic solvent can be increased.
Examples of the high-pressure homogenizer include an apparatus including a high-pressure generating unit that pressurizes a liquid to be dispersed and an opposing collision unit, an orifice unit, or a slit unit that performs dispersion. A known high pressure pump such as a plunger pump is used as the high pressure generator. Specific examples of the high-pressure homogenizer include a trade name Nanomizer manufactured by Yoshida Kikai Kogyo Co., Ltd., a trade name Microfluidizer manufactured by Microfluidics, and an optimizer manufactured by Sugino Machine.

In the lyophilization in the method (b), the water in the aqueous dispersion of the conductive composite is frozen and vacuum dried. Thereby, a freeze-dried product is obtained.
The temperature during lyophilization is preferably -60 to 60 ° C, more preferably -40 to 40 ° C. If the lyophilization temperature is equal to or higher than the lower limit, it is easy to adjust the temperature, and if the lyophilization temperature is equal to or lower than the upper limit, the aqueous dispersion of the conductive composite can be easily lyophilized.

When at least one of the amine compound and the epoxy compound, the acrylate compound (A), and the organic solvent are added to the lyophilized product, the order of addition is not particularly limited.
After adding at least one of the amine compound and the epoxy compound, the acrylate compound (A) and the organic solvent to the lyophilized product, it is preferable to perform a dispersion treatment. If the dispersion treatment is performed, the dispersibility of the conductive composite in the conductive polymer dispersion can be improved. The distributed processing is the same as the distributed processing in the method (a).

  In the methods (a) and (b), the acrylate compound (B), the highly conductive agent and the additive may be added as appropriate, but it is preferably added together with the organic solvent.

(Function and effect)
The conductive polymer dispersion of this embodiment contains an acrylate compound (A) having a perfluoropolyether group in addition to the conductive composite. Since this acrylate compound (A) has a radically polymerizable double bond, it can be polymerized and cured when the conductive layer is formed. The cured product of the acrylate compound (A) is a fluororesin.
In general, a fluororesin has high water and oil repellency and excellent antifouling properties. The cured product of the acrylate compound (A) in this embodiment has particularly high water repellency and oil repellency, and is particularly excellent in antifouling properties.
In addition, the cured product of the acrylate compound in this embodiment hardly inhibits the conductivity exhibited by the conductive composite in the conductive layer. Therefore, the conductive layer formed from the conductive polymer dispersion of this aspect is excellent in conductivity.
Also, the acrylate compound (A) is excellent in affinity with the acrylate compound (B) containing no fluorine and the organic solvent containing no fluorine, and the acrylate compound (B) containing no fluorine and the organic solvent containing no fluorine Hard to separate and easy to use.
Furthermore, the acrylate compound (A) can be cured by irradiating active energy rays in the presence of a photopolymerization initiator.

<Conductive film>
One aspect of the method for producing a conductive film of the present invention will be described.
The conductive film in this aspect includes a film base and a conductive layer formed on at least one surface of the film base.

Examples of the resin constituting the film substrate include polyolefin resin, ethylene-vinyl acetate copolymer resin, ethylene-methyl methacrylate copolymer resin, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate. Phthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene elastomer, polyester elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate, etc. Can be mentioned. Examples of the polyolefin resin include polyethylene, polypropylene, ethylene-α olefin copolymer resin, and propylene-α olefin copolymer resin.
Further, the film substrate may be unstretched or stretched.

The average thickness of the film substrate is preferably 10 μm or more and 500 μm or less, and more preferably 20 μm or more and 200 μm or less. If the average thickness of the film substrate is equal to or greater than the lower limit value, it is difficult to break, and if it is equal to or less than the upper limit value, sufficient flexibility as a film can be ensured.
The thickness of the film substrate is a value obtained by measuring the thickness of any 10 or more locations using an optical microscope or an electron microscope and averaging the measured values.

The conductive layer in this aspect is a layer formed by applying the conductive polymer dispersion liquid of the above aspect. Therefore, the conductive layer in this embodiment contains at least the conductive composite and a cured product of the acrylate compound (A).
When the conductive polymer dispersion further contains the acrylate compound (B), the conductive layer in this embodiment is a cured product of the acrylate compound (B), the acrylate (A), and the acrylate compound (B). ) And a cured product.
Further, when the conductive polymer dispersion further contains at least one of a high conductivity agent and an additive, the conductive layer further contains at least one of the high conductivity agent and the additive.

The average thickness of the conductive layer is preferably 10 nm or more and 20000 nm or less, more preferably 20 nm or more and 10,000 nm or less, and further preferably 30 nm or more and 5000 nm or less. If the average thickness of the conductive layer is not less than the lower limit, sufficiently high conductivity and antifouling properties can be exhibited, and if the average thickness is not more than the upper limit, the conductive layer can be easily formed.
The thickness of the conductive layer is a value obtained by measuring the thickness of any 10 or more locations using an optical microscope or an electron microscope and averaging the measured values.

The conductive layer is formed by coating the conductive polymer dispersion on at least one surface of the film substrate.
Examples of the method for applying the conductive polymer dispersion include a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a fountain coater, a rod coater, an air doctor coater, a knife coater, A method using a coater such as a blade coater, cast coater or screen coater, a spray method using a sprayer such as air spray, airless spray or rotor dampening, a dipping method or the like can be applied.
Of these, a bar coater may be used because the conductive polymer dispersion can be easily applied. In the bar coater, the coating thickness varies depending on the type, and in the commercially available bar coater, a number is assigned to each type, and the larger the number, the thicker the coating can be made.

After coating the conductive polymer dispersion, it is preferable to dry the coated conductive polymer dispersion.
Examples of the drying method include heat drying and vacuum drying. As heat drying, for example, a normal method such as hot air heating or infrared heating can be employed.
When heat drying is applied, the heating temperature is usually in the range of 50 ° C. or higher and 150 ° C. or lower, preferably 60 ° C. or higher and 130 ° C. or lower, more preferably 70 ° C. or higher and 120 ° C. or lower. Here, the heating temperature is a set temperature of the drying apparatus.
Also, the drying time is preferably 5 minutes or more from the viewpoint of sufficiently removing the dispersion medium.

The acrylate compound (A) contained in the conductive polymer dispersion is cured by irradiation with active energy rays in the presence of a photopolymerization initiator. Therefore, when the conductive polymer dispersion contains a photopolymerization initiator, active energy rays may be irradiated after the coated conductive polymer dispersion is dried.
Examples of the active energy ray include ultraviolet rays, electron beams, and visible rays. As the ultraviolet light source, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used.
The illuminance upon UV irradiation is preferably 100 mW / cm ² or more. When the illuminance is less than 100 mW / cm ² , the active energy ray-curable binder component may not be sufficiently cured. Further, the integrated light quantity is preferably 50 mJ / cm ² or more. If the integrated light quantity is less than 50 mJ / cm ² , crosslinking may not be sufficient. In addition, the illumination intensity and integrated light quantity in this specification are using Topcon UVR-T1 (industrial UV checker, light receiver; UD-T36, measurement wavelength range: 300 nm to 390 nm, peak sensitivity wavelength: about 355 nm). It is a measured value.

In the method for producing a conductive film of this embodiment, a dispersion containing the acrylate compound (A) in addition to the conductive composite is used as the conductive polymer dispersion applied to the film substrate. Therefore, the conductive layer formed from the conductive polymer dispersion has both excellent conductivity and antifouling properties.
Therefore, according to the method for producing a conductive film of this aspect, it is possible to easily produce a conductive film including a conductive layer that is sufficiently excellent in both conductivity and antifouling property.

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

(Production Example 2)
14.2 g of 3,4-ethylenedioxythiophene and a solution obtained by dissolving 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 in 2000 ml of ion-exchanged water were mixed at 20 ° C. While stirring the mixed solution obtained at 20 ° C., 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added. The reaction was stirred for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solvent was removed using an ultrafiltration method. This operation was repeated three times. Next, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the resulting solution, and about 2000 ml of solvent was removed using an ultrafiltration method. 2000 ml of ion-exchanged water was added to the remaining liquid, about 2000 ml of the solvent was removed using an ultrafiltration method, and polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS) was washed with water. This operation was repeated 8 times to obtain a PEDOT-PSS aqueous dispersion having a solid concentration of 1.2% by mass.

(Production Example 3)
2.5 g of 3,4-ethylenedioxythiophene and 12.5 g of a solution of polystyrene sulfonic acid of Production Example 1 dissolved in 500 ml of ion-exchanged water were mixed at 30 ° C.
While maintaining the mixed solution at 30 ° C. with stirring, 5.5 g of ammonium persulfate and 0.15 g of ferric sulfate oxidation catalyst solution dissolved in 44.35 ml of ion exchange water were slowly added. And stirred for 8 hours to react. As a result, a 2.7% by mass polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) aqueous dispersion (PEDOT-PSS aqueous dispersion) was obtained.
A mixed solution of 53.0 g of trioctylamine and 500 g of isopropanol was added to 565.0 g of the PEDOT-PSS aqueous dispersion to precipitate a trioctylamine adduct of PEDOT-PSS. The precipitated trioctylamine adduct of PEDOT-PSS was collected by filtration and washed with 100 g of water, and then washed with 100 g of acetone, and 18.8 g of PEDOT-PSS trioctylamine adduct was taken out as a solid.
To the obtained solid, 3760 g of isopropanol was added and subjected to dispersion treatment using a high-pressure homogenizer to obtain a conductive polymer dispersion.

(Production Example 4)
1000 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was freeze-dried to obtain 12 g of a freeze-dried product.
5.0 g of the lyophilized product and 1.4 g of tributylamine were added to 1000 g of isopropanol, and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion.

(Production Example 5)
To 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 300 g of methanol and 25 g of an epoxy compound (Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.) are added, and 4 at 60 ° C. Stir with heating for hours. At this time, since the epoxy group of the epoxy compound reacted with the sulfonic acid group of PSS, the free sulfonic acid group disappeared, the water dispersibility of PEDOT-PSS was lowered, and PEDOT-PSS was precipitated. The resulting precipitate was collected by filtration. 1.575 g of the precipitate was added to 315 g of methyl ethyl ketone and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion.

(Production Example 6)
300 g of methanol and 25 g of butylene oxide were added to 100 g of the aqueous PEDOT-PSS dispersion obtained in Production Example 2, and the mixture was heated and stirred at 60 ° C. for 4 hours. At this time, since the epoxy group of butylene oxide reacted with the sulfonic acid group of PSS, the free sulfonic acid group disappeared, the water dispersibility of PEDOT-PSS was lowered, and PEDOT-PSS was deposited. The resulting precipitate was collected by filtration. 1.45 g of the precipitate was added to 290 g of methyl ethyl ketone and dispersed using a high pressure homogenizer to obtain a conductive polymer dispersion.

(Production Example 7)
Under a dry nitrogen atmosphere, in a 2000 ml three-necked flask equipped with a reflux device and a stirrer, 500 g of perfluoropolyether having α-unsaturated bonds at both ends represented by the following formula (34), 700 g of m-xylene hexafluoride , And 361 g of tetramethylcyclotetrasiloxane were added and heated to 90 ° C. with stirring. To this mixture, 0.442 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (including 1.1 × 10 ⁻⁶ mol of platinum alone) was added, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours. After confirming disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure, and activated carbon treatment was performed. As a result, 498 g of a colorless and transparent liquid perfluoropolyether-containing compound represented by the following formula (35) was obtained (Compound I).

Under a dry air atmosphere, 7.05 g of 2-allyloxyethanol, 50.0 g of m-xylene hexafluoride, and a toluene solution of a chloroplatinic acid / vinylsiloxane complex in an amount of 0.000 with respect to 50.0 g of compound (I). 0442 g (including 1.1 × 10 ⁻⁷ mol of platinum alone) was mixed and stirred at 100 ° C. for 4 hours. After confirming disappearance of the Si-H group by ¹ H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, and activated carbon treatment was performed. As a result, 55.2 g of a pale yellow transparent liquid perfluoropolyether-containing compound represented by the following formula (36) was obtained (Compound II).

Under a dry air atmosphere, 50.0 g of Compound (II) and 50.0 g of tetrahydrofuran and 9.00 g of acryloyloxyethyl isocyanate were mixed and heated to 50 ° C. Dioctyltin laurate 0.05g was added to the mixture obtained by this, and it stirred at 50 degreeC for 24 hours. After completion of the heating, vacuum distillation was performed at 80 ° C. and 2 Torr. As a result, 58.7 g of a pale yellow paste-like substance was obtained (Compound III). ^From the results of ¹ H-NMR and IR, it was confirmed to be an acrylate compound represented by the following formula (37).

(Production Example 8)
Example 1 except that instead of 2-allyloxyethanol, 11.9 g of a compound represented by the following formula (38) and 7.05 g of acryloyloxyethyl isocyanate were used for 50 g of compound (I). In the same procedure, 56.1 g of an acrylate compound represented by the following formula (39) was obtained (Compound IV).

(Production Example 9)
In a dry nitrogen atmosphere, 50.0 g of a fluorine-containing cyclic siloxane represented by the following formula (40) and 20.0 g of toluene were charged into a 100 ml three-necked flask equipped with a reflux apparatus and a stirring apparatus, and the mixture was stirred up to 90 ° C. Heated. To the mixture thus obtained, 9.75 g of polyoxyethylene methyl allyl ether represented by the following formula (41) and 0.0110 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (2.73 × 10 ⁻ as a simple substance of platinum). containing ⁸ mol.) mixed solution was added dropwise over 1 hour to obtain a reaction solution was stirred for 12 hours at 90 ° C..
Separately, in a 100 ml three-necked flask equipped with a reflux apparatus and a stirrer in a dry nitrogen atmosphere, 16.9 g of allyl alcohol was charged and heated to 90 ° C., and the reaction mixture once cooled to room temperature was added to the obtained reaction solution. After dropwise addition over time, the mixture was stirred at 90 ° C. for 16 hours. In the obtained solution, unreacted allyl alcohol was distilled off under reduced pressure at 100 ° C. and 6 Torr for 2 hours to obtain a compound (V).
Under a dry air atmosphere, 7.01 g of 2-isocyanatoethyl acrylate and 0.010 g of dioctyltin laurate were mixed with 60.0 g of the obtained compound (V), and the mixture was stirred at 25 ° C. for 12 hours. An acrylate compound having the average composition shown in (42) was obtained (Compound VI). In addition, RF in Formula (42) is the same as RF in Formula (40).

Example 1
40 g of the conductive polymer dispersion of Production Example 3, 1.4 g of the acrylate compound represented by Formula (37) of Production Example 7 and urethane acrylate (Negami Kogyo Co., Ltd. Art Resin UN904M, solid content concentration 80% by mass, 45.5 g of a methyl ethyl ketone solution), 1.5 g of a photopolymerization initiator (Irgacure 184 manufactured by BASF) and 11.6 g of diacetone alcohol were mixed to obtain a conductive polymer dispersion.
The obtained conductive polymer dispersion was designated as No.1. 6 bar coater was applied to one side of a polyethylene terephthalate film (Lumirror T-60 manufactured by Toray Industries, Inc.), dried at 100 ° C. for 1 minute, and then irradiated with 400 mJ ultraviolet rays. As a result, the conductive polymer dispersion applied to the polyethylene terephthalate film was cured to form a conductive layer to obtain a conductive film.

(Example 2)
A conductive film was obtained in the same manner as in Example 1 except that the conductive polymer dispersion of Production Example 3 was changed to the conductive polymer dispersion of Production Example 4.

Example 3
A conductive film was obtained in the same manner as in Example 1 except that the conductive polymer dispersion of Production Example 3 was changed to the conductive polymer dispersion of Production Example 5.

Example 4
A conductive film was obtained in the same manner as in Example 1 except that the conductive polymer dispersion of Production Example 3 was changed to the conductive polymer dispersion of Production Example 6.

(Example 5)
A conductive film was obtained in the same manner as in Example 1 except that the acrylate compound represented by Formula (37) in Production Example 7 was changed to the acrylate compound represented by Formula (39) in Production Example 8. .

(Comparative Example 1)
A conductive film was obtained in the same manner as in Example 1 except that the acrylate compound represented by Formula (37) in Production Example 7 was changed to the acrylate compound represented by Formula (42) in Production Example 9. .

(Comparative Example 2)
A conductive film was obtained in the same manner as in Example 1 except that the acrylate compound represented by the formula (37) in Production Example 7 was changed to trifluoroethyl methacrylate.

<Evaluation>
The surface resistance value of the conductive film in each example was measured using a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytech Co., Ltd.) under the conditions of an applied voltage of 10 V and an applied time of 10 seconds. The smaller the surface resistance value, the better the conductivity.
In the conductive film of each example, the contact angle of water and the contact angle of oleic acid were measured using an automatic contact angle meter DMs-200 (manufactured by Kyowa Interface Science Co., Ltd.). The greater the contact angle, the better the antifouling property.

<Result>
The conductive film of each Example provided with the conductive layer containing an acrylate compound (A) had a small surface resistance value and a large contact angle with water and a contact angle with oleic acid.
The conductive film of Comparative Example 1 in which the conductive layer contained the acrylate compound represented by Formula (42) of Production Example 9 instead of the acrylate compound (A) had a large surface resistance value and low conductivity.
The conductive film of Comparative Example 2 in which the conductive layer contained trifluoroethyl methacrylate instead of the acrylate compound (A) had a small contact angle with water and a contact angle with oleic acid, and had low antifouling properties.
From these results, it was shown that the conductive layer formed from the conductive polymer dispersion of the present invention is excellent in both conductivity and antifouling property.

Claims (15)

Conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an acrylate compound having a perfluoropolyether group represented by the following formula (1), and a dispersion medium liquid.

[In the formula (1), Rf is a difluoro perfluoropolyether group having a molecular weight of 500 or more and 30000 or less and may contain a branch in the middle,
X ¹ is independently of each other a group represented by the following formula (2):

(In the formula (2), a and c are each independently 0 or more and 4 or less, b is an integer of 1 or more and 4 or less, provided that a + b + c is 2, 3 or 4, and R ¹ is independently of each other the following formula ( 3) a group represented by

(In the formula (3), d, e, f and g are integers of 0 or more and 20 or less independently of each other within the range where the molecular weight of R ¹ is 30 or more and 600 or less, and the arrangement of each repeating unit is random. R ³ is a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms.
R ² is an acrylic group or α-substituted acrylic group-containing group represented by the following formula (4),

(In Formula (4), R ⁴ is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and R ⁵ is at least one of an ether bond and an ester bond having 1 to 18 carbon atoms. A divalent or trivalent linking group optionally containing n. N is an integer of 1 or 2.)
Q ¹ and Q ² are divalent linking groups that may contain an ether bond, an ester bond, an amide bond, or a urethane bond having 3 to 20 carbon atoms, each independently containing a cyclic structure or a branch. They may be the same or different. )
X ² is independently a group represented by the following formula (5),

(In Formula (5), R ¹ , R ² , Q ¹ and Q ² are the same as in Formula (2), h, i and j are each independently an integer of 0 or more and 3 or less, and h + i + j is 1 Any one of the values above and below 3, and the arrangement of the repeating units may be random.)
Z is a divalent organic group, may contain an oxygen atom, a nitrogen atom, or a fluorine atom, or may be a group having a cyclic structure or an unsaturated bond, and v is an integer of 0 or more and 5 or less. It is. ] 2. The conductive polymer dispersion according to claim 1, wherein Rf in Formula (1) of the acrylate compound includes 1 or more and 500 or less repeating units represented by Formula (6) below.
-C _i F _2i O- (6)
(I is an integer of 1 to 6 independently for each unit.) The conductive polymer dispersion according to claim 1 or 2, wherein Rf in the formula (1) of the acrylate compound is selected from groups represented by any of the following formulas (7) to (9).

(In Formula (7), Y is independently F or CF ₃ group, r is an integer of 2 or more and 6 or less, m and n are each independently an integer of 0 or more and 200 or less, provided that m + n is 2 or more and 200 or less. S is an integer of 0 to 6, and each repeating unit may be bonded at random.)

(In formula (8), j is an integer from 1 to 3, and k is an integer from 1 to 200.)

(In Formula (9), Y is F or CF ₃ group, j is an integer of 1 or more and 3 or less, m and n are each independently an integer of 0 or more and 200 or less, provided that m + n is 2 or more and 200 or less. (Repeating units may be combined randomly.) The conductive polymer dispersion according to any one of claims 1 to 3, wherein Z in the formula (1) of the acrylate compound is any group of the following formulas (10) to (14).

5. The acrylate compound according to claim ^1, wherein Q ¹ and Q ² in the formula (2) are each independently a group of the following formulas (15) to (20). Conductive polymer dispersion liquid.

The conductive polymer dispersion according to any one of claims 1 to 5, wherein R ² in the formula (2) of the acrylate compound is any group of the following formulas (21) to (24).

The conductive polymer dispersion according to any one of claims 1 to 6, wherein R ¹ in the formula (2) of the acrylate compound is a group represented by the following formula (25).

(P and q in the formula (25) are each independently an integer of 0 or more and 20 or less, p + q is 1 or more and 40 or less, the propylene group in the formula may be branched, and each repeating unit is randomly selected. May be combined.)   The conductive polymer dispersion according to any one of claims 1 to 7, wherein the dispersion medium is an organic solvent.   The conductive polymer dispersion according to any one of claims 1 to 8, wherein an amine compound is bonded to a part of the anion group of the polyanion.   The conductive polymer dispersion according to any one of claims 1 to 8, wherein an epoxy compound is bonded to a part of the anion group of the polyanion. A method for producing a conductive polymer dispersion for producing the conductive polymer dispersion according to claim 9, comprising:
adding an amine compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, and depositing the conductive complex to form a precipitate;
Recovering the precipitate;
Adding the acrylate compound and the organic solvent to the collected precipitate;
A process for producing a conductive polymer dispersion having: A method for producing a conductive polymer dispersion for producing the conductive polymer dispersion according to claim 9, comprising:
a step of lyophilizing an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion to obtain a lyophilized product;
Adding an amine compound, the acrylate compound and an organic solvent to the lyophilized product;
A process for producing a conductive polymer dispersion having: A method for producing a conductive polymer dispersion for producing the conductive polymer dispersion according to claim 10, comprising:
adding an epoxy compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, and depositing the conductive complex to form a precipitate;
Recovering the precipitate;
Adding the acrylate compound and the organic solvent to the collected precipitate;
A process for producing a conductive polymer dispersion having:   The manufacturing method of an electroconductive film which apply | coats the electroconductive polymer dispersion liquid as described in any one of Claim 1 to 10 to a film base material.   The method for producing a conductive film according to claim 14, wherein the conductive polymer dispersion is applied to a film substrate, then dried and irradiated with active energy rays.