JP7049125B2 - Conductive polymer dispersion liquid and its manufacturing method, and a method for manufacturing a conductive film - Google Patents

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 base material is used for applications requiring antistatic conditions, 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 has excellent conductivity and transparency and its conductivity is stable regardless of humidity. ..
As a method for producing a conductive film, for example, a conductive polymer dispersion liquid in which a conductive composite 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 film to obtain 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 enhancing antifouling property, it is known to add a silicone-modified acrylic resin in addition to a conductive composite containing a π-conjugated conductive polymer and a polyanion in a conductive polymer dispersion (patented). Document 2).

International Publication No. 2015/108001 Japanese Unexamined Patent Publication No. 2008-156452

However, the conductive polymer dispersion liquid described in Patent Document 2 could not form a conductive layer having sufficiently excellent conductivity and antifouling property. That is, in the conductive polymer dispersion liquid described in Patent Document 2, when the amount of the silicone-modified acrylic resin is increased in order to enhance the antifouling property, the conductivity tends to decrease, and the silicone-modified to enhance the conductivity. When the amount of acrylic resin was reduced, the antifouling property tended to decrease.
An object of the present invention is to provide a conductive polymer dispersion liquid capable of easily forming a conductive layer having excellent conductivity and antifouling property, and a method for producing the same. Another object of the present invention is to provide a method for producing a conductive film, which can easily produce a conductive film having a conductive layer having excellent conductivity and antifouling property.

The present invention includes the following aspects.
[1] Conductivity containing a conductive composite 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. Polymer dispersion.

[In the formula (1), Rf is a perfluoropolyether group having a divalent molecular weight of 500 or more and 30,000 or less, and may contain an intermediate branch.
X ¹ is a group represented by the following formula (2) independently of each other.

(In equation (2), a and c are independently 0 or more and 4 or less, b is an integer of 1 or more and 4 or less, where a + b + c is 2, 3, or 4, and R ¹ is independent of each other. It is a group represented by 3).

(In formula (3), d, e, f, and g are integers of 0 or more and 20 or less independently of each other in the range where the molecular weight of R ¹ is 30 or more and 600 or less, and the sequence of each repetition unit is random. R3 may be a saturated hydrocarbon group or an unsaturated hydrocarbon group having ¹ or more and 10 or less carbon atoms.)
R ² is an acrylic group represented by the following formula (4) or an α-substituted acrylic group-containing group.

(In the formula (4), R ⁴ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group independently of each other, and R ⁵ is at least one of an ether bond and an ester bond having 1 to 18 carbon atoms. It is a divalent or trivalent linking group that may contain. N is an integer of 1 or 2.)
^Q1 and ^Q2 are divalent linking groups that may contain an ether bond, an ester bond, an amide bond, and a urethane bond having 3 or more and 20 or less carbon atoms independently of each other, and include a cyclic structure and a branch in the middle. They may be the same or different from each other. )
X ² is a group represented by the following formula (5) independently of each other.

(In equation (5), R ¹ , R ² , Q ¹ , and Q ² are the same as in equation (2), h, i, and j are independently integers of 0 or more and 3 or less, and h + i + j is 1. Any value of 3 or more and 3 or less, and the array of repeating units may be random.)
Z is a divalent organic group and 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. Is. ]

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

(In equation (7), Y is F or CF ₃ groups independently of each other, r is an integer of 2 or more and 6 or less, m and n are independently integers of 0 or more and 200 or less, and m + n is 2 or more and 200 or less. .S is an integer of 0 or more and 6 or less, and each repeating unit may be randomly combined.)

(In equation (8), j is an integer of 1 or more and 3 or less, and k is an integer of 1 or more and 200 or less.)

(In the formula (9), Y is F or CF ₃ groups, j is an integer of 1 or more and 3 or less, m and n are independently integers of 0 or more and 200 or less, and m + n is 2 or more and 200 or less. Repeat units may be randomly combined.)

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

[5] Any of [1] to [4], wherein ^Q1 and Q2 in the formula ( ² ) of the acrylate compound are independent of each other and are the basis of any of the following formulas (15) to (20). The conductive polymer dispersion liquid according to Kaichi.

[6] The conductive polymer according to any one of [1] to [5], wherein R ² in the formula (2) of the acrylate compound is a group of any of the following formulas (21) to (24). Dispersion solution.

[7] The conductive polymer dispersion according to any one of [1] to [6], wherein ^R1 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 independently integers 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. It may be combined.)

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

[11] The method for producing a conductive polymer dispersion according to [9], which is an aqueous dispersion of a conductive composite containing a π-conjugated conductive polymer and a polyanion. A step of adding an amine compound to the precipitate to form a precipitate by precipitating the conductive composite, a step of recovering the precipitate, and a step of adding the acrylate compound and an organic solvent to the recovered precipitate. , A method for producing a conductive polymer dispersion.
[12] The method for producing a conductive polymer dispersion liquid according to [9], wherein the water dispersion liquid is a conductive composite containing a π-conjugated conductive polymer and a polyanion. A method for producing a conductive polymer dispersion, which comprises a step of lyophilizing to obtain a lyophilized product and a step of adding an amine compound, the acrylate compound and an organic solvent to the lyophilized product.
[13] The method for producing a conductive polymer dispersion according to [10], which is an aqueous dispersion of a conductive composite containing a π-conjugated conductive polymer and a polyanion. A step of adding an epoxy compound to the precipitate to form a precipitate by precipitating the conductive composite, a step of recovering the precipitate, and a step of adding the acrylate compound and an organic solvent to the recovered precipitate. , A method for producing a conductive polymer dispersion.
[14] A method for producing a conductive film, wherein the conductive polymer dispersion liquid according to any one of [1] to [10] is applied 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, dried, and irradiated with active energy rays.

According to the conductive polymer dispersion liquid of the present invention, a conductive layer having excellent conductivity and antifouling property can be easily formed.
According to the method for producing a conductive polymer dispersion liquid of the present invention, the conductive polymer dispersion liquid 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 provided with a conductive layer having excellent conductivity and antifouling property.

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

(Conductive complex)
The conductive composite in this embodiment includes a π-conjugated conductive polymer and a polyanion.
In this embodiment, the polyanion coordinates with the π-conjugated conductive polymer, and the anionic group of the polyanion is doped with the π-conjugated conductive polymer to form a conductive composite having conductivity.
In the polyanion, all the anion groups are not doped in the π-conjugated conductive polymer and have an extra 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 excess anion group. If at least one of the amine compound and the epoxy compound is bonded to the excess anion group, the conductive complex can be hydrophobized. The hydrophobized conductive complex has an excellent affinity with the acrylate compound (A).

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

Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-hexylthiophene). , Poly (3-heptylthiophene), Poly (3-octylthiophene), Poly (3-decylthiophene), Poly (3-dodecylthiophene), Poly (3-octadecylthiophene), Poly (3-bromothiophene), Poly (3-Chlorothiophene), Poly (3-iodothiophene), Poly (3-cyanothiophene), Poly (3-phenylthiophene), Poly (3,4-dimethylthiophene), Poly (3,4-dibutylthiophene) , Poly (3-hydroxythiophene), Poly (3-methoxythiophene), Poly (3-ethoxythiophene), Poly (3-butoxythiophene), Poly (3-hexyloxythiophene), Poly (3-Heptyloxythiophene) , Poly (3-octyloxythiophene), Poly (3-decyloxythiophene), Poly (3-dodecyloxythiophene), Poly (3-octadecyloxythiophene), Poly (3,4-dihydroxythiophene), Poly (3) , 4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene) , Poly (3,4-diheptyloxythiophene), Poly (3,4-dioctyloxythiophene), Poly (3,4-didecyloxythiophene), Poly (3,4-didodecyloxythiophene), Poly (3,4-didodecyloxythiophene) 3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3- Methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxyphene) Butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and poly (3-butyl). Pyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3) -Carboxypyrrole), Poly (3-Methyl-4-carboxypyrrole), Poly (3-Methyl-4-carboxyethylpyrrole), Poly (3-Methyl-4-carboxybutylpyrrole), Poly (3-Hydroxypyrrole) , Poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole).
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
Among the above-mentioned 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 of 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 anionic group of this polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic sulfonic acid, polymethacrylic sulfonic acid, poly (2-acrylamide-2-methylpropanesulfonic acid), and polyisoprene sulfonic acid. Polymers with sulfonic acid groups such as acid, polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzenesulfonic acid, polyvinylcarboxylic acid, polystyrene carboxylic acid, polyallylcarboxylic acid, polyacrylic carboxylic acid. , Polymethacrylcarboxylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, polyacrylic acid and other polymers with carboxylic acid groups. These homopolymers may be used, or two or more kinds of copolymers may be used.
Among these polyanions, a polymer having a sulfonic acid group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be made higher.
The polyanion may be used alone or in combination of two or more.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight of the polyanion is a mass-based molecular weight obtained by measuring the elution time using gel permeation chromatography (GPC) and obtaining an elution time vs. molecular weight calibration curve obtained in advance from a polystyrene standard material 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 by at least one of the amine compound and the epoxy compound, the hydrophobicity of the conductive complex is increased. The bond may be any of a covalent bond, an ionic bond, a coordinate bond or a hydrogen bond.
Although detailed analysis of the conductive complex is not always easy, it is presumed that the reaction between the anion group of the polyanion and the amine compound forms the hydrophobic substituent represented by −HNR ¹ R ² R ³ . To. The ^R1 , ^R2 , and R3 ^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 is substituted with an alkyl group, an aryl group, a hydroxy group, or the like). Is. Of ^R1 , ^R2 , and R3 ^, those that are not hydrocarbon groups are hydrogen atoms.
It is presumed that the reaction between the anion group of the polyanion and the epoxy compound forms the hydrophobic substituent represented by -CH ₂ CHOHR ⁴ . The ^R4 is a substituent derived from an epoxy compound described later. For example, ^R4 is a hydrocarbon group (provided that at least one hydrogen atom of the hydrocarbon group is substituted with an alkyl group, an aryl group, a hydroxy group, or the like).
The hydrophobic substituent binds 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. One type of amine compound may be used alone, or two or more types may be used in combination.
Examples of the primary amine include aniline, toluidine, benzylamine, ethanolamine and the like.
Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, trinaphthylamine and the like.
Of the amine compounds, tertiary amines are preferable, and at least one of 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. From the viewpoint of preventing aggregation or gelation, the epoxy compound is preferably a compound having one epoxy group in one molecule.
One type of epoxy compound may be used alone, or two or more types may be used in combination.

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, and 1,2-. Epoxide heptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monooxide, 1,2-epoxytetradecane, glycidylmethyl ether, 1,2-epoxyoctadecane, 1,2-Epoxyhexadecane, ethylglycidyl ether, glycidylisopropyl ether, tert-butylglycidyl ether, 1,2-epoxyeikosan, 2- (chloromethyl) -1,2-epoxypropane, glycidol, epichlorohydrin, epibromohydr. 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, glycidylmethacrylate, 1,2-epoxycyclododecane, 1-methyl -1,2-Epoxide cyclohexane, 1,2-Epoxycyclopentadecane, 1,2-Epoxycyclopentane, 1,2-Epoxide cyclohexane, 1,2-Epoxide-1H, 1H, 2H, 2H, 3H, 3H-Hepta Decafluorobutane, 3,4-epoxytetralate, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzyl glycidyl ether , Diethoxy (3-glycidyloxypropyl) methylsilane, 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxide propane, 1,1,1,3,5,5,5-heptamethyl-3-( 3-Glysidyloxypropyl) trisiloxane, 9,10-epoxy-1,5-cyclododecadien, 4-tert-butyl glycidyl benzoate, 2,2-bis (4-glycidyloxyphenyl) propane, 2-tert- Butyl-2- [2- (4-chlorophenyl)] ethyloxylan , Styrene oxide, glycidyl trityl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylprepylene oxide, cholesterol-5α, 6α-epoxide, stillben oxide, glycidyl p-toluenesulfonate, 3- Ethyl Methyl-3-phenylglycidate, N-propyl-N- (2,3-epoxypropyl) perfluoro-n-octylsulfonic acid, (2S, 3S) -1,2-epoxy-3- (tert-butoxy) Carbonylamino) -4-phenylbutane, 3-nitrobenzenesulfonic acid (R) -glycidyl, 3-nitrobenzenesulfonic acid-glycidyl, parthenolide, N-glycidylphthalimide, endolin, dirdoline, 4-glycidyloxycarbazole, 7,7-dimethyl Examples thereof include octanoic acid [oxylanylmethyl], 1,2-epoxy-4-vinylcyclohexane, and 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-octadiendiepoxide, neopentyl glycol diglycidyl ether, and 4-butanediol. Diglycidyl ether, 1,2: 3,4-diepoxybutane, 1,2-cyclohexanedicarboxylate diglycidyl, 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 diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, tri Methylol propane triglycidyl ether, trimethylol propane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycidyl polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol-based polyglycidyl Examples thereof include ether, ethylene oxide lauryl alcohol glycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate and the like.

The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer, and is 10 parts by mass or more and 700 parts by mass or less. It is more preferable that the amount is 100 parts by mass or more and 500 parts by mass or less. When the content ratio of the polyanion is at least the above lower limit value, the doping effect on the π-conjugated conductive polymer tends to be strong, and the conductivity becomes higher. On the other hand, when the content of the polyanion is not more than the 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 above formula (1).
In the formula (1), Rf is a perfluoropolyether group having a divalent molecular weight of 500 or more and 30,000 or less, and may contain an intermediate branch.
Rf is preferably a divalent perfluoropolyether residue containing 1 or more and 500 or less repeating units represented by the following formula (6).
-C _i F _2i O- (6)
I in the equation (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 of the above formulas (7) to (9).
In formula (7), Y is independently F or CF ₃ groups, respectively. r is an integer of 2 or more and 6 or less, m and n are independently integers of 0 or more and 200 or less, and 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 randomly combined.
In the formula (8), j is an integer of 1 or more and 3 or less, and k is an integer of 1 or more and 200 or less.
In formula (9), Y is F or CF ₃ groups. j is an integer of 1 or more and 3 or less, m and n are independently integers of 0 or more and 200 or less, and m + n is 2 or more and 200 or less. Each repeating unit may be randomly combined.

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

In the formula (2), Q ¹ and Q ² are divalent linking groups which may contain an ether bond, an ester bond, an amide bond, and a urethane bond having 3 or more and 20 or less carbon atoms independently of each other. It may contain an annular structure or a branch, and may be the same or different from each other.
^Q1 and ^Q2 are preferably groups of any of the above formulas (15) to (20) independently of each other.

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

Among the R ¹ , the group represented by the formula (25) is preferable.
In the formula (25), p and q are independently integers of 0 or more and 20 or less, and p + q is 1 or more and 40 or less. The propylene group in the formula (25) may be branched. Each repeating unit may be randomly combined.

^R2 is a monovalent organic group having 1 or more and 20 or less carbon atoms having either an acrylic group represented by the above formula (4) or an α-substituted acrylic group.
In the formula (4), R ⁴ is either a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group independently of each other, and a hydrogen atom or a methyl group is preferable.
R5 in the formula ( ⁴ ) is a divalent or trivalent linking group having 1 or more and 18 or less carbon atoms, and may contain at least one of an ether bond and an ester bond.
In equation (4), n is an integer of 1 or 2.
^R2 is preferably a group according to any one of the above formulas (21) to (24), and among them, a group having an ethylene group is preferable.

In the formula (2), when a> 1, the preferable combination of R ¹ and Q ¹ is as follows. It is preferable that R ¹ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and Q ¹ is a combination of a methylene group, an ethylene group, a propylene group, a butylene group, or a hexylene group.
In the formula (2), when b> 1, the preferable combination of R ² and Q ² is as follows. It is preferable that R ² is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and Q ² is a combination of a methylene group, an ethylene group, a propylene group, a butylene group, or a hexylene group.
In the formula (2), when c> 1, the preferable ^Q2 is any one of a methylene group, an ethylene group, a propylene group, a butylene group and a hexylene group.
In the formula (2), when a> 1 and b> 1, a compound in which the above-mentioned preferred combination of R ¹ and Q ¹ and the above-mentioned preferred combination of R ² and Q ² are further combined is preferable.
In the formula (2), when a> 1 and c> 1, a compound in which the above-mentioned preferable combination of R ¹ and Q ¹ and the above-mentioned preferable combination of Q ² is further combined is preferable.
In the formula (2), when b> 1 and c> 1, a compound in which the above-mentioned preferable combination of R ² and Q ² and the above-mentioned preferable combination of Q ² is further combined is preferable.
In the formula (2), when a> 1, b> 1, c> 1, the above-mentioned preferable combination of R ¹ and Q ¹ , the above-mentioned combination of the preferable R ² and Q ² , and the above-mentioned preferable Q ² A compound in which the above is further combined is preferable.

In the formula (1), X ² is a group represented by the above formula (5) independently of each other.
In the formula (5), R ¹ , R ² , Q ¹ , and Q ² are the same as those in the formula (2).
In equation (5), h, i, and j are independently integers of 0 or more and 3 or less, and h + i + j is any value of 1, 2, or 3. The repeating unit array may be random. )

In the formula (1), Z is a divalent organic group and may contain an oxygen atom, a nitrogen atom and a fluorine atom. Further, Z may be a group having a cyclic structure and 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 the acrylic group. Preferred Z includes any group of the above formulas (10) to (14).
A more preferable example of Z is a group 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).

One type of acrylate compound may be used alone, or two or more types may be used in combination.
A method for synthesizing the acrylate compound (A) is described in, for example, Japanese Patent Application Laid-Open No. 2010-285501.

In the conductive polymer dispersion liquid of this embodiment, the content of the acrylate compound (A) is preferably 0.01 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the conductive composite, preferably 0.05. It is more preferably 5 parts by mass or more and 500 parts by mass or less, and further preferably 0.1 part by mass or more and 100 parts by mass or less. When the content of the acrylate compound (A) is at least the lower limit value, the antifouling property of the conductive layer can be further improved, and when the content is at least the lower limit value, sufficient conductivity can be ensured.

(Other acrylate compounds)
The conductive polymer dispersion liquid 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 containing no fluorine. A fluorine-free acrylate compound is preferable because it is easily available and the conductive hardness can be easily increased.

Examples of the fluorine-free acrylate compound (B) include urethane acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and isocyanuric acid ethylene oxide modification. 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 (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol penta Examples thereof include bifunctional or higher and hexafunctional or lower (meth) acrylic compounds such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and sorbitol hexa (meth) acrylate.
Further, the fluorine-free acrylate compound (B) is an epoxy acrylate obtained by reacting the (meth) acrylic compound with an epoxy compound, and a (meth) acryloyl group is introduced into the side chain of the acrylic acid ester copolymer. It may be a polymer or the like.
As the acrylate compound (B), one type may be used alone, or two or more types may be used in combination.

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

When the conductive polymer dispersion liquid of this embodiment contains the acrylate compound (B), the content of the acrylate compound (B) is 0.1 part by mass or more and 10,000 parts by mass with respect to 100 parts by mass of the acrylate compound (A). It is preferably 0.5 parts by mass or more, more preferably 5000 parts by mass or less, and further preferably 1.0 part by mass or more and 1000 parts by mass or less. When the content of the acrylate compound (B) is at least the above lower limit value, it can sufficiently react with the acrylate compound (A) to increase the hardness of the conductive layer. When the content of the acrylate compound (B) is not more than the upper limit value, the conductivity of the conductive layer can be ensured.

(Dispersion medium)
In the conductive polymer dispersion liquid of this embodiment, when the conductive composite is hydrophobic, it is preferable to use an organic solvent as the main component of the dispersion medium. However, the dispersion medium may contain not only an organic solvent but also water.
As the organic solvent, it is preferable to use an alcohol-based solvent, a ketone-based solvent, or an ester-based solvent, and it is more preferable to use at least one of the ketone-based solvent and the alcohol-based solvent because the dispersibility of the conductive composite can be increased. .. The organic solvent is preferably a solvent that does not contain fluorine.
Examples of the alcohol solvent 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 thereof 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, preferably 80% by mass, when the conductive polymer dispersion is 100% by mass. It is more preferably 90% by mass or more and less than 100% by mass, and further preferably 90% by mass or more and less than 100% by mass. The conductive polymer dispersion liquid does not have to contain water at all.
In the conductive polymer dispersion liquid of this embodiment, the content of the conductive composite with respect to the total mass of the conductive polymer dispersion liquid is, for example, preferably 0.1% by mass or more and 20% by mass or less, preferably 0.5. It is more preferably 1% by mass or more and 10% by mass or less, and further preferably 1.0% by mass or more and 5.0% by mass or less.

(Highly conductive agent)
The conductive polymer dispersion liquid may contain a highly conductive agent in order to further improve the conductivity of the conductive layer. Here, the above-mentioned π-conjugated conductive polymer, polyanion, amine compound, epoxy compound, acrylate compound (A), acrylate compound (B) and organic solvent are not classified as high conductivity agents.
The high conductivity 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, and the like. 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 kind or two or more kinds.
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, and 100 parts by mass with respect to 100 parts by mass of the conductive composite. It is more preferably 2 parts or more and 2500 parts by mass or less. When the content ratio of the high conductive agent is at least the above lower limit value, the effect of improving the conductivity by adding the high conductivity agent is sufficiently exhibited, and when it is at least the above upper limit value, the concentration of the π-conjugated conductive polymer is lowered. 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 effect of the present invention can be obtained, and for example, a polymerization initiator, a surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like are used. can. However, the additive is composed of a compound other than the above-mentioned 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 preferable from the viewpoint of storage stability. Further, a polymer-based surfactant such as polyvinylpyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving the metal salt in water.
Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the coupling agent include a silane coupling agent having a vinyl group or an amino group.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, saccharides and the like.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, etc. Can be mentioned.
When the conductive polymer dispersion liquid contains the above additive, the content ratio thereof is appropriately determined depending on the type of the additive. For example, 0. The range may be 001 parts by mass or more and 5 parts by mass or less.

(Manufacturing method of conductive polymer dispersion liquid)
The conductive polymer dispersion used in this embodiment can be produced by the method (a) or (b) below.
(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 precipitating the conductive complex to form a precipitate. A method comprising 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 freeze-drying an aqueous dispersion of a conductive composite containing a π-conjugated conductive polymer and a polyanion to obtain a freeze-dried product, and at least one of an amine compound and an epoxy compound in the freeze-dried product. A method comprising a step of 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 water and a conductive composite containing a π-conjugated conductive polymer and a polyanion. .. The aqueous dispersion may contain an organic solvent, but since the conductive complex is not hydrophobized at this point, it is preferable that the content of the organic solvent is low from the viewpoint of enhancing the dispersibility of the conductive complex. .. 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. It is more preferably 10% by mass or less.

Examples of the method for producing an aqueous dispersion of a conductive composite include a method of chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous solution of a polyanion.
Further, 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, catalysts and oxidizing agents can be used. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate and ferric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidant can restore the reduced catalyst to its original oxidized state.
The 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, and is 0.3. More preferably, it is by mass% or more and 5% by mass or less.

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

When the amine compound is added, the amount of the amine compound added is preferably 1 part by mass or more and 100,000 parts by mass or less, and 10 parts by mass or more and 50,000 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. When the amount of the amine compound added is at least the lower limit value, the hydrophobicity of the conductive complex can be sufficiently improved, and when it is at least the upper limit value, the decrease in conductivity of the conductive layer can be prevented.

When the epoxy compound is added, the amount of the epoxy compound added is preferably 10 parts by mass or more and 10,000 parts by mass or less, and 100 parts by mass or more and 5000 parts by mass or less with respect to 100 parts by mass of the conductive composite. Is more preferable, and more preferably 200 parts by mass or more and 500 parts by mass or less. When the amount of the epoxy compound added is at least the lower limit value, the hydrophobicity of the conductive complex can be sufficiently improved, and when it is at least the upper limit value, the decrease in conductivity of the conductive layer can be prevented.

When precipitating the conductive complex, an organic solvent may be added. Examples of the organic solvent added at the time of precipitation include alcohol-based solvents, ketone-based solvents, and ester-based solvents. As the organic solvent added at the time of precipitation, one kind may be used alone, or two or more kinds may be used in combination.

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

In the step of recovering the precipitate in the method (a), for example, a known sorting method such as filtration, precipitation, or extraction can be applied. Among these preparative methods, filtration is preferable, and it is preferable to filter using a filter having a coarse mesh so that the polyanion used for forming the conductive complex can pass through with the filtrate. According to this filtration method, the precipitate can be separated and the excess polyanion which does not form a conductive complex can be separated from the precipitate by leaving the excess polyanion on the filtrate side. By removing the excess polyanion, the conductivity of the precipitate can be enhanced.

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

In the step of adding the acrylate compound (A) and the organic solvent to the precipitate in the method (a), the precipitate and the acrylate compound (A) are contained after adding the acrylate compound (A) and the organic solvent to the precipitate. It is preferable to apply a dispersion treatment to the organic solvent.
In the dispersion processing, it is preferable to use a disperser. Examples of the disperser include a homogenizer, a high-pressure homogenizer, a bead mill, and the like. Among the dispersers, a high-pressure homogenizer is preferable in that the dispersibility of the precipitate in an organic solvent can be improved.
Examples of the high-pressure homogenizer include a device including a high-pressure generating portion that pressurizes a liquid to be dispersed to be dispersed, and an opposed collision portion, an orifice portion, or a slit portion that performs dispersion. As the high pressure generating part, a known high pressure pump such as a plunger pump is used. Specific examples of the high-pressure homogenizer include a product name nanomizer manufactured by Yoshida Kikai Kogyo Co., Ltd., a product name microfluidizer manufactured by Microfluidisk, and an ultimateizer manufactured by Sugino Machine Limited.

In the freeze-drying method of (b), the water content in the aqueous dispersion of the conductive complex is frozen and vacuum-dried. As a result, a freeze-dried product is obtained.
The temperature during freeze-drying is preferably −60 to 60 ° C., more preferably −40 to 40 ° C. If the freeze-drying temperature is at least the lower limit value, the temperature can be easily adjusted, and if it is at least the upper limit value, the aqueous dispersion of the conductive complex can be easily freeze-dried.

When adding at least one of the amine compound and the epoxy compound, the acrylate compound (A) and the organic solvent to the freeze-dried product, the order of addition thereof 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 freeze-dried product, it is preferable to carry out a dispersion treatment. By performing the dispersion treatment, the dispersibility of the conductive complex 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 high conductivity agent and the additive may be added as appropriate, but it is preferable to add the acrylate compound (B) together with the organic solvent.

(Action effect)
The conductive polymer dispersion liquid of this embodiment contains an acrylate compound (A) having a perfluoropolyether group in addition to the conductive complex. 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.
Generally, fluororesin has high water repellency and oil repellency, and is excellent in antifouling property. 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 property.
Further, the cured product of the acrylate compound in this embodiment does not easily inhibit the conductivity exhibited by the conductive complex in the conductive layer. Therefore, the conductive layer formed from the conductive polymer dispersion liquid of this embodiment has excellent conductivity.
Further, the acrylate compound (A) has an excellent affinity with the fluorine-free acrylate compound (B) and the fluorine-free organic solvent, and is compatible with the fluorine-free acrylate compound (B) and the fluorine-free organic solvent. It is difficult to separate and easy to use.
Further, the acrylate compound (A) can be cured by irradiating it with active energy rays in the presence of a photopolymerization initiator.

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

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, polyvinylidene terephthalate, and polyethylene na. Phtalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene-based elastomer, polyester-based elastomer, polyether sulfone, polyetherimide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate, etc. Can be mentioned. Examples of the polyolefin-based resin include polyethylene, polypropylene, an ethylene-α-olefin copolymer resin, and a 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. When the average thickness of the film substrate is at least the lower limit value, it is difficult to break, and when it is at least 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 points using an optical microscope or an electron microscope and averaging the measured values.

The conductive layer in this embodiment is a layer formed by applying the conductive polymer dispersion liquid of the above embodiment. Therefore, the conductive layer in this embodiment contains at least the conductive composite and the 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 the high conductivity agent and the additive, the conductive layer also 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 10000 nm or less, and further preferably 30 nm or more and 5000 nm or less. When the average thickness of the conductive layer is not less than the lower limit value, sufficiently high conductivity and antifouling property can be exhibited, and when it is not more than the upper limit value, 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 points using an optical microscope or an electron microscope and averaging the measured values.

The conductive layer is formed by applying the conductive polymer dispersion liquid to at least one surface of the film substrate.
Examples of the method of applying the conductive polymer dispersion liquid 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, and a knife coater. A method using a coater such as a blade coater, a cast coater, or a screen coater, a spraying method using an atomizer such as an air spray, an airless spray, or a rotor dampening, a dipping method such as a dip, or the like can be applied.
Of the above, a bar coater may be used because the conductive polymer dispersion can be easily applied. In the bar coater, the coating thickness differs 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 performed.

After applying the conductive polymer dispersion, it is preferable to dry the applied conductive polymer dispersion.
Examples of the drying method include heat drying and vacuum drying. As the heat drying, for example, a usual method such as hot air heating or infrared heating can be adopted.
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, and more preferably 70 ° C. or higher and 120 ° C. or lower. Here, the heating temperature is a set temperature of the drying device.
Further, the drying time is preferably 5 minutes or more in order to sufficiently remove the dispersion medium.

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

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

(Manufacturing Example 1)
206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of an ammonium persulfate oxidant solution previously dissolved in 10 ml of water was added dropwise to the solution at 80 ° C. for 20 minutes. Stir for hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium styrene sulfonate-containing solution, and 1000 ml of the solvent of the polystyrene sulfonic acid-containing solution was removed by using an ultrafiltration method. 2000 ml of ion-exchanged water was added to the residual 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 3 times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.

(Manufacturing Example 2)
14.2 g of 3,4-ethylenedioxythiophene and a solution of 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 keeping the resulting mixed solution at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of a ferric sulfate oxidation catalyst solution were slowly added. The mixture was stirred for 3 hours and reacted.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solvent was removed by using an ultrafiltration method. This operation was repeated 3 times. Next, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solvent was removed using an ultrafiltration method. 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by an ultrafiltration method, and polystyrene sulfonate-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 content concentration of 1.2% by mass.

(Manufacturing Example 3)
A solution of 2.5 g of 3,4-ethylenedioxythiophene and 12.5 g of polystyrene sulfonic acid of Production Example 1 in 500 ml of ion-exchanged water was mixed at 30 ° C.
The mixed solution thus obtained was kept at 30 ° C., and while stirring, 5.5 g of ammonium persulfate dissolved in 44.35 ml of ion-exchanged water and 0.15 g of an oxidation catalyst solution of ferric sulfate were slowly added. Then, the mixture was stirred for 8 hours and reacted. As a result, a 2.7% by mass polystyrene sulfonic 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 PEDOT-PSS trioctylamine adduct was collected by filtration and washed with 100 g of water, and then washed with 100 g of acetone to remove 18.8 g of the PEDOT-PSS trioctylamine adduct as a solid.
3760 g of isopropanol was added to the obtained solid and subjected to dispersion treatment using a high-pressure homogenizer to obtain a conductive polymer dispersion.

(Manufacturing 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.

(Manufacturing 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.) were added, and 4 at 60 ° C. The mixture was heated and stirred for hours. At this time, since the epoxy group of the epoxy compound reacts with the sulfonic acid group of PSS, the free sulfonic acid group disappears, the water dispersibility of PEDOT-PSS decreases, and PEDOT-PSS precipitates. The precipitate thus obtained was recovered by filtration. 1.575 g of the precipitate was added to 315 g of methyl ethyl ketone and subjected to dispersion treatment using a high-pressure homogenizer to obtain a conductive polymer dispersion.

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

(Manufacturing Example 7)
Under a dry nitrogen atmosphere, in a 2000 ml three-necked flask equipped with a recirculation device and a stirrer, 500 g of perfluoropolyether having α-unsaturated bonds at both ends represented by the following formula (34) and 700 g of m-xylene hexafloride. , And 361 g of tetramethylcyclotetrasiloxane were added and heated to 90 ° C. with stirring. To the mixture thus obtained, 0.442 g of a toluene solution of a platinum chloride acid / vinylsiloxane complex (containing 1.1 × ^10-6 mol as a simple substance of platinum) was added, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours. ¹ After confirming that the allyl group of the raw material had disappeared by 1 H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure and treated with activated carbon. 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, with respect to 50.0 g of compound (I), 7.05 g of 2-allyloxyethanol, 50.0 g of m-xylene hexafloride, and a toluene solution of platinum chloride acid / vinylsiloxane complex 0. 0442 g (containing 1.1 × ^10-7 mol of platinum alone) was mixed and stirred at 100 ° C. for 4 hours. ¹ After confirming that the Si—H group had disappeared 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 tetrahydrofuran and 9.00 g of acryloyloxyethyl isocyanate were mixed with 50.0 g of compound (II) and heated to 50 ° C. To the mixture thus obtained, 0.05 g of dioctyl tin laurate was added, and the mixture was stirred at 50 ° C. for 24 hours. After the heating was completed, distillation was performed under reduced pressure at 80 ° C. and 2 Torr. As a result, 58.7 g of a pale yellow paste-like substance was obtained (Compound III). ¹ From the results of 1 H-NMR and IR, it was confirmed that the acrylate compound was represented by the following formula (37).

(Manufacturing Example 8)
Example 1 and Example 1 except that 11.9 g of the compound represented by the following formula (38) and 7.05 g of acryloyloxyethyl isocyanate were used in place of 2-allyloxyethanol with respect to 50 g of the compound (I). In the same procedure, 56.1 g of the acrylate compound represented by the following formula (39) was obtained (Compound IV).

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

(Example 1)
40 g of the conductive polymer dispersion liquid of Production Example 3, 1.4 g of the acrylate compound represented by the above formula (37) of Production Example 7, and urethane acrylate (Art Resin UN904M manufactured by Negami Kogyo Co., Ltd., 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 liquid was subjected to No. It was applied to one side of a polyethylene terephthalate film (Lumirror T-60 manufactured by Toray Industries, Inc.) using the bar coater of No. 6, dried at 100 ° C. for 1 minute, and then irradiated with ultraviolet rays of 400 mJ. As a result, the conductive polymer dispersion liquid coated on the polyethylene terephthalate film was cured to form a conductive layer, and a conductive film was obtained.

(Example 2)
A conductive film was obtained in the same manner as in Example 1 except that the conductive polymer dispersion liquid of Production Example 3 was changed to the conductive polymer dispersion liquid 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 liquid of Production Example 3 was changed to the conductive polymer dispersion liquid 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 liquid of Production Example 3 was changed to the conductive polymer dispersion liquid 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 the formula (37) in Production Example 7 was changed to the acrylate compound represented by the 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 the formula (37) in Production Example 7 was changed to the acrylate compound represented by the 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 above formula (37) in Production Example 7 was changed to trifluoroethyl methacrylate.

<Evaluation>
The surface resistance value of the conductive film of each example was measured using a resistivity meter (High Restor 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 larger the contact angle, the better the antifouling property.

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

Claims (15)

Conductive polymer dispersion containing a conductive composite 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 perfluoropolyether group having a divalent molecular weight of 500 or more and 30,000 or less, and may contain an intermediate branch.
X ¹ is a group represented by the following formula (2) independently of each other.

(In equation (2), a and c are independently 0 or more and 4 or less, b is an integer of 1 or more and 4 or less, where a + b + c is 2, 3, or 4, and R ¹ is independent of each other. It is a group represented by 3).

(In formula (3), d, e, f, and g are integers of 0 or more and 20 or less independently of each other in the range where the molecular weight of R ¹ is 30 or more and 600 or less, and the sequence of each repetition unit is random. R3 may be a saturated hydrocarbon group or an unsaturated hydrocarbon group having ¹ or more and 10 or less carbon atoms.)
R ² is an acrylic group represented by the following formula (4) or an α-substituted acrylic group-containing group.

(In the formula (4), R ⁴ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group independently of each other, and R ⁵ is at least one of an ether bond and an ester bond having 1 to 18 carbon atoms. It is a divalent or trivalent linking group that may contain. N is an integer of 1 or 2.)
^Q1 and ^Q2 are divalent linking groups that may contain an ether bond, an ester bond, an amide bond, and a urethane bond having 3 or more and 20 or less carbon atoms independently of each other, and include a cyclic structure and a branch in the middle. They may be the same or different from each other. )
X ² is a group represented by the following formula (5) independently of each other.

(In equation (5), R ¹ , R ² , Q ¹ , and Q ² are the same as in equation (2), h, i, and j are independently integers of 0 or more and 3 or less, and h + i + j is 1. Any value of 3 or more and 3 or less, and the array of repeating units may be random.)
Z is a divalent organic group and 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. Is. ] The conductive polymer dispersion liquid according to claim 1, wherein Rf in the formula (1) of the acrylate compound contains 1 or more and 500 or less repeating units represented by the following formula (6).
-C _i F _2i O- (6)
(I is an integer of 1 or more and 6 or less 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 the groups represented by any of the following formulas (7) to (9).

(In equation (7), Y is F or CF ₃ groups independently of each other, r is an integer of 2 or more and 6 or less, m and n are independently integers of 0 or more and 200 or less, and m + n is 2 or more and 200 or less. .S is an integer of 0 or more and 6 or less, and each repeating unit may be randomly combined.)

(In equation (8), j is an integer of 1 or more and 3 or less, and k is an integer of 1 or more and 200 or less.)

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

The invention according to any one of claims 1 to 4, wherein Q ¹ and Q ² in the formula (2) of the acrylate compound are independently based on any one of the following formulas (15) to (20). Conductive polymer dispersion.

The conductive polymer dispersion liquid according to any one of claims 1 to 5, wherein R ² in the formula (2) of the acrylate compound is a group according to any one 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 independently integers 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. It may be combined.) The conductive polymer dispersion liquid according to any one of claims 1 to 7, wherein the dispersion medium is an organic solvent. The conductive polymer dispersion liquid according to any one of claims 1 to 8, wherein the amine compound is bonded to a part of the anion group of the polyanion. The conductive polymer dispersion liquid according to any one of claims 1 to 8, wherein the epoxy compound is bonded to a part of the anion group of the polyanion. The method for producing a conductive polymer dispersion liquid according to claim 9, wherein the conductive polymer dispersion liquid is produced.
A step of adding an amine compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, and precipitating the conductive complex to form a precipitate.
The step of collecting the precipitate and
The step of adding the acrylate compound and the organic solvent to the recovered precipitate, and
A method for producing a conductive polymer dispersion liquid. The method for producing a conductive polymer dispersion liquid according to claim 9, wherein the conductive polymer dispersion liquid is produced.
A step of freeze-drying an aqueous dispersion of a conductive composite containing a π-conjugated conductive polymer and a polyanion to obtain a freeze-dried product.
The step of adding the amine compound, the acrylate compound and the organic solvent to the freeze-dried product, and
A method for producing a conductive polymer dispersion liquid. The method for producing a conductive polymer dispersion liquid according to claim 10, wherein the conductive polymer dispersion liquid is produced.
A step of adding an epoxy compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, and precipitating the conductive complex to form a precipitate.
The step of collecting the precipitate and
The step of adding the acrylate compound and the organic solvent to the recovered precipitate, and
A method for producing a conductive polymer dispersion liquid. A method for producing a conductive film, wherein the conductive polymer dispersion liquid according to any one of claims 1 to 10 is applied to a film substrate. The method for producing a conductive film according to claim 14, wherein the conductive polymer dispersion is applied to a film substrate, dried, and irradiated with active energy rays.