JP2018111738A - Conductive polymer dispersion liquid and method for producing the same, and conductive film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive film having excellent scratch resistance and peeling property, a method for producing the same, a conductive polymer dispersion and a method for producing the same. [1] A conductive polymer dispersion liquid containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an acrylic curable silicone, polyvinyl alcohol, and water. [2] The conductive polymer dispersion according to [1], in which the acrylic curable silicone is emulsified. [3] The conductive polymer dispersion liquid according to [1] or [2], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). [4] The conductive polymer dispersion liquid according to any one of [1] to [3], wherein the polyanion is polystyrene sulfonic acid. [5] The conductive polymer dispersion liquid according to any one of [1] to [4], wherein the conductive polymer dispersion liquid further contains a nonionic surfactant. [Selection diagram] None

Description

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

The conductive film is widely used as an antistatic film for preventing the generation of static electricity that causes a failure of the electronic component when packaging the electronic component.
As a conventional method for producing an antistatic film, a method has been proposed in which an antistatic layer containing a π-conjugated conductive polymer and a polyanion is provided on at least one surface of a film substrate and stretched as necessary ( For example, Patent Document 1).

Japanese Patent Laid-Open No. 2006-047501

  However, Patent Document 1 does not discuss improving the scratch resistance (scratch resistance) and releasability (ease of peeling of the attached adhesive tape) of the antistatic film.

  The present invention provides a conductive film having excellent scratch resistance and peelability and a method for producing the same, and a conductive polymer dispersion and a method for producing the same.

[1] A conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, acrylic curable silicone, polyvinyl alcohol, and water.
[2] The conductive polymer dispersion according to [1], wherein the acrylic curable silicone is emulsified.
[3] The conductive polymer dispersion according to [1] or [2], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[4] The conductive polymer dispersion according to any one of [1] to [3], wherein the polyanion is polystyrene sulfonic acid.
[5] The conductive polymer dispersion according to any one of [1] to [4], wherein the conductive polymer dispersion further contains a nonionic surfactant.
[6] The conductive polymer dispersion according to [5], wherein the nonionic surfactant is a polyoxyalkylene branched decyl ether.
[7] The conductive polymer dispersion according to any one of [1] to [6], wherein the conductive polymer dispersion further includes a reactive acrylic compound other than the acrylic-curable silicone.
[8] The conductive polymer dispersion according to any one of [1] to [7], wherein the conductive polymer dispersion further contains a radical photopolymerization initiator.
[9] The conductive polymer dispersion according to any one of [1] to [8], wherein the conductive polymer dispersion further contains an azo radical initiator.
[10] A mixing step of mixing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an acrylic curable silicone, polyvinyl alcohol, and an aqueous dispersion medium, and emulsifying the acrylic curable silicone. A process for producing a conductive polymer dispersion having:
[11] The method for producing a conductive polymer dispersion according to [10], wherein in the mixing step, a nonionic surfactant is further mixed to emulsify the acrylic curable silicone.
[12] A conductive film having a film substrate and a conductive layer formed on at least one surface of the film substrate, wherein the conductive layer includes a π-conjugated conductive polymer and a polyanion. A conductive film containing a conductive composite, an acrylic curable silicone, and polyvinyl alcohol.
[13] A conductive material having a coating step of coating the conductive polymer dispersion according to any one of [1] to [9] on at least one surface of a film substrate to obtain a coated film. For producing a conductive film.
[14] The method for producing a conductive film according to [13], comprising at least one of a drying step of heating and drying the coating film and a light irradiation step of irradiating the coating film with ultraviolet rays.
[15] The conductive film according to [14], wherein the film substrate is an amorphous film substrate, and includes a stretching step of heating and drying the coated film and stretching to obtain a stretched film. Production method.
[16] The method for producing a conductive film according to [15], further including a crystallization step of crystallizing the amorphous film substrate by heating and then cooling the stretched film.
[17] The method for producing a conductive film according to [16], wherein the heating temperature of the stretched film in the crystallization step is set to 200 ° C or higher.
[18] The method for producing a conductive film according to any one of [15] to [17], wherein the amorphous film substrate is an amorphous polyethylene terephthalate film.

According to the method for producing a conductive film of the present invention, a conductive film having excellent scratch resistance and peelability can be produced.
The conductive film of the present invention has excellent scratch resistance and peelability. Moreover, even after passing through the stretching treatment and after the heat treatment for crystallizing the film substrate, the increase in the surface resistance value is suppressed, and excellent conductivity, scratch resistance and peelability are obtained. For this reason, the electroconductive film of this invention is suitable for the use of an antistatic film.
The conductive polymer dispersion of the present invention is suitably used for the production of a conductive film.
According to the method for producing a conductive polymer dispersion of the present invention, it is possible to easily obtain a dispersion in which the components of the conductive composite, the acrylic curable silicone, and the polyvinyl alcohol are uniformly dispersed without phase separation. Can do.

<< Conductive polymer dispersion >>
The first aspect of the present invention is a conductive polymer dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, acrylic curable silicone, polyvinyl alcohol, and water.
The conductive polymer dispersion may contain a nonionic surfactant, a reactive acrylic compound that does not correspond to the acrylic curable silicone, a binder component, a highly conductive agent, and other additives as necessary. Good.

<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 forming the conductive composite may be one type or two or more types.

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 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 sulfonic acid, poly Polymers having a sulfonic acid group such as sulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacrylic acid Examples thereof include polymers having a carboxylic acid group such as carboxylic acid, poly (2-acrylamido-2-methylpropanecarboxylic acid), polyisoprene carboxylic acid, and polyacrylic acid.
The polyanion may be a polymer composed of a single type of monomer, or may be a copolymer composed of two or more types of monomers.
Among the above polyanions, a polymer having a sulfonic acid group is preferable and polystyrene sulfonic acid is more preferable because conductivity can be further increased.
The polyanion that forms the conductive complex may be one type or two or more types.
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 in the present specification is a value obtained by measuring with gel permeation chromatography and obtaining the standard substance as polystyrene.

The range of the weight ratio of π-conjugated conductive polymer: polyanion in the conductive composite is preferably, for example, 1: 2 to 1: 7.5, preferably 1: 2.5 to 1: 6.0, 1: 2.5-1: 4.5 is more preferable.
When the weight ratio is 1: 2 or more, the doping effect on the π-conjugated conductive polymer is increased, and the conductivity is improved. Moreover, the dispersibility of the conductive composite in the conductive polymer dispersion is increased.
When the weight ratio is 1: 7.5 or less, the relative content of the π-conjugated conductive polymer increases, and sufficient conductivity is easily obtained.

<Polyvinyl alcohol>
Polyvinyl alcohol functions as a dispersant for the conductive composite in the conductive polymer-containing liquid and also has a function of improving the stretchability of the conductive layer formed on the film substrate. That is, the conductive layer containing polyvinyl alcohol tends to follow the stretching of the film, and the conductive layer is less likely to be cracked or peeled off.
Polyvinyl alcohol is produced by saponifying acetyl groups of polyvinyl acetate, but some acetyl groups may not be saponified. Therefore, polyvinyl alcohol may contain vinyl acetate units. The saponification degree of the polyvinyl alcohol used in this embodiment is preferably 70% or more and 100% or less. If the saponification degree of polyvinyl alcohol is not less than the lower limit, it can be easily dissolved in water.
The mass average molecular weight of polyvinyl alcohol is preferably 1000 or more and 100,000 or less, and more preferably 1300 or more and 60000 or less. If the mass average molecular weight of polyvinyl alcohol is not less than the above lower limit value, the stretchability of the conductive layer can be sufficiently improved, and if it is not more than the above upper limit value, the solubility in water can be improved.
The mass average molecular weight in the present specification is a value obtained by measuring with gel permeation chromatography and obtaining the standard substance as polystyrene.

The polyvinyl alcohol contained in the conductive polymer dispersion may be one kind or two or more kinds.
The content ratio of polyvinyl alcohol in the conductive polymer dispersion is, for example, preferably 10 parts by mass to 1000 parts by mass, and more preferably 100 parts by mass to 500 parts by mass with respect to 100 parts by mass of the conductive composite. 150 parts by mass or more and 300 parts by mass or less is more preferable. When the content ratio is 10 parts by mass or more, the dispersibility of the acrylic curable silicone in the conductive polymer dispersion can be improved, and the stretchability of the coating film described later can be further increased. When the content ratio is 1000 parts by mass or less, a decrease in conductivity can be suppressed.

<Acrylic curable silicone>
The acrylic curable silicone contained in the conductive polymer dispersion has one main skeleton composed of polysiloxane having a siloxane bond (Si—O—Si) and one acryloyl group represented by the following formula (1). It is the silicone which has the above.
Equation ^{_{(1): CH 2 = C}} (-R 1) -C (= O) -R 2 -

In formula (1), R ¹ represents hydrogen, a methyl group or a halogen atom, and R ² represents a single bond or a divalent linking group linked to the main skeleton.
Examples of the divalent linking group include a divalent hydrocarbon group having 1 to 10 carbon atoms, —R ³ —N (—R ⁵ ) —R ⁴ —, —R ³ —SR ⁴ —, and the like. Can be mentioned. R ³ and R ⁴ each independently represent a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. One or more methylene groups constituting the hydrocarbon group are —O—, —CO—, —CH ₂ O—, —OCH ₂ —, —CO—O—, except when oxygen atoms are adjacent to each other. It may be substituted with —O—CO—, —O—CO—O—, —CH═CH—, —C≡C— or the like.

The site where the acryloyl group is bonded to the main skeleton may be a side chain of polysiloxane, one or both ends of polysiloxane, or a side chain of polysiloxane and at least one of both ends. May be.
The number of the acryloyl groups bonded to the polysiloxane is preferably two or more. When the number is two or more, the molecules of the acrylic curable silicone can be cross-linked with each other to form a conductive layer having better scratch resistance and peelability.
The number of the acryloyl groups that the acrylic curable silicone has is preferably 2 or more and 10 or less, for example.

The side chain of the polysiloxane is the same as the side chain of a known polysiloxane, and examples thereof include a hydrogen atom, a methyl group, and a phenyl group.
The molecular weight of the polysiloxane is not particularly limited. For example, the molecular weight is preferably such that the viscosity (unit: mPa · s) at 25 ° C. is 100 or more and 500 or less.

  Specific examples of the acrylic curable silicone include, for example, KF-2005, X-62-7205, Momentive Performance, which are solvent-free UV curable silicones sold as a release agent by Shin-Etsu Chemical Co., Ltd. TPR6500, TPR6501, TPR6502, UV9300, UV9315, XS56-A2982, UV9430, etc. sold by Materials Japan LLC are preferable.

The acrylic curable silicone contained in the conductive polymer dispersion may be one type or two or more types.
The content of the acrylic curable silicone in the conductive polymer dispersion is preferably, for example, 100 parts by mass or more and 50000 parts by mass or less, and 1000 parts by mass or more and 25000 parts by mass with respect to 100 parts by mass of the conductive composite. The following is more preferable, and 5000 parts by mass or more and 10000 parts by mass or less are more preferable.
When the amount is 100 parts by mass or more, the scratch resistance and peelability of the conductive layer to be formed can be further improved. When the content is 50000 parts by mass or less, the content of the conductive composite is prevented from extremely decreasing, and good conductivity is obtained.

  The acrylic curable silicone is preferably emulsified in the conductive polymer dispersion. By being emulsified, the acrylic curable silicone is suppressed from phase separation and can be more easily dispersed uniformly. The dispersion medium of the conductive polymer dispersion is preferably an aqueous dispersion medium. The acrylic-curable silicone emulsion is preferably an O / W emulsion.

  Confirmation that the acrylic curable silicone is emulsified can be performed by the following method. First, the conductive polymer dispersion is observed visually or with a microscope to confirm that fine droplets are dispersed. Next, the droplets are collected, and it is confirmed by a chemical method that the acrylic curable silicone is contained in the droplets. If it is contained, it can be said that the acrylic curable silicone is emulsified.

<Aqueous dispersion medium>
The aqueous dispersion medium in this embodiment is a liquid in which the conductive composite, the acrylic curable silicone, and polyvinyl alcohol are dispersed, and is water or a mixed liquid of water and an organic solvent.
The content ratio of water in the aqueous dispersion medium is preferably 60% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more with respect to the total mass (100% by mass) of the aqueous dispersion medium. More preferably. When the content ratio of water in the aqueous dispersion medium is equal to or more than the lower limit, dispersibility of the conductive composite in the conductive polymer dispersion is further improved.
Here, when a binder component described later is included in the conductive polymer dispersion and the binder component includes moisture, the moisture contained in the binder component and the moisture that disperses the conductive composite are not distinguished. That is, all the water contained in the conductive polymer dispersion constitutes an aqueous dispersion medium. Further, the aqueous dispersion medium may be contained in the binder component to form an emulsion.

Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, and the like.
1 type may be sufficient as the said organic solvent, and 2 or more types may be sufficient as it.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, and allyl alcohol.
Examples of ether solvents include propylene glycol monoalkyl ethers such as diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, and propylene glycol monomethyl ether, propylene glycol dialkyl ethers, and the like.
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.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, and the like.

<Nonionic surfactant>
The conductive polymer dispersion of the present invention preferably contains a nonionic surfactant. By including a non-on surfactant, the dispersibility of the acrylic curable silicone can be improved.

As the nonionic surfactant, a polyoxyalkylene branched decyl ether represented by the following formula (2) is preferable. In the following formula (2), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents the number of repetitions. The plurality of R ¹¹ may be the same as or different from each other. n is appropriately set according to HLB (Hydrophilic-Lipophilic Balance). Here, HLB is calculated by the Griffin equation.
Equation _{(2): C 10 H 21} O (CH 2 CR 11 HO) n H

The HLB of the polyoxyalkylene branched decyl ether is preferably 8 or more and 20 or less, more preferably 9 or more and 15 or less, further preferably 10 or more and 12 or less, and particularly preferably 10 or more and 11 or less.
Specific examples of the polyoxyalkylene branched decyl ether include, for example, Neugen XL series listed below, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. The numbers in the following parentheses are HLB values; Neugen XL-40 (10.5), Neugen XL-41 (10.5), Neugen XL-50 (11.6), Neugen XL-60 (12.5 ), Neugen XL-6190 (12.5), Neugen XL-70 (13.2), Neugen XL-80 (13.8), Neugen XL-100 (14.7), Neugen XL-140 (15.9) ), Neugen XL-160 (16.3), Neugen XL-400D (18.4), Neugen XL-1000 (19.3).
The nonionic surfactant contained in the conductive polymer dispersion may be one kind or two or more kinds.
The content of the nonionic surfactant with respect to the total mass (100% by mass) of the conductive polymer dispersion is, for example, preferably 0.01% by mass to 5% by mass, and more preferably 0.1% by mass to 1% by mass. % Or less is more preferable, and 0.2% by mass or more and 0.5% by mass or less is more preferable.
When the content is 0.01% by mass or more, the dispersibility of the acrylic curable silicone in the conductive polymer dispersion can be further improved. When the content is 5% by mass or less, the content of the conductive composite is prevented from extremely decreasing, and good conductivity is obtained.

<Binder component>
The conductive polymer dispersion of the present invention may contain a binder component as an optional component. The binder component is a component other than the conductive composite, the acrylic curable silicone, the polyvinyl alcohol, and the nonionic surfactant, and the mechanical strength of the conductive layer formed by applying a conductive polymer dispersion. And a component that can improve hardness.
Examples of the binder component include a resin, a thermosetting compound, and an active energy ray curable compound. When the conductive polymer dispersion contains a thermosetting compound, it is preferable that a thermal polymerization initiator is also contained, and when an active energy ray-curable compound is contained, a photopolymerization initiator. Are also preferably contained.

Examples of the resin that can be used as the binder component include acrylic resins other than the above acrylic curable silicone, polyester resins, epoxy resins, oxetane resins, polyurethane resins, polyimide resins, melamine resins, silicone resins other than the above acrylic curable silicones, and vinyl acetate resins. Etc. are used.
Examples of the thermosetting compound and the active energy ray curable compound include a compound having a vinyl group, a compound having an epoxy group, and a compound having an oxetane group. These may be monomers or oligomers.
Among these binder components, a water-soluble or water-dispersible reactive acrylic compound is preferable because it can be easily dispersed or dissolved in an aqueous solvent and can be easily cured. Here, “reactivity” means the property of curing by radical polymerization upon irradiation or heating with active energy rays (ultraviolet rays, electron beams, visible rays).
Examples of the active energy ray-curable acrylic compound include acrylate, methacrylate, (meth) acrylamide, vinyl ether, carboxylic acid vinyl ester and the like. The number of radical polymerizable functional groups in the molecule of the active energy ray-curable acrylic compound may be one or plural.

Examples of the acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polyethylene glycol diacrylate. 1,6-hexanediol diacrylate, bisphenol A / ethylene oxide modified diacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol monohydroxypentaacrylate, trimethylolpropane triacrylate, Such as glycerin propoxytriacrylate It is below.
Examples of the methacrylate include n-butyl methacrylate, t-butyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, and glycidyl methacrylate. , Tetrahydrofurfuryl methacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate and the like.
Examples of (meth) acrylamide include methacrylamide, 2-hydroxyethylacrylamide, N-methylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N-phenylacrylamide, N-methylolacrylamide, dimethylaminopropylacrylamide, Examples thereof include dimethylaminopropyl methacrylamide, diacetone acrylamide, N, N-dimethylacrylamide, N-vinylformamide, acryloylmorpholine, acryloylpiperidine and the like.
Examples of the vinyl ether include 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, and the like.
Examples of the vinyl carboxylate include vinyl butyrate, vinyl monochloroacetate, vinyl pivalate and the like.
The reactive acrylic compound may be an acrylate obtained by reacting an acrylic monomer with another compound, such as epoxy acrylate, urethane acrylate, polyester acrylate, or polyacryl acrylate.
The reactive acrylic compound contained in the conductive polymer dispersion may be one type or two or more types.

  The content ratio of the solid content of the binder component is preferably, for example, 10 parts by mass or more and 100000 parts by mass or less, and 100 parts by mass or more and 10000 parts by mass or less with respect to 100 parts by mass of the conductive composite. More preferably, it is 500 parts by mass or more and 5000 parts by mass or less. When the content ratio of the binder component is 10 parts by mass or more, the strength and hardness of the obtained conductive layer can be further improved, and when the content is 100,000 parts by mass or less, the content of the conductive composite is decreased. And good electrical conductivity can be secured.

<Polymerization initiator>
Examples of the polymerization initiator for the acrylic curable silicone and the reactive acrylic compound include a known radical photopolymerization initiator and a known thermal polymerization initiator.
Examples of the radical photopolymerization initiator include Irgacure series manufactured by BASF.
Examples of the thermal polymerization initiator include VA-044, VA-046B, V-50, VA-057, and VA, which are water-soluble azo radical initiators (azo polymerization initiator) manufactured by Wako Pure Chemical Industries, Ltd. -061, VA-086, V-501 and the like.
The polymerization initiator contained in the conductive polymer dispersion may be one type or two or more types.
The content ratio of the polymerization initiator with respect to the total mass of the conductive polymer dispersion is not particularly limited, and may be a general content ratio range of the polymerization initiator.

<High conductivity agent>
The conductive polymer dispersion may contain a highly conductive agent. The highly conductive agent is a compound that improves the conductivity of the conductive layer formed by the conductive polymer dispersion. The conductive composite, acrylic curable silicone, polyvinyl alcohol and nonionic surfactant described above are not classified as highly conductive agents. However, the organic solvent and the binder component may correspond to a highly conductive agent.
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, a lactam compound, and a compound having a glycidyl group.
The highly conductive agent contained in the conductive polymer dispersion may be one kind or two or more kinds.

It is preferable that the conductive polymer dispersion contains a basic compound as a highly conductive agent because the conductivity is further improved.
Here, the “basic compound” refers to a compound containing an atom (hetero atom) other than a carbon atom having a lone electron pair (lone pair) capable of binding a proton.
As the basic compound, a nitrogen-containing compound is preferable, and a nitrogen-containing aromatic cyclic compound is more preferable.

  Examples of nitrogen-containing aromatic cyclic compounds include pyridines and derivatives thereof containing one nitrogen atom, imidazoles and derivatives thereof containing two nitrogen atoms, pyrimidines and derivatives thereof, pyrazines and derivatives thereof And triazines containing three nitrogen atoms and derivatives thereof. From the viewpoint of solvent solubility and the like, pyridines and derivatives thereof, imidazoles and derivatives thereof, and pyrimidines and derivatives thereof are preferable.

  Specific examples of pyridines and derivatives thereof include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, N-vinylpyridine, 2,4-dimethylpyridine, 2,4. , 6-trimethylpyridine, 3-cyano-5-methylpyridine, 2-pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 4-pyridinecarboxaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2 , 6-diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 4-pyridinemethanol, 2,6-dihydroxypyridine, 2,6-pyridinedimethanol, methyl 6-hydroxynicotinate, 2 -Hydroxy-5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4-pi Lysine methanol, 4-pyridineethanol, 2-phenylpyridine, 3-methylquinoline, 3-ethylquinoline, quinolinol, 2,3-cyclopentenopyridine, 2,3-cyclohexanopyridine, 1,2-di (4- Pyridyl) ethane, 1,2-di (4-pyridyl) propane, 2-pyridinecarboxaldehyde, 2-pyridinecarboxylic acid, 2-pyridinecarbonitrile, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, Examples include 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, and 3-pyridinesulfonic acid.

  Specific examples of imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, N-vinylimidazole, and N-allylimidazole. 1- (2-hydroxyethyl) imidazole (N-hydroxyethylimidazole), 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazoledicarbo Acid, dimethyl 4,5-imidazole dicarboxylate, benzimidazole, 2-aminobenzimidazole, 2-aminobenzimidazole-2-sulfonic acid, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, 2- ( 2-pyridyl) benzimidazole and the like.

  Specific examples of pyrimidines and derivatives thereof include 2-amino-4-chloro-6-methylpyrimidine, 2-amino-6-chloro-4-methoxypyrimidine, 2-amino-4,6-dichloropyrimidine, 2-amino-4,6-dihydroxypyrimidine, 2-amino-4,6-dimethylpyrimidine, 2-amino-4,6-dimethoxypyrimidine, 2-aminopyrimidine, 2-amino-4-methylpyrimidine, 4,6 -Dihydroxypyrimidine, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4,6-triaminopyrimidine, 2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine, 2,4-pyrimidinediol, etc. Is mentioned.

  Specific examples of the pyrazines and derivatives thereof include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5-methylpyrazinecarboxylic acid, pyrazineamide, 5 -Methylpyrazine amide, 2-cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,3-diethylpyrazine and the like.

  Specific examples of triazines and derivatives thereof include 1,3,5-triazine, 2-amino-1,3,5-triazine, 3-amino-1,2,4-triazine, and 2,4-diamino. -6-phenyl-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine, 2,4,6-tris (trifluoromethyl) -1,3,5-triazine, 2,4,6-tri-2-pyridine-1,3,5-triazine, 3- (2-pyridine) -5,6-bis (4-phenylsulfonic acid) -1,2,4-triazine disodium 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine, 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine-ρ, ρ′- Disodium disulphonate, 2-hydroxy-4,6-dichloro -1,3,5-triazine and the like.

  Examples of the compound having two or more hydroxy groups include propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, D-glucose, D-glucitol, isoprene glycol, dimethylolpropionic acid, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, thiodiethanol, glucose, tartaric acid, D-glucar Polyhydric aliphatic alcohols such as acid and glutaconic acid; polymer alcohols such as cellulose, polysaccharide and sugar alcohol; 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecyl , 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, 2,6-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4'-dihydroxy Diphenyl sulfone, 2,2 ′, 5,5′-tetrahydroxydiphenyl sulfone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfone, hydroxyquinonecarboxylic acid and salts thereof, 2, 3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 1,4-hydroquinonesulfonic acid and salts thereof, 4 , 5-Hydroxybenzene 1,3-disulfonic acid and its salts, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxy Naphthalene-2,6-dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5-dihydroxynaphthoic acid, 1,4-dihydroxy-2-naphthoic acid phenyl ester, 4,5-dihydroxynaphthalene -2,7-disulfonic acid and its salts, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid and its salts, 6,7-dihydroxy-2-naphthalenesulfonic acid and its salts, 1,2,3-tri Hydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene 5-methyl-1,2,3-trihydroxybenzene, 5-ethyl-1,2,3-trihydroxybenzene, 5-propyl-1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxy Acetophenone, trihydroxybenzophenone, trihydroxybenzaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetrahydroxy-p-benzoquinone, tetrahydroxyanthraquinone, methyl garlic acid (methyl gallate), ethyl garlic acid (gallic acid) Aromatic compounds such as ethyl acetate), potassium hydroquinone sulfonate and the like.

  Examples of the compound having one or more hydroxy groups and one or more carboxy groups include tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylolpropanoic acid, D-glucaric acid, and glutaconic acid.

The compound having an amide group is a monomolecular compound having an amide bond represented by -CO-NH- (CO portion is a double bond) in the molecule. That is, as the amide compound, for example, a compound having functional groups at both ends of the bond, a compound in which a cyclic compound is bonded to one end of the bond, urea and urea derivatives in which the functional groups at both ends are hydrogen Etc.
Specific examples of amide compounds include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, N-methylformamide, propionamide , Propioluamide, butyramide, isobutylamide, palmitoamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citrulamide, glyoxylamide, pyruvamide, acetoacetamide, dimethylacetamide, benzyl Amide, anthranilamide, ethylenediaminetetraacetamide, Acetamide, triacetamide, dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea and derivatives thereof Is mentioned.

Moreover, acrylamide can also be used as an amide compound. As acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, Examples thereof include N-diethyl methacrylamide, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.
The molecular weight of the amide compound is preferably 46 or more and 10,000 or less, more preferably 46 or more and 5,000 or less, and particularly preferably 46 or more and 1,000 or less.

  As the amide compound, a monomolecular compound having an imide bond (hereinafter referred to as an imide compound) is preferable because of higher conductivity. Examples of the imide compound include phthalimide and phthalimide derivatives, succinimide and succinimide derivatives, benzimide and benzimide derivatives, maleimide and maleimide derivatives, naphthalimide and naphthalimide derivatives from the skeleton.

Moreover, although an imide compound is classified into an aliphatic imide, an aromatic imide, etc. by the kind of functional group of both terminal, an aliphatic imide is preferable from a soluble viewpoint.
Furthermore, the aliphatic imide compound is classified into a saturated aliphatic imide compound having no unsaturated bond between carbons in the molecule and an unsaturated aliphatic imide compound having an unsaturated bond between carbons in the molecule. .
The saturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and is a compound in which both R ¹ and R ² are saturated hydrocarbons. Specifically, cyclohexane-1,2-dicarboximide, allantoin, hydantoin, barbituric acid, alloxan, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5 , 5-trimethylhydantoin, 5-hydantoin acetic acid, N-hydroxy-5-norbornene-2,3-dicarboximide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimidooxycarbonyloxy) Ethyl] sulfone, α-methyl-α-propylsuccinimide, cyclohexylimide and the like.
The unsaturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and one or both of R ¹ and R ² are one or more unsaturated bonds. Specific examples are 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1,8-bis. Maleimide octane, N-carboxyheptylmaleimide and the like can be mentioned.
The molecular weight of the imide compound is preferably 60 or more and 5,000 or less, more preferably 70 or more and 1,000 or less, and particularly preferably 80 or more and 500 or less.

The lactam compound is an intramolecular cyclic amide of an aminocarboxylic acid, and a part of the ring is —CO—NR— (R is hydrogen or an arbitrary substituent). However, one or more carbon atoms in the ring may be replaced with an unsaturated or heteroatom.
Examples of the lactam compound include pentano-4-lactam, 4-pentanelactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexane lactam and the like.

  Examples of the compound having a glycidyl group include ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A, diglycidyl ether, glycidyl acrylate, methacrylic acid Examples thereof include glycidyl compounds such as glycidyl ether.

The content ratio of the highly conductive agent in the conductive polymer dispersion is preferably, for example, 10 parts by mass or more and 10,000 parts by mass or less, and 100 parts by mass or more with respect to 100 parts by mass of the conductive composite. The amount is more preferably 5000 parts by mass or less, and further preferably 500 parts by mass or more and 1000 parts by mass or less.
When the content ratio of the high conductivity agent is 10 parts by mass or more, the effect of improving the conductivity due to the addition of the high conductivity agent is sufficiently exhibited, and when the content ratio is 10000 parts by mass or less, the content of the conductive composite The decrease is suppressed and good conductivity is obtained.

The conductive polymer dispersion may contain a known additive.
The additive is not particularly limited as long as the effect of the present invention is obtained. For example, surfactants other than the nonionic surfactant, inorganic conductive agent, antifoaming agent, coupling agent, antioxidant, ultraviolet absorption Agents can be used. However, the additive is a compound other than the conductive composite, acrylic curable silicone, polyvinyl alcohol, binder component, and high conductive agent described above.
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 silane coupling agents having a vinyl group, an amino group, an epoxy group, and the like.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, 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, but is generally 0. 10 parts by mass relative to 100 parts by mass of the solid content of the conductive composite. It is preferably within the range of 001 parts by mass to 5 parts by mass.

In the total mass (100% by mass) of the conductive polymer dispersion, the remainder excluding the conductive composite, the acrylic curable silicone, the polyvinyl alcohol, the binder component, and the highly conductive agent described above is composed of other optional components. A dispersion medium which may be contained is preferable.
The content of the aqueous dispersion medium with respect to the total mass (100% by mass) of the conductive polymer dispersion is, for example, preferably 30% by mass to 95% by mass, and more preferably 40% by mass to 80% by mass. When it is 50% by mass or more, the dispersibility of the conductive composite becomes better, and when it is 95% by mass or less, the coating property to the film substrate becomes better.

<< Method for Producing Conductive Polymer Dispersion >>
In a second aspect of the present invention, a conductive composite containing a π-conjugated conductive polymer and a polyanion, an acrylic curable silicone, polyvinyl alcohol, and an aqueous dispersion medium are mixed, and the acrylic curable silicone is mixed. It is a manufacturing method of the conductive polymer dispersion which has the mixing process to emulsify. Each component used in this embodiment is the same as that described in the first embodiment.
The method for mixing the components is not particularly limited, and for example, a known stirring method for producing an emulsion is applied.
In the mixing step, it is preferable to further emulsify the acrylic curable silicone by further mixing a non-surfactant. When a non-surfactant is added, it can be emulsified more easily. Confirmation that the acrylic curable silicone is emulsified can be performed by the method described above.
The conductive polymer dispersion of the first aspect can be manufactured by the manufacturing method of this aspect. The mixing ratio of each component is appropriately adjusted based on the content ratio described in the first aspect.

<< Method for producing conductive film >>
3rd aspect of this invention is a manufacturing method of an electroconductive film which has the coating process which applies the conductive polymer dispersion liquid of 1st aspect to at least one surface of a film base material, and obtains a coating film. is there.

[Coating process]
By applying the conductive polymer dispersion of the first aspect to at least one surface of the film substrate, a coating film (conductive layer) is formed on the coated surface.

A plastic film is mentioned as a film base material used in a coating process.
Examples of the resin for the film base material constituting the plastic film include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate. , Polyethylene naphthalate, Polyacrylate, Polycarbonate, Polyvinylidene fluoride, Polyarylate, Styrenic elastomer, Polyester elastomer, Polyethersulfone, Polyetherimide, Polyetheretherketone, Polyphenylene sulfide, Polyimide, Cellulose triacetate, Cellulose acetate propio And the like. Among these resins for film base materials, polyethylene terephthalate (PET) is preferable because it is inexpensive and has excellent mechanical strength.
The resin constituting the film base material may be amorphous or crystalline. Any of them can be a crystalline film substrate in any subsequent crystallization step, but an amorphous film is preferred from the viewpoint of good stretchability.
The film substrate may be unstretched or stretched, but when stretched in a subsequent stretching step, it is preferably unstretched in at least one direction.
Moreover, in order to improve the adhesiveness of the conductive layer formed by applying the conductive polymer dispersion on the film base material, the film base material is subjected to corona discharge treatment, plasma treatment, flame treatment, etc. A surface treatment may be applied.

The average thickness of the film substrate is preferably 10 μm or more and 1000 μm or less, and more preferably 20 μm or more and 500 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 in the present specification is a value obtained by measuring the thickness at any 10 locations and averaging the measured values.

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, and a knife coater. A coating method using a coater such as a blade coater, cast coater or screen coater, a spraying method using a sprayer such as air spray, airless spray, or rotor dampening, a dipping method or the like can be applied.
Of these, a bar coater may be used because it can be applied easily. 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.
The amount of the conductive polymer dispersion applied to the film substrate is not particularly limited, but the solid content is preferably in the range of 0.1 g / m ² or more and 10.0 g / m ² or less.

  In the coating step, the conductive polymer dispersion may be applied only on one side of the film substrate to form a coating film only on one side, or the conductive polymer dispersion on both sides of the film substrate. May be applied to form a coating film on both sides. A film formed on a film substrate is referred to as a coating film.

  In the drying process of drying the coating film of the coating film, the coating film is dried while being heated while being stretched in the stretching process or before the stretching process in order to improve the uniformity in the thickness direction. It is preferable.

Examples of the method for drying the coated film 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 appropriately set according to the dispersion medium to be used, but is usually in the range of 50 ° C to 150 ° C. Here, the heating temperature is a set temperature of the drying apparatus.
When the thermal polymerization initiator is contained in the coating film, polymerization of the acrylic curable silicone and the optional reactive acrylic compound can be initiated by heat drying. A conductive layer cured by this polymerization can be formed.

  When the coating film contains a photopolymerization initiator, instead of the method of drying the coating film, or in addition to the method of drying the coating film, an active energy ray is applied to the coating film. You may have the light irradiation process to irradiate. By this light irradiation, polymerization of the acrylic curable silicone and the optional reactive acrylic compound can be initiated. A conductive layer cured by this polymerization can be formed. The light irradiation step may be performed during the drying step, or may be performed before or after the drying step.

As said active energy ray, an ultraviolet-ray, an electron beam, visible light etc. are mentioned, for example. Examples of the ultraviolet light source include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp.
The illuminance of ultraviolet irradiation is preferably 100 mW / cm ² or more, and the integrated light quantity is preferably 50 mJ / cm ² or more. Under these suitable irradiation conditions, the acrylic curable silicone and the reactive acrylic compound as an optional component can be more easily cured to form a crosslink.
Illuminance and integrated light quantity exemplified here were measured 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). Value.

  The average thickness of the conductive layer formed by curing the coating film is preferably 10 nm or more and 5000 nm or less, more preferably 20 nm or more and 1000 nm or less, and further preferably 30 nm or more and 500 nm or less. When the average thickness of the conductive layer is 10 nm or more, good conductivity is obtained, and when the average thickness is 5000 nm or less, the conductive layer can be easily formed.

[Stretching process]
The coated film obtained in the coating process is stretched to obtain a stretched film. By stretching the coating film, a large-area conductive film can be obtained even if the coating area of the conductive polymer dispersion is reduced, and the productivity of the conductive film is improved.

The coating film (conductive layer) of the coating film may be cured or may not be cured. The stretching process may be performed during the drying process or the light irradiation process, or may be performed before or after the drying process or the light irradiation process.
From the viewpoint of enhancing the followability of the conductive layer in stretching and reliably preventing cracking and peeling of the conductive layer, the coated film can be heated to dry the conductive layer and stretched to obtain a stretched film. preferable.

In the stretching step, the coated film may be stretched simultaneously with heating, or may be stretched immediately after the coated film is heated. If the film is stretched at the same time as the heating, or is stretched immediately after the heating, the coated film is softened to facilitate the stretching. If the heating for stretching is also used for drying, energy efficiency can be further increased.
In addition, since a part of polyvinyl alcohol may decompose | disassemble and lose | disappear with heating, not all the polyvinyl alcohol contained in the said conductive polymer dispersion liquid is necessarily contained in a conductive layer.

  Although the temperature at the time of heating a coating film in an extending | stretching process is suitably set according to the kind of film base material to be used, it can be 50 degreeC or more and 150 degrees C or less, for example. The heating temperature in the stretching step is preferably lower than the temperature for heating for the purpose of crystallizing the film substrate in the subsequent crystallization step. Here, the heating temperature is a set temperature of the heating device.

The stretching may be uniaxial stretching or biaxial stretching, but when a uniaxially stretched film is used as the film substrate, it is preferably stretched in a direction perpendicular to the already stretched direction. For example, when a uniaxially stretched film stretched along the longitudinal direction is used as a film substrate, it is preferably stretched along the width direction (short direction).
The stretch ratio of the coated film is preferably 2 to 20 times. If the draw ratio is 2 times or more, the productivity of the conductive film can be further increased, and if it is 20 times or less, the film can be prevented from being broken.

[Crystalling process]
The resin constituting the film substrate can be crystallized by heating and then cooling the stretched film obtained in the stretching step. Usually, a crystallized film has higher mechanical strength than an amorphous film (amorphous film).

The temperature at which the stretched film is heated depends on the type of film substrate, but is preferably 200 ° C. or higher. When heated to 200 ° C. or higher, at least a part of the resin constituting the film substrate starts to melt. After the melting, when cooled to a temperature lower than the crystallization temperature of the resin, the molten resin crystallizes and solidifies. Thereby, a film base material can be made into the crystalline film base material which consists of crystalline resin.
Moreover, when the thermal polymerization initiator is contained in the coating film by heating to 200 ° C. or higher, curing of the coating film with the thermal polymerization initiator can be completely completed.

The temperature lowering temperature to be cooled after heating depends on the type of film substrate, but is preferably 1 ° C./min to 200 ° C./min, and more preferably 10 ° C./min to 100 ° C./min.
Within the above range, the mechanical strength of the film substrate can be easily improved.

As the resin constituting the film substrate, polyethylene terephthalate (PET) is preferable. A film substrate made of a crystalline PET film is excellent in mechanical properties such as tensile strength.
By the crystallization process described above, a conductive film having a conductive layer on one side or both sides of the crystalline film substrate can be obtained.

<< Conductive film >>
A fourth aspect of the present invention is a conductive film having a film substrate and a conductive layer formed on at least one surface of the film substrate, wherein the conductive layer has a π-conjugated conductive polymer. And a conductive composite containing a polyanion, an acrylic curable silicone, and polyvinyl alcohol.
The conductive film of the fourth aspect may be obtained by the production method of the third aspect, or may be obtained by another production method.

As content of the said electroconductive complex with respect to the gross mass (100 mass%) of the said conductive layer in the electroconductive film of this aspect, 0.1 mass% or more and 10 mass% or less are preferable, for example, 0.3 mass% The content is more preferably 6% by mass or less, and further preferably 0.6% by mass or more and 3% by mass or less. When the amount is in the above range, good conductivity is easily exhibited.
As content of the said acrylic curable silicone with respect to the gross mass (100 mass%) of the said conductive layer in the conductive film of this aspect, 30 mass% or more and 99 mass% or less are preferable, for example, 40 mass% or more and 95 mass% The following is more preferable. Within the above range, more excellent scratch resistance and peelability are likely to be exhibited.
As content of the said polyvinyl alcohol with respect to the gross mass (100 mass%) of the said conductive layer in the electroconductive film of this aspect, 0.1 mass% or more and 20 mass% or less are preferable, for example, 0.5 mass% or more and 10 mass% The mass is preferably 1% by mass or less, and more preferably 1% by mass or more and 5% by mass or less. Within the above range, more excellent scratch resistance, stretchability and conductivity are easily exhibited.

<Effect>
The conductive layer of the conductive film of the present invention uniformly contains a cured product obtained by polymerizing acryloyl groups of acrylic curable silicone in the conductive layer. For this reason, it is considered that the mechanical strength of the conductive layer is enhanced by the cured product, and the scratch resistance, peelability, and heat resistance of the conductive layer are improved. As described above, the reason why the cured product can be uniformly dispersed in the conductive layer is that the polyvinyl alcohol contained in the conductive polymer dispersion applied when forming the conductive layer has the dispersibility of the acrylic curable silicone. It is thought that the effect which raises is demonstrated. Polyvinyl alcohol also improves the adhesion of the conductive layer to the base film, suppresses the occurrence of cracking and peeling of the conductive layer when stretched, and also exhibits the effect of increasing the stretchability of the conductive layer.

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

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

Example 1
80 g of X-62-7205 (manufactured by Shin-Etsu Chemical Co., Ltd., acrylic silicone), 96 g of PEDOT-PSS aqueous dispersion and PVA-217 (manufactured by Kuraray Co., Ltd., polyvinyl alcohol, 10% aqueous solution, degree of saponification 87-89%, polymerization Degree 1700) 24 g, Neugen XL-41 (Daiichi Kogyo Seiyaku Co., Ltd., nonionic surfactant) 0.8 g and propylene glycol 9 g are added and dispersed using a high-pressure homogenizer. Got.

(Example 2)
To 80 g of KF-2005 (manufactured by Shin-Etsu Chemical Co., Ltd., acrylic silicone), 96 g of PEDOT-PSS aqueous dispersion, 24 g of PVA-217, 0.8 g of Neugen XL-41, and 9 g of propylene glycol are added. Dispersion was performed using a homogenizer to obtain a conductive polymer dispersion.

(Example 3)
60 g of X-62-7205, 96 g of PEDOT-PSS aqueous dispersion, 24 g of PVA-217, 0.8 g of Neugen XL-41, 9 g of propylene glycol, UCECOAT 7200 (manufactured by Daicel Ornex, water Dispersed acrylic emulsion, solid content 65%) 20 g was added and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion.

Example 4
To 60 g of KF-2005, 96 g of PEDOT-PSS aqueous dispersion, 24 g of PVA-217, 0.8 g of Neugen XL-41, 9 g of propylene glycol, and 20 g of UCECOAT 7200 were added, and a high-pressure homogenizer To obtain a conductive polymer dispersion.

(Comparative Example 1)
To 80 g of X-62-7205, 96 g of PEDOT-PSS aqueous dispersion, 0.8 g of Neugen XL-41 and 9 g of propylene glycol are added, and dispersed using a high-pressure homogenizer. Obtained. However, since X-62-7205 and water were separated and a uniform dispersion was not obtained, the subsequent processing was stopped.

(Comparative Example 2)
To 80 g of KF-2005, 96 g of PEDOT-PSS aqueous dispersion, 0.8 g of Neugen XL-41, and 9 g of propylene glycol were added and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion. . However, KF-2005 and water were separated, and a uniform dispersion could not be obtained, so the subsequent processing was stopped.

(Example 5)
To 10 g of the conductive polymer dispersion prepared in Example 1, 0.16 g of Irgacure 2959 (manufactured by BASF, photopolymerization initiator) was added to prepare a paint. The prepared paint was applied onto a crystalline PET film using a # 4 bar coater, dried at 100 ° C. for 1 minute, and then irradiated with ultraviolet rays of 400 mJ. The resulting film was evaluated for surface resistance, peel strength, and scratch resistance by the following methods. The results are shown in Table 2.

<Evaluation>
[Measurement of surface resistance]
The surface resistance value (unit: Ω / □) of the conductive layer of the produced film was measured using a resistivity meter (Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Analytic Co., Ltd.) under an applied voltage of 10V.
[Measurement of peel force]
A polyester adhesive tape having a width of 25 mm (No. 31B, manufactured by Nitto Denko Corporation) was placed on the surface of the conductive layer of the produced film, and a load of 1976 Pa was placed on the adhesive tape and heat-treated at 25 ° C. for 20 hours. Next, the adhesive tape affixed to the conductive layer was peeled off at an angle of 180 ° (peeling speed 0.3 m / min) using a tensile tester, and the peeling force (unit: N) was measured. The smaller the peeling force, the higher the release property of the conductive layer.
[Evaluation of scratch resistance]
A non-woven fabric was applied to the surface of the conductive layer of the produced film, and the state of the appearance after rubbing 10 reciprocations with a load of 10 g / cm ² was visually evaluated.

(Example 6)
A film was prepared and evaluated in the same manner as in Example 5 except that the conductive polymer dispersion prepared in Example 1 was changed to the conductive polymer dispersion prepared in Example 2. The results are shown in Table 1.

(Example 7)
A film was prepared and evaluated in the same manner as in Example 5 except that the conductive polymer dispersion prepared in Example 1 was changed to the conductive polymer dispersion prepared in Example 3. The results are shown in Table 1.

(Example 8)
A film was prepared and evaluated in the same manner as in Example 5 except that the conductive polymer dispersion prepared in Example 1 was changed to the conductive polymer dispersion prepared in Example 4. The results are shown in Table 1.

Example 9
To 10 g of the conductive polymer dispersion obtained in Example 1, VA-086 (manufactured by Wako Pure Chemical Industries, Ltd., water-soluble azo polymerization initiator: 2,2′-Azobis [2-methyl-N- (2- Hydroxyethyl) propionamide]) was added at 0.16 g to create a paint. The prepared paint was applied onto an amorphous PET film using a # 4 bar coater and dried at 100 ° C. for 1 minute to obtain a coated film. Next, using a biaxial stretching apparatus (11A9, manufactured by Imoto Seisakusho Co., Ltd.), the film was stretched twice to obtain a stretched film. The stretched film was heated at 240 ° C. for 30 seconds, and then slowly cooled so that the temperature lowering rate was 80 ° C./min to 100 ° C./min. Thereby, the amorphous PET film of the film base was crystallized to obtain a crystalline PET film. The obtained crystalline film was evaluated for surface resistance, peel strength, and scratch resistance by the methods described above. The results are shown in Table 1.

(Example 10)
A crystalline film was prepared and evaluated in the same manner as in Example 9, except that the conductive polymer dispersion prepared in Example 1 was changed to the conductive polymer dispersion prepared in Example 2. The results are shown in Table 1.

(Example 11)
A crystalline film was prepared and evaluated in the same manner as in Example 9 except that the conductive polymer dispersion prepared in Example 1 was changed to the conductive polymer dispersion prepared in Example 3. The results are shown in Table 1.

(Example 12)
A crystalline film was prepared and evaluated in the same manner as in Example 9 except that the conductive polymer dispersion prepared in Example 1 was changed to the conductive polymer dispersion prepared in Example 4. The results are shown in Table 1.

(Comparative Example 3)
To 80 g of hydroxyethyl acrylate, 96 g of PEDOT-PSS aqueous dispersion, 24 g of PVA-217 (manufactured by Kuraray Co., Ltd., polyvinyl alcohol, 10% aqueous solution, degree of saponification 87-89%, degree of polymerization 1700) and Neugen XL-41 (No. 0.8 g of non-ionic surfactant (manufactured by Ichiko Pharmaceutical Co., Ltd.) and 9 g of propylene glycol were added and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion.

(Comparative Example 4)
A crystalline film was prepared and evaluated in the same manner as in Example 9 except that the conductive polymer dispersion prepared in Example 1 was changed to the conductive polymer dispersion prepared in Comparative Example 3. The results are shown in Table 1.

<Discussion>
Since the conductive polymer dispersions of Examples 1 to 4 contain polyvinyl alcohol together with the conductive composite and the acrylic curable silicone, the conductive composite and the acrylic curable silicone are not phase separated from water. Shows good dispersibility.
In manufacture of the conductive film of Examples 5-12, since the conductive polymer dispersion which shows favorable dispersibility is apply | coated to the film base material, the composition bias of the coating film (conductive layer) formed Thus, a conductive layer having a uniform composition distribution can be formed. As a result, a conductive film having a low surface resistance, a high peel strength, and excellent scratch resistance is obtained. These excellent properties are not deteriorated even after passing through the stretching step and the crystallization step, and the conductive film according to the present invention is further excellent in stretchability and heat resistance.
From the above, it is clear that the conductive film according to the present invention has excellent conductivity, peelability, scratch resistance, stretchability, and heat resistance.

Claims (18)

  A conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, an acrylic curable silicone, polyvinyl alcohol, and water.   2. The conductive polymer dispersion according to claim 1, wherein the acrylic curable silicone is emulsified.   3. The conductive polymer dispersion according to claim 1, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).   4. The conductive polymer dispersion according to any one of claims 1 to 3, wherein the polyanion is polystyrene sulfonic acid.   5. The conductive polymer dispersion according to any one of claims 1 to 4, wherein the conductive polymer dispersion further contains a nonionic surfactant.   6. The conductive polymer dispersion according to claim 5, wherein the nonionic surfactant is a polyoxyalkylene branched decyl ether.   7. The conductive polymer dispersion according to any one of claims 1 to 6, wherein the conductive polymer dispersion further contains a reactive acrylic compound other than the acrylic curable silicone.   8. The conductive polymer dispersion according to claim 1, wherein the conductive polymer dispersion further contains a radical photopolymerization initiator.   9. The conductive polymer dispersion according to any one of claims 1 to 8, wherein the conductive polymer dispersion further contains an azo radical initiator.   a mixing step of mixing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an acrylic curable silicone, polyvinyl alcohol, and an aqueous dispersion medium, and emulsifying the acrylic curable silicone; A method for producing a conductive polymer dispersion.   11. The method for producing a conductive polymer dispersion according to claim 10, wherein in the mixing step, a nonionic surfactant is further mixed to emulsify the acrylic curable silicone. A conductive film having a film base and a conductive layer formed on at least one surface of the film base,
A conductive film comprising a conductive composite containing a π-conjugated conductive polymer and a polyanion, an acrylic curable silicone, and polyvinyl alcohol in the conductive layer.   A method for producing a conductive film, comprising a coating step of coating the conductive polymer dispersion according to any one of claims 1 to 9 on at least one surface of a film substrate to obtain a coated film. .   14. The method for producing a conductive film according to claim 13, comprising at least one of a drying step of heating and drying the coated film and a light irradiation step of irradiating the coated film with ultraviolet rays.   15. The method for producing a conductive film according to claim 14, wherein the film substrate is an amorphous film substrate, and has a stretching step of heating and drying the coated film and stretching to obtain a stretched film.   16. The method for producing a conductive film according to claim 15, further comprising a crystallization step in which the stretched film is heated and then cooled to crystallize the amorphous film substrate.   17. The method for producing a conductive film according to claim 16, wherein a heating temperature of the stretched film in the crystallization step is set to 200 ° C. or higher.   The method for producing a conductive film according to any one of claims 15 to 17, wherein the amorphous film base material is an amorphous polyethylene terephthalate film.