JP6829080B2 - Conductive polymer dispersion liquid and its manufacturing method, and conductive film and its manufacturing method - Google Patents

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 an 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 base material and stretched as necessary. For example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2016-047501

However, Patent Document 1 does not study improving the scratch resistance (scratch resistance) and the peelability (easiness 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 liquid containing a conductive composite 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], 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 contains 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 photoradical polymerization 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 to emulsify the acrylic curable silicone. A method 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 base material and a conductive layer formed on at least one surface of the film base material, wherein the conductive layer contains a π-conjugated conductive polymer and a polyanion. A conductive film containing a sex composite, acrylic curable silicone, and polyvinyl alcohol.
[13] Conductive having a coating step of applying the conductive polymer dispersion liquid according to any one of [1] to [9] to at least one surface of a film substrate to obtain a coated film. A method for producing a sex film.
[14] The method for producing a conductive film according to [13], which comprises 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 base material is an amorphous film base material, and has a stretching step of heating and drying the coating film and stretching to obtain a stretched film. Production method.
[16] The method for producing a conductive film according to [15], which comprises a crystallization step of heating and then cooling the stretched film to crystallize the amorphous film substrate.
[17] The method for producing a conductive film according to [16], wherein the heating temperature of the stretched film in the crystallization step is 200 ° C. or higher.
[18] The method for producing a conductive film according to any one of [15] to [17], wherein the amorphous film base material 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. Further, even after the stretching treatment and the heat treatment for crystallizing the film base material, the increase in the surface resistance value is suppressed, and the film has excellent conductivity, scratch resistance and peelability. Therefore, the conductive film of the present invention is suitable for use as an antistatic film.
The conductive polymer dispersion liquid of the present invention is suitably used for producing a conductive film.
According to the method for producing a conductive polymer dispersion liquid of the present invention, it is possible to easily obtain a dispersion liquid in which each component of a conductive composite, acrylic curable silicone and polyvinyl alcohol is uniformly dispersed without phase separation. Can be done.

<< Conductive polymer dispersion >>
The first aspect of the present invention is a conductive polymer dispersion liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, an acrylic curable silicone, polyvinyl alcohol, and water.
The conductive polymer dispersion may contain a nonionic surfactant, a reactive acrylic compound not corresponding to the acrylic curable silicone, a binder component, a highly conductive agent, and other additives, if 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 it is an organic polymer whose main chain is composed of a π-conjugated system. For example, a polypyrrole-based conductive polymer or a polythiophene-based polymer Conductive polymer, polyacetylene-based conductive polymer, polyphenylene-based conductive polymer, polyphenylene vinylene-based conductive polymer, polyaniline-based conductive polymer, polyacene-based conductive polymer, polythiophene vinylene-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).
Examples of the polypyrrole-based 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-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 forming the conductive composite may be of one type or two or more types.

The polyanion is a polymer having two or more monomer units having an anionic group in the molecule. The anionic 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 anionic group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of the polyanion include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic sulfonic acid, polymethacrylic sulfonic acid, poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, and poly. Polymers with sulfonic acid groups such as sulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzenesulfonic acid, polyvinylcarboxylic acid, polystyrenecarboxylic acid, polyallylcarboxylic acid, polyacryliccarboxylic acid, polymethacryl Examples thereof include polymers having a carboxylic acid group such as carboxylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, and polyacrylic acid.
The polyanion may be a polymer composed of a single type of monomer or 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 the conductivity can be made higher.
The polyanion forming the conductive composite may be one kind or two or more kinds.
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 in the present specification is a value obtained by measuring by gel permeation chromatography and using polystyrene as a standard substance.

The range of the weight ratio of the 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. More preferably 1: 2.5 to 1: 4.5.
When the weight ratio is 1: 2 or more, the doping effect on the π-conjugated conductive polymer is enhanced, and the conductivity is improved. In addition, 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 can be 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 easily follows the stretching of the film, and the conductive layer is less likely to be cracked or peeled off.
Polyvinyl alcohol is produced by saponifying the 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 polyvinyl alcohol used in this embodiment is preferably 70% or more and 100% or less. When the saponification degree of polyvinyl alcohol is at least the above lower limit value, 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 60,000 or less. When the mass average molecular weight of polyvinyl alcohol is at least the lower limit value, the stretchability of the conductive layer can be sufficiently improved, and when it is at least the 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 by gel permeation chromatography and using polystyrene as a standard substance.

The polyvinyl alcohol contained in the conductive polymer dispersion may be of one kind or two or more kinds.
The content ratio of polyvinyl alcohol in the conductive polymer dispersion is preferably, for example, 10 parts by mass or more and 1000 parts by mass or less, and more preferably 100 parts by mass or more and 500 parts by mass or less 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 improved. When the content ratio is 1000 parts by mass or less, the decrease in conductivity can be suppressed.

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

In formula (1), R ¹ represents a hydrogen, methyl group or 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 -S-R 4 - and the like Can be mentioned. R ³ and R ⁴ 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. The 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 replaced with −O—CO−, −O—CO—O−, −CH = CH−, −C≡C−, or the like.

The site where the acryloyl group binds to the main skeleton may be a side chain of polysiloxane, one or both ends of polysiloxane, or at least one of the side chain and both ends of polysiloxane. You may.
The number of the acryloyl group 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 crosslinked with each other to form a conductive layer having better scratch resistance and peelability.
The number of acryloyl groups contained in the acrylic curable silicone is preferably 2 or more and 10 or less, for example.

As the side chain of the polysiloxane, the same side chain as that of a known polysiloxane is applied, and examples thereof include a hydrogen atom, a methyl group, and a phenyl group.
The molecular weight of the polysiloxane is not particularly limited, and is preferably a molecular weight 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 KF-2005, X-62-7205, Momentive Performance Materials, which are solvent-free UV curable silicones sold by Shin-Etsu Chemical Co., Ltd. as a mold release agent. TPR6500, TPR6501, TPR6502, UV9300, UV9315, XS56-A2982, UV9430 and the like sold by Materials Japan GK are preferable.

The acrylic curable silicone contained in the conductive polymer dispersion may be of one type or two or more types.
The content of the acrylic curable silicone in the conductive polymer dispersion is preferably 100 parts by mass or more and 50,000 parts by mass or less, and 1000 parts by mass or more and 25,000 parts by mass with respect to 100 parts by mass of the conductive composite. The following is more preferable, and more preferably 5000 parts by mass or more and 10000 parts by mass or less.
When it is 100 parts by mass or more, the scratch resistance and peelability of the formed conductive layer can be further improved. When it is 50,000 parts by mass or less, the content of the conductive composite is prevented from being extremely lowered, and good conductivity can be obtained.

The acrylic curable silicone is preferably emulsified in the conductive polymer dispersion. By being emulsified, the acrylic curable silicone is prevented from being phase-separated, and it becomes easier to uniformly disperse the silicone. 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 liquid is visually or microscopically observed to confirm that fine droplets are dispersed. Next, the droplets are separated, 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 that disperses the conductive composite, the acrylic curable silicone, and polyvinyl alcohol, and is water or a mixed solution 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 80% by mass or more, based on the total mass (100% by mass) of the aqueous dispersion medium. Is more preferable. When the content ratio of water in the aqueous dispersion medium is at least the above lower limit value, the dispersibility of the conductive composite or the like in the conductive polymer dispersion is further improved.
Here, when the binder component described later is contained in the conductive polymer dispersion liquid and the binder component contains water, the water contained in the binder component and the water in which the conductive composite is dispersed are not distinguished. That is, all the water contained in the conductive polymer dispersion liquid 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.
The organic solvent may be one kind or two or more kinds.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, allyl alcohol and the like.
Examples of the ether solvent include propylene glycol monoalkyl ethers such as diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, and propylene glycol monomethyl ether, and propylene glycol dialkyl ethers.
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 ^11s may be the same as each other or may be different from each other. n is appropriately set by HLB (Hydrophilic-Lipophilic Balance). Here, the HLB is calculated by Griffin's formula.
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 the Neugen XL series listed below manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. The numbers in parentheses below 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 or more and 5% by mass or less, and 0.1% by mass or more and 1% by mass. % Or less is more preferable, and 0.2% by mass or more and 0.5% by mass or less is further preferable.
When it is 0.01% by mass or more, the dispersibility of the acrylic curable silicone in the conductive polymer dispersion can be further improved. When it is 5% by mass or less, the content of the conductive composite is prevented from being extremely lowered, and good conductivity can be obtained.

<Binder component>
The conductive polymer dispersion liquid 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, polyvinyl alcohol, and the nonionic surfactant, and the mechanical strength of the conductive layer formed by applying the conductive polymer dispersion liquid. It is a component that can improve the hardness.
Examples of the binder component include resins, thermosetting compounds, and active energy ray-curable compounds. When the conductive polymer dispersion contains a thermosetting compound, it is preferable that a thermosetting initiator is also contained, and when an active energy ray-curable compound is contained, a photopolymerization initiator is also contained. Is also preferably contained.

Examples of the resin that can be used as the binder component include acrylic resin other than the acrylic curable silicone, polyester resin, epoxy resin, oxetane resin, polyurethane resin, polyimide resin, melamine resin, silicone resin other than the acrylic curable silicone, and vinyl acetate resin. 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 is easily dispersed or dissolved in an aqueous solvent and easily cured. Here, "reactivity" means a property of being radically polymerized and cured by 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, and carboxylic acid vinyl ester. The number of radically polymerizable functional groups contained 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, trimethylolpropantriacrylate, Examples thereof include glycerin propoxytriacrylate.
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, trimethylpropantrimethacrylate and the like.
Examples of (meth) acrylamide include methacrylamide, 2-hydroxyethylacrylamide, N-methylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N-phenylacrylamide, N-methylolacrylamide, and dimethylaminopropylacrylamide. Examples thereof include dimethylaminopropyl methacrylamide, diacetone acrylamide, N, N-dimethylacrylamide, N-vinylformamide, acryloylmorpholin, acryloylpiperidin 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 carboxylic acid vinyl ester include vinyl butyrate, vinyl monochloroacetate, vinyl pivalate and the like.
Further, 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, and polyacrylic acrylate.
The reactive acrylic compound contained in the conductive polymer dispersion may be one kind or two or more kinds.

The solid content of the binder component is preferably, for example, 10 parts by mass or more and 100,000 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 it is 100,000 parts by mass or less, the content ratio of the conductive composite is lowered. Can be suppressed and good conductivity can be ensured.

<Polymerization initiator>
Examples of the polymerization initiator of the acrylic curable silicone and the reactive acrylic compound include known photoradical polymerization initiators and known thermal polymerization initiators.
Examples of the photoradical polymerization initiator include the 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 initiators) manufactured by Wako Pure Chemical Industries, Ltd. Examples thereof include -061, VA-086, V-501 and the like.
The polymerization initiator contained in the conductive polymer dispersion may be one kind or two or more kinds.
The content ratio of the polymerization initiator to the total mass of the conductive polymer dispersion is not particularly limited, and may be in the range of the general content ratio 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 above-mentioned conductive composites, acrylic curable silicones, polyvinyl alcohols and nonionic surfactants are not classified as highly conductive agents. However, the organic solvent and the binder component may correspond to the highly conductive agent.
Highly conductive agents include saccharides, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxy groups, compounds having one or more hydroxy groups and one or more carboxy groups, and compounds having amide groups. 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 high conductivity agent contained in the conductive polymer dispersion may be one kind or two or more kinds.

It is preferable that the conductive polymer dispersion liquid 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 (heteroatom) 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 the nitrogen-containing aromatic cyclic compound 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. , Triazines containing three nitrogen atoms and their derivatives and the like. From the viewpoint of solvent solubility and the like, pyridines and their derivatives, imidazoles and their derivatives, pyrimidines and their derivatives are preferable.

Specific examples of pyridines and their derivatives 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-pyridinecarboxyaldehyde, 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, -Hydridine-5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4-pyridinemethanol, 4-pyridineethanol, 2-phenylpyridine, 3-methylquinoline, 3-ethylquinolin, quinolinol, 2,3-cyclopentenopyridine , 2,3-Cyclohexanopyridine, 1,2-di (4-pyridyl) ethane, 1,2-di (4-pyridyl) propane, 2-pyridinecarboxyaldehyde, 2-pyridinecarboxylic acid, 2-pyridinecarbonitrile , 2,3-Pyridine dicarboxylic acid, 2,4-Pyridine dicarboxylic acid, 2,5-Pyridine dicarboxylic acid, 2,6-Pyridine dicarboxylic acid, 3-Pyridine sulfonic acid and the like.

Specific examples of imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-propyl imidazole, 2-undyluimidazole, 2-phenylimidazole, N-methylimidazole, N-vinyl imidazole, and N-allyl imidazole. , 1- (2-Hydroxyethyl) imidazole (N-hydroxyethyl imidazole), 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, 1-benzyl-2-methyl imidazole, 1-benzyl-2-phenyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazole dicarboxylic acid, 4 , 5-Imidazole Dicarboxylate dimethyl, benzimidazole, 2-aminobenzimidazole, 2-aminobenzimidazole-2-sulfonic acid, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, 2- (2-pyridyl) ) Benzimidazole and the like can be mentioned.

Specific examples of pyrimidines and their derivatives 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. Can be mentioned.

Specific examples of pyrazines and their derivatives include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5-methylpyrazinecarboxylic acid, pyrazineamide, 5 -Methylpyrazineamide, 2-cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,3-diethylpyrazine and the like can be mentioned.

Specific examples of triazines and their derivatives 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'- Examples thereof include disodium disulfonate, 2-hydroxy-4,6-dichloro-1,3,5-triazine.

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, and the like. 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, thiodiethanol, glucose, tartrate, D-glucal Polyhydric aliphatic alcohols such as acids and glutaconic acids; high molecular weight alcohols such as cellulose, polysaccharides and sugar alcohols; 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecylbenzene , 2,4-Dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, 2,6-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4'-dihydroxydiphenyl Sulphon, 2,2', 5,5'-tetrahydroxydiphenyl sulphon, 3,3', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulphon, hydroxyquinonecarboxylic acid and its salts, 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 its salts, 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-Dihydroxynaphthalene-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-Trihydroxybenzene (pyrogalol), 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 Acetphenone, trihydroxybenzophenone, trihydroxybenzoaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetrahydroxy-p-benzoquinone, tetrahydroxyanthraquinone, methyl garlic acid (methyl gallicate), ethyl garlic acid (corrosive) Examples include aromatic compounds such as ethyl acid) and potassium hydroquinone sulfonate.

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, glutaconic acid and the like.

The compound having an amide group is a monomolecular compound having an amide bond in the molecule represented by -CO-NH- (the CO portion is a double bond). That is, examples of the amide compound include 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, and urea and a urea derivative in which the functional groups at both ends are hydrogen. And so on.
Specific examples of the amide compound include acetamide, malonamide, succinamide, maleamide, fumalamide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotine amide, isonicotine amide, 2-fluamide, formamide, N-methylformamide and propionamide. , Propiolamide, Butylamide, Isobutylamide, Palmitoamide, Stearylamide, Oleamide, Oxamide, Glutalamide, Adipamide, Sinnamamide, Glycolamide, Lactoamide, Glyceramide, Tartaramide, Citramide, Glyoxylamide, Pyrvoamide, Acetacetamide, Dimethylacetamide, benzyl Amide, anthranilamide, ethylenediaminetetraacetamide, diacetamide, triacetamide, dibenzamide, tribenzamide, rodonine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1 , 3-Diethylurea and derivatives thereof.

In addition, acrylamide can also be used as the amide compound. Examples of acrylamide include N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, Examples thereof include N-diethylmethacrylamide, 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide.
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 the conductivity becomes higher. 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, and the like.

Further, the imide compound is classified into an aliphatic imide, an aromatic imide and the like according to the type of the functional group at both ends, and the aliphatic imide is preferable from the viewpoint of solubility.
Further, 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 both R ¹ and R ² are saturated hydrocarbon compounds. Specifically, cyclohexane-1,2-dicarboxyimide, allantin, hydantoin, barbitulic acid, alloxan, glutarimide, succinimide, 5-butylhydantoinic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5 , 5-trimethylhydantoin, 5-hydantoin acetate, N-hydroxy-5-norbornene-2,3-dicarboxyimide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimideoxycarbonyloxy) Ethyl] sulfone, α-methyl-α-propylsuccinimide, cyclohexylimide and the like can be mentioned.
The unsaturated aliphatic imide compound is a compound represented by R ¹ -CO-NH-CO-R ² , and is a compound in which one or both of R ¹ and R ² have one or more unsaturated bonds. Specific examples include 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimidebutane, 1,6-bismaleimidehexane, and 1,8-bis. Maleimide octane, N-carboxyheptyl maleimide 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 is a compound in which 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 unsaturated or heteroatoms.
Examples of the lactam compound include pentano-4-lactam, 4-pentane lactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexanelactam 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 ether, and 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. It 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 conductive agent is 10 parts by mass or more, the effect of improving the conductivity by adding the high conductive agent is sufficiently exhibited, and when it is 10000 parts by mass or less, the content ratio of the conductive composite is high. The decrease is suppressed and good conductivity can be obtained.

The conductive polymer dispersion may contain known additives.
The additive is not particularly limited as long as the effect of the present invention can be obtained, and for example, a surfactant other than the nonionic surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant, and an ultraviolet absorbing agent. Agents can be used. However, the additive is a compound other than the above-mentioned conductive composite, acrylic curable silicone, polyvinyl alcohol, binder component, and high conductivity agent.
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, an amino group, an epoxy group and the like.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and sugars.
Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxanilide-based UV absorbers, hindered amine-based UV absorbers, benzoate-based UV absorbers, etc. Can be mentioned.

When the conductive polymer dispersion liquid contains the above-mentioned additive, the content ratio thereof is appropriately determined according to the type of the additive, but usually, with respect to 100 parts by mass of the solid content of the conductive composite, 0. It is preferably in the range of 001 parts by mass or more and 5 parts by mass or less.

In the total mass (100% by mass) of the conductive polymer dispersion, the balance excluding the above-mentioned conductive composite, acrylic curable silicone, polyvinyl alcohol, binder component, and high conductivity agent contains other optional components. It is preferably a dispersion medium that may be contained.
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 or more and 95% by mass or less, and more preferably 40% by mass or more and 80% by mass or less. 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 coatability on the film substrate becomes better.

<< Manufacturing method of conductive polymer dispersion >>
In the 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 to obtain the acrylic curable silicone. It is a method for producing a conductive polymer dispersion having a mixing step of emulsifying. Each component used in this embodiment is the same as that described in the first embodiment.
The method of mixing each component is not particularly limited, and for example, a stirring method for producing a known emulsion is applied.
In the mixing step, it is preferable to further mix a nonionic surfactant to emulsify the acrylic curable silicone. Emulsification can be achieved more easily by adding a nonionic surfactant. Confirmation that the acrylic curable silicone has been emulsified can be performed by the method described above.
By the production method of this aspect, the conductive polymer dispersion of the first aspect can be produced. The mixing ratio of each component is appropriately adjusted based on the content ratio described in the first aspect.

<< Manufacturing method of conductive film >>
A third aspect of the present invention is a method for producing a conductive film, which comprises a coating step of applying the conductive polymer dispersion liquid of the first aspect to at least one surface of a film substrate to obtain a coated film. is there.

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

Examples of the film base material used in the coating process include a plastic film.
Examples of the resin for the film base material constituting the plastic film include ethylene-methylmethacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, and polybutylene terephthalate. , Polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene-based elastomer, polyester-based elastomer, polyether sulfone, polyetherimide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio Examples include Nate. Among these resins for film substrates, 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. In any case, it can be a crystalline film base material in an arbitrary crystallization step in the subsequent stage, but an amorphous film is preferable from the viewpoint of good stretchability.
The film substrate may be unstretched or stretched, but when stretched in the subsequent stretching step, it is preferably unstretched in at least one direction.
Further, in order to improve the adhesion of the conductive layer formed by applying the conductive polymer dispersion liquid to the film base material, the film base material is subjected to corona discharge treatment, plasma treatment, flame treatment, etc. 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 at least the lower limit value, it is difficult to break, and if it is at least 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 points and averaging the measured values.

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 coating method using a coater such as a blade coater, a cast coater, 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 it can be easily applied. In bar coaters, the coating thickness differs depending on the type, and in commercially available bar coaters, a number is assigned to each type, and the larger the number, the thicker the coating can be applied.
The amount of the conductive polymer dispersion liquid 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 to only one side of the film substrate to form a coating film on only one side, or the conductive polymer dispersion may be applied to both sides of the film substrate. May be applied to form a coating film on both sides. A film in which a coating film is formed on a film substrate is called a coating film.

The drying step of drying the coating film of the coating film is performed after the coating step, before the stretching step, or while stretching and heating in the stretching step in order to improve the uniformity in the thickness direction. Is preferable.

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

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

Examples of the active energy ray include ultraviolet rays, electron beams, visible rays and the like. Examples of the light source of ultraviolet rays include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps and the like.
The illuminance of ultraviolet irradiation is preferably 100 mW / cm ² or more, and the integrated light intensity is preferably 50 mJ / cm ² or more. Under these suitable irradiation conditions, the acrylic curable silicone and the reactive acrylic compound of any component can be more easily cured to form crosslinks.
The illuminance and integrated light amount exemplified here were measured using UVR-T1 manufactured by Topcon (industrial UV checker, receiver; UD-T36, measurement wavelength range: 300 nm or more and 390 nm or less, peak sensitivity wavelength: about 355 nm). The value.

The average thickness of the conductive layer obtained 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 can be obtained, and when it is 5000 nm or less, the conductive layer can be easily formed.

[Stretching process]
The coating film obtained in the coating step 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) contained in the coating film may or may not be cured. The stretching step may be performed during the drying step or the light irradiation step, or may be performed before or after the drying step or the light irradiation step.
From the viewpoint of enhancing the followability of the conductive layer in stretching and surely preventing cracking and peeling of the conductive layer, the coating film can be heated to dry and stretch the conductive layer to obtain a stretched film. preferable.

In the stretching step, the coating film may be stretched at the same time as it is heated, or it may be stretched immediately after the coating film is heated. If the coating film is stretched at the same time as heating or immediately after heating, the coating film is softened and stretched easily. If the heating for stretching is also used for drying, the energy efficiency can be further improved.
Since a part of polyvinyl alcohol may be decomposed and disappear by heating, not all of the polyvinyl alcohol contained in the conductive polymer dispersion is contained in the conductive layer.

The temperature at which the coating film is heated in the stretching step is appropriately set according to the type of film substrate used, and can be, for example, 50 ° C. or higher and 150 ° C. or lower. The heating temperature in the stretching step is preferably lower than the temperature at which the film substrate is heated for the purpose of crystallization 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 base material, 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 base material, it is preferably stretched along the width direction (short direction).
The draw ratio of the coating film is preferably 2 times or more and 20 times or less. 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 breaking.

[Crystallization process]
The resin constituting the film base material can be crystallized by heating and then cooling the stretched film obtained in the stretching step. Crystallized films usually have stronger mechanical strength than non-crystalline films (amorphous films).

The temperature at which the stretched film is heated depends on the type of film base material, 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 begins to melt. After the melting, when the resin is cooled to a temperature lower than the crystallization temperature of the resin, the melted resin crystallizes and solidifies. As a result, the film base material can be made into a crystalline film base material made of a crystalline resin.
Further, by heating to 200 ° C. or higher, when the coating film contains a thermal polymerization initiator, the curing of the coating film by the thermal polymerization initiator can be completely completed.

The temperature lowering temperature for cooling after heating is preferably 1 ° C./min or more and 200 ° C./min or less, and more preferably 10 ° C./min or more and 100 ° C./min or less, although it depends on the type of film substrate.
Within the above range, the mechanical strength of the film base material can be easily improved.

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

《Conductive film》
A fourth aspect of the present invention is a conductive film having a film base material and a conductive layer formed on at least one surface of the film base material, wherein the conductive layer is a π-conjugated conductive polymer. A conductive film containing a conductive composite containing polyanions, 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.

The content of the conductive composite with respect to the total mass (100% by mass) of the conductive layer in the conductive film of this embodiment is, for example, preferably 0.1% by mass or more and 10% by mass or less, preferably 0.3% by mass. More than 6% by mass is more preferable, and 0.6% by mass or more and 3% by mass or less is further preferable. Within the above range, good conductivity is likely to be exhibited.
The content of the acrylic curable silicone with respect to the total mass (100% by mass) of the conductive layer in the conductive film of this embodiment is preferably, for example, 30% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or more. The following is more preferable. Within the above range, more excellent scratch resistance and peelability are likely to be exhibited.
The content of the polyvinyl alcohol with respect to the total mass (100% by mass) of the conductive layer in the conductive film of this embodiment is, for example, preferably 0.1% by mass or more and 20% by mass or less, and 0.5% by mass or more and 10%. It 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 likely to be exhibited.

<Effect>
The conductive layer of the conductive film of the present invention uniformly contains a cured product formed by polymerizing the acryloyl group of the acrylic curable silicone in the conductive layer. Therefore, 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. 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 liquid applied when forming the conductive layer determines the dispersibility of the acrylic curable silicone. It is thought that it has the effect of enhancing. Further, polyvinyl alcohol 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 exerts the effect of enhancing the stretchability of the conductive layer.

(Manufacturing Example 1)
206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and 1.14 g of ammonium persulfate oxidant solution previously dissolved in 10 ml of water was added dropwise for 20 minutes while stirring at 80 ° C., and this solution was added dropwise for 12 hours. Stirred.
1000 ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium polystyrene sulfonate-containing solution, and about 1000 ml of the solvent of the obtained polystyrene sulfonate-containing solution was removed. Next, 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 sulfonic acid was washed with water. This washing operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain 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 dissolved in 2000 ml of ion-exchanged water were mixed at 20 ° C.
The mixed solution thus obtained was kept at 20 ° C., and while 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 reaction was carried out with stirring for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. This operation was repeated 3 times.
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 by an ultrafiltration method. Next, 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 washing operation was repeated 3 times to obtain a 1.2% by mass polystyrene sulfonate-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, saponification degree 87-89%, polymerization Degree 1700) 24 g, Neugen XL-41 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., nonionic surfactant) 0.8 g, and propylene glycol 9 g were added and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion. Got

(Example 2)
To 80 g of KF-2005 (made 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, and high pressure is added. The mixture was dispersed 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, and 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 was added. 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 were added and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion. Obtained. However, since X-62-7205 and water were separated and a uniform dispersion could not be obtained, the subsequent treatment was stopped.

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

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

<Evaluation>
[Measurement of surface resistance value]
The surface resistance value (unit: Ω / □) of the conductive layer of the produced film was measured using a resistivity meter (High Resta MCP-HT450 manufactured by Mitsubishi Chemical Analytical Co., Ltd.) under the condition of an applied voltage of 10 V.
[Measurement of peeling force]
A polyester adhesive tape having a width of 25 mm (Nitto Denko KK, No. 31B) 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, using a tensile tester, the adhesive tape attached to the conductive layer was peeled off at an angle of 180 ° (peeling speed 0.3 m / min), and the peeling force (unit: N) was measured. The smaller the peeling force, the higher the releasability 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 a load of 10 g / cm ² was applied and rubbed 10 times back and forth, and the appearance 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 in an amount of 0.16 g to prepare a paint. The prepared paint was applied onto a non-crystalline PET film using a # 4 bar coater and dried at 100 ° C. for 1 minute to obtain a coated film. Next, a stretched film was obtained by stretching twice using a biaxial stretching device (manufactured by Imoto Seisakusho Co., Ltd., 11A9). 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 or more and 100 ° C./min or less. As a result, the amorphous PET film of the film base material was crystallized to obtain a crystalline PET film. The surface resistance value, peeling force, and scratch resistance of the obtained crystalline film were evaluated by the above-mentioned methods. 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, polyvinyl alcohol, 10% aqueous solution, saponification degree 87-89%, degree of polymerization 1700), and Neugen XL-41 (No. 1). 0.8 g of (nonionic 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 do not undergo phase separation from water. , Shows good dispersibility.
In the production of the conductive films of Examples 5 to 12, since the conductive polymer dispersion liquid showing good dispersibility is applied to the film base material, the composition of the coating film (conductive layer) formed is uneven. It is possible to form a conductive layer having a uniform composition distribution. As a result, a conductive film having a low surface resistance value, a high peeling force, and excellent scratch resistance has been obtained. These excellent properties have not deteriorated even after undergoing 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 (15)

containing a conductive composite comprising a π conjugated conductive polymer and polyanion, and acrylic curable silicone, polyvinyl alcohol, and water-based dispersion medium, and a nonionic surfactant other than the acrylic curable silicone , a conductive polymer dispersion liquid,
The content of water with respect to the total mass of the aqueous dispersion medium is 60% by mass or more.
A conductive polymer dispersion in which the acrylic curable silicone is emulsified . The conductive polymer dispersion according to claim 1 , wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). The conductive polymer dispersion according to claim 1 or 2 , wherein the polyanion is polystyrene sulfonic acid. The conductive polymer dispersion according to any one of claims 1 to 3, wherein the nonionic surfactant is a polyoxyalkylene branched decyl ether. The conductive polymer dispersion according to any one of claims 1 to 4 , wherein the conductive polymer dispersion further contains a reactive acrylic compound other than the acrylic curable silicone. The conductive polymer dispersion according to any one of claims 1 to 5 , wherein the conductive polymer dispersion further contains a photoradical polymerization initiator. The conductive polymer dispersion according to any one of claims 1 to 6 , wherein the conductive polymer dispersion further contains an azo radical initiator. A conductive composite containing a π-conjugated conductive polymer and a polyanion, an acrylic curable silicone, polyvinyl alcohol, an aqueous dispersion medium, and a nonionic surfactant other than the acrylic curable silicone were mixed . the mixture obtained, the acrylic-curable silicone have a mixing step to be emulsified,
A method for producing a conductive polymer dispersion, wherein the content of water with respect to the total mass of the aqueous dispersion medium is 60% by mass or more . A conductive film having a film base material and a conductive layer formed on at least one surface of the film base material.
The conductive film is a cured product of the conductive polymer dispersion liquid according to any one of claims 1 to 7 . A method for producing a conductive film, which comprises a coating step of applying the conductive polymer dispersion liquid according to any one of claims 1 to 7 to at least one surface of a film substrate to obtain a coated film. .. The method for producing a conductive film according to claim 10 , further 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. The method for producing a conductive film according to claim 11 , wherein the film base material is an amorphous film base material, and the coating film is heated to dry and stretched to obtain a stretched film. The method for producing a conductive film according to claim 12 , further comprising a crystallization step of heating and then cooling the stretched film to crystallize the amorphous film substrate. The method for producing a conductive film according to claim 13 , wherein the heating temperature of the stretched film in the crystallization step is 200 ° C. or higher. The method for producing a conductive film according to any one of claims 12 to 14 , wherein the amorphous film base material is an amorphous polyethylene terephthalate film.