JP6845096B2 - Method for manufacturing conductive polymer dispersion - Google Patents

Description

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

In various electronic devices such as smartphones, personal computers, automated teller machines, automatic ticket vending machines, vending machines, etc., input / output devices provided with a touch panel on the screen side of the liquid crystal display device are widely used.
In recent years, an in-cell capacitive touch panel may be used as an input / output device for the purpose of reducing the thickness and improving the optical performance. In the in-cell capacitive touch panel, the capacitive touch panel is built in the liquid crystal cell, and the electrode for displaying the image and the electrode for the touch panel sensor are shared to make it thinner (for example, patented). Document 1). Further, by sharing the electrodes, it is possible to reduce the reflection and refraction of light and improve the optical performance.

The in-cell capacitive touch panel includes a liquid crystal cell in which electrodes and liquid crystal molecules are provided between a pair of glass substrates, and a polarizing film attached to both sides of the liquid crystal cell.
By the way, the orientation of the liquid crystal molecules enclosed inside the liquid crystal cell is easily affected by static electricity, but static electricity may be generated when the polarizing film is attached. Therefore, in order to prevent the liquid crystal cell from being charged, a transparent antistatic layer may be laminated on the liquid crystal cell, and a polarizing film may be attached to the antistatic layer. However, if the antistatic layer is provided, there is a problem that the number of steps for manufacturing the in-cell type capacitance type touch panel increases.
Patent Document 2 discloses that an antistatic agent is contained in an adhesive layer for attaching a polarizing film to a liquid crystal cell to impart conductivity. By including the antistatic agent in the pressure-sensitive adhesive layer, the step of separately providing the antistatic layer can be omitted. Patent Document 2 describes that a π-conjugated conductive polymer such as polythiophene, an ionic compound, a surfactant, or the like is used as an antistatic agent contained in the pressure-sensitive adhesive layer.

International Publication No. 2014/042248 JP-A-2017-68026

Among the antistatic agents described in Patent Document 2, when an ionic compound or a surfactant is used, the heat resistance of the pressure-sensitive adhesive layer may be lowered. On the other hand, when a π-conjugated conductive polymer is used as the antistatic agent, it can be a heat-resistant conductive pressure-sensitive adhesive layer.
Since the π-conjugated conductive polymer does not disperse in water or an organic solvent as it is, it is usually made hydrophilic by being composited with a polyanion such as polystyrene sulfonic acid. Therefore, the π-conjugated conductive polymer is an acrylic adhesive and an acrylic adhesive having low hydrophilicity (hereinafter, the acrylic adhesive and the acrylic adhesive are collectively referred to as "acrylic adhesive". It has a low affinity with () and tends to have low dispersibility in acrylic adhesives. However, Patent Document 2 does not disclose any method for improving the dispersibility of the π-conjugated conductive polymer in the acrylic adhesive layer. Therefore, when a π-conjugated conductive polymer is used as an antistatic agent in the pressure-sensitive adhesive layer described in Patent Document 2, the π-conjugated conductive polymer cannot form a sufficient conductive network, resulting in poor conductivity. It could be low.

An object of the present invention is to provide a conductive polymer dispersion liquid and a method for producing the same, which can easily form a conductive adhesive layer having high dispersibility of a conductive composite and high conductivity and heat resistance. And. Another object of the present invention is to provide a conductive film provided with a conductive adhesive layer having high conductivity and heat resistance, a method for producing the same, and a conductive glass base material and a method for producing the same.

The present invention has the following aspects.
[1] A conductive composite containing a π-conjugated conductive polymer and a polyanion, an acrylic adhesive, and an organic solvent are contained.
A conductive polymer dispersion in which at least one amine compound selected from the group consisting of primary amines, secondary amines and tertiary amines is added to some anionic groups of the polyanions.
[2] The conductive polymer dispersion according to [1], which further contains a polyfunctional isocyanate having two or more isocyanate groups in one molecule.
[3] The conductive polymer dispersion according to [1] or [2], wherein the organic solvent is a ketone solvent.
[4] The conductive polymer dispersion according to [3], wherein the organic solvent is methyl ethyl ketone.
[5] The conductive polymer dispersion according to any one of [1] to [4], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[6] The conductive polymer dispersion liquid according to any one of [1] to [5], wherein the polyanion is polystyrene sulfonic acid.
[7] A conductive adhesive layer formed from the film base material and at least one surface of the film base material from the conductive polymer dispersion liquid according to any one of [1] to [6]. Conductive film with and.
[8] The conductive film according to [7], wherein the film base material is a polarizing film.
[9] A conductive glass base material comprising the conductive film according to [7] or [8] and a glass base material adhered to a conductive adhesive layer of the conductive film.
[10] The conductive glass base material according to [9], wherein the glass base material is a glass plate constituting a liquid crystal cell.

[11] At least one amine compound selected from the group consisting of primary amines, secondary amines and tertiary amines in an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion. And a precipitation step of precipitating the conductive composite to form a precipitate.
A recovery step for recovering the precipitate and
A method for producing a conductive polymer dispersion, which comprises a step of adding an acrylic adhesive to the recovered precipitate.
[12] The method for producing a conductive polymer dispersion liquid according to [11], wherein in the adhesive adhesive addition step, an organic solvent is further added to the precipitate.
[13] The method for producing a conductive polymer dispersion according to [11] or [12], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[14] The method for producing a conductive polymer dispersion liquid according to any one of [11] to [13], wherein the polyanion is polystyrene sulfonic acid.
[15] Adhesion to form a conductive adhesive layer by applying the conductive polymer dispersion liquid according to any one of [1] to [6] on at least one surface of the film substrate. A method for producing a conductive film, which comprises a coating layer forming step.
[16] The method for producing a conductive film according to [15], wherein the film base material is a polarizing film.
[17] By the conductive film manufacturing step of manufacturing the conductive film by the method of manufacturing the conductive film according to [15] or [16], and by attaching the conductive adhesive layer to the glass base material. A method for producing a conductive glass base material, which comprises an bonding step of adhering the conductive film to the glass base material.
[18] The method for producing a conductive glass base material according to [17], wherein the glass base material is a glass plate constituting a liquid crystal cell.

The conductive polymer dispersion liquid of the present invention has high dispersibility of the conductive composite, and can easily form a conductive adhesive layer having high conductivity and heat resistance.
According to the method for producing a conductive polymer dispersion liquid of the present invention, a conductive polymer dispersion liquid having the above-mentioned effect can be easily produced.
The conductive film of the present invention includes a conductive adhesive layer having high conductivity and heat resistance.
According to the method for producing a conductive film of the present invention, a conductive film having the above-mentioned effect can be easily produced.
The conductive glass substrate of the present invention includes a conductive adhesive layer having high conductivity and heat resistance.
According to the method for producing a conductive glass substrate of the present invention, a conductive glass substrate having the above-mentioned effect can be easily produced.

It is sectional drawing which shows one Embodiment of the conductive glass base material of this invention.

<Conductive polymer dispersion>
The conductive polymer dispersion liquid of one aspect of the present invention contains a conductive composite, an acrylic adhesive, and an organic solvent.

(Conductive complex)
The conductive complex in this embodiment includes a π-conjugated conductive polymer and a polyanion having two or more anion groups. The polyanion coordinates with the π-conjugated conductive polymer, and the anion group of the polyanion is doped with the π-conjugated conductive polymer to form a conductive composite having conductivity.
In the poly anion, all the anion groups are not doped in the π-conjugated conductive polymer and have an extra anion group. In the state before the addition of the amine compound occurs, the excess anion group is a hydrophilic group, so that the conductive complex has water dispersibility. However, in the conductive composite contained in the conductive polymer complex of this embodiment, an amine compound is added to the anion group of the polyanion, particularly the surplus anion group.
The conductive complex is made hydrophobized by adding an amine compound to the anionic group of the polyanion (hereinafter, may be referred to as "hydrophobic conductive complex").
Although detailed analysis of the conductive complex is not always easy, it is presumed that the substituent (A) represented by the following chemical formula (A) is formed by the addition of the amine compound to the anion group of the polyanion. ..

^{R 1} , R ² , and R ³ in the chemical formula (A) are substituents derived from the amine compounds described later. For example, ^{at least one of R 1} , R ² , and R ³ is a hydrocarbon group (however, at least one of the hydrogen atoms of the hydrocarbon group may be substituted with an alkyl group, an aryl group, a hydroxy group, or the like). Is. R ^{1, R} 2, is not an hydrocarbon group of ^{R 3} is a hydrogen atom.
The substituent (A) is bonded to the oxygen atom of the anion group.

The content of the hydrophobic conductive composite with respect to the total mass of the conductive polymer dispersion is, for example, preferably 0.1% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less. , 1.0% by mass or more and 5.0% by mass or less is more preferable.

[Π-conjugated conductive polymer]
The π-conjugated conductive polymer is not particularly limited as long as it has the effect of the present invention as long as it is an organic polymer whose main chain is composed of a π-conjugated system. 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-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3- Methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxyphene) Butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and poly (3-butyl). Pyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3) -Carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole) , Poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole).
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
Among the π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity, transparency and heat resistance.
The π-conjugated conductive polymer contained in the conductive complex may be of one type or two or more types.

[Polyanion]
The polyanion is a polymer having two or more monomer units having an anion group in the molecule. The anionic group of this polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic sulfonic acid, polymethacrylsulfonic acid, poly (2-acrylamide-2-methylpropanesulfonic acid), and polyisoprene sulfonic acid. Polymers having a sulfonic acid group such as acid, polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethacryloxybenzene sulfonic acid, polyvinylcarboxylic acid, polystyrene carboxylic acid, polyallylcarboxylic acid, polyacrylic carboxylic acid. , Polymethacrylcarboxylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, polyacrylic acid and other polymers with carboxylic acid groups. These homopolymers may be used, or two or more kinds of copolymers may be used.
Among these polyanions, a polymer having a sulfonic acid group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be made higher.
The polyanion may be used alone or in combination of two or more.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight in the present specification is a value obtained by measuring by gel permeation chromatography and based on standard polystyrene having a known molecular weight.

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

[Amine compound]
The amine compound used in this embodiment is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. One type of amine compound may be used alone, or two or more types may be used in combination.
The amine compound may have a hydrocarbon group or a substituent thereof. Examples of the hydrocarbon group or a substituent thereof that the amine compound may have include a linear or branched alkyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carbon number of carbon atoms. Aralkyl groups with 7 or more and 12 or less, alkylene groups with 2 or more and 12 or less carbon atoms, arylene groups with 6 or more and 12 or less carbon atoms, aralkylene groups with 7 or more and 12 or less carbon atoms, oxyalkylene groups with 2 or more and 12 or less carbon atoms, etc. Can be mentioned. Further, the amine compound may have a hydroxy group.

The amine compound is added to the anion group of the polyanion, particularly the surplus anion group that does not participate in doping the π-conjugated conductive polymer. As a result, the conductive complex becomes less hydrophilic and becomes hydrophobic, and the dispersibility in an organic solvent is improved.

Examples of the primary amine include aniline, toluidine, benzylamine, ethanolamine and the like.
Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine.
Among the amine compounds, a tertiary amine is preferable, and at least one of tributylamine and trioctylamine is more preferable because the conductive complex can be easily hydrophobized.

[Epoxy compound]
The conductive polymer dispersion liquid of this embodiment may contain an epoxy compound.
The epoxy compound is a compound having one or more epoxy groups in one molecule, and a monofunctional epoxy compound having one epoxy group in one molecule and a polyfunctional epoxy compound having two or more epoxy groups in one molecule. Can be mentioned. From the viewpoint of preventing aggregation or gelation, the epoxy compound is preferably a compound having one epoxy group in one molecule. One type of epoxy compound may be used alone, or two or more types may be used in combination.

The epoxy compound reacts with the anion group of the polyanion, particularly the surplus anion group that does not participate in doping the π-conjugated conductive polymer to form an ester. As a result, the conductive complex becomes less hydrophilic and becomes hydrophobic, and the dispersibility in an organic solvent is improved.

Examples of the monofunctional epoxy compound include propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxypentane, and the like. 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monooxide, 1,2-epoxytetradecane, glycidylmethyl ether, 1,2-epoxyoctadecane, 1,2-epoxyhexadecan, ethylglycidyl ether , Glysidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2- (chloromethyl) -1,2-epoxypropane, glycidol, epichlorohydrin, epibromohydrin, butyl glycidyl ether, 1,2- Epoxy hexane, 1,2-epoxy-9-decane, 2- (chloromethyl) -1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2-epoxy-1H, 1H, 2H, 2H, 3H, 3H -Trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-methyl-1,2-epoxycyclohexane, 1, 2-Epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H, 1H, 2H, 2H, 3H, 3H-heptadecafluorobutane, 3,4-epoxy tetrahydrofuran , Glycidyl stearate, 3-glycidyl oxypropyltrimethoxysilane, epoxy succinic acid, glycidyl phenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzyl glycidyl ether, diethoxy (3-glycidyl oxypropyl) methyl silane , 3- [2- (Perfluorohexyl) ethoxy] -1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl-3- (3-glycidyloxypropyl) trisiloxane, 9 , 10-Epoxy-1,5-cyclododecadien, 4-tert-butyl glycidyl benzoate, 2,2-bis (4-glycidyloxyphenyl) propane, 2-tert-butyl-2- [2- (4- (4-) Chlorophenyl)] ethyloxylane, styrene oxide, glycidyl Trityl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylprepylene oxide, cholesterol-5α, 6α-epoxide, stillbenoxide, glycidyl p-toluenesulfonate, 3-methyl-3-phenyl Ethyl glycidate, N-propyl-N- (2,3-epoxypropyl) perfluoro-n-octylsulfonamide, (2S, 3S) -1,2-epoxy-3- (tert-butoxycarbonylamino) -4 -Phenylbutane, 3-nitrobenzene sulfonic acid (R) -glycidyl, 3-nitrobenzene sulfonic acid-glycidyl, parthenolide, N-glycidyl phthalimide, endolin, dildrin, 4-glycidyl oxycarbazole, 7,7-dimethyloctanoic acid [oxyla Nylmethyl], 1,2-epoxide-4-vinylcyclohexane, C12, C13 mixed higher alcohol glycidyl ether and the like.

Examples of the polyfunctional epoxy compound include 1,6-hexanediol diglycidyl ether, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, 4-butanediol diglycidyl ether, 1, 2: 3, 4 − Diepoxybutane, 1,2-cyclohexanedicarboxylate diglycidyl, triglycidyl neopentyl glycol diglycidyl ether isocyanurate, 1,2: 3,4-diepoxybutane, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropanepolyglycidyl Ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol polyglycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, triglycidyl tris (2-Hydroxyethyl) isocyanate and the like can be mentioned.

The epoxy compound preferably has a molecular weight of 50 or more and 2,000 or less, and preferably has 10 or more and 30 or less carbon atoms, because it has high solubility in an organic solvent.

(Acrylic adhesive)
The acrylic adhesive used in this embodiment is one in which the surfaces of solids of the same type or different types are bonded and integrated, and specifically, an acrylic adhesive or an acrylic adhesive. is there. The adhesive is one that can be adhered semi-permanently, and the adhesive is one that can be temporarily adhered. However, even if it is an adhesive, it is possible to make it semi-permanently adhesive by a curing treatment.

The acrylic adhesive contains an acrylic polymer. The content of the acrylic polymer in the acrylic adhesive is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and 100% by mass. It may be.
Specific examples of the acrylic monomer forming the acrylic polymer include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-methoxyethyl acrylate. Ditrimethylolpropane tetraacrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A / ethylene oxide modified diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, dipropylene glycol diacrylate , Trimethylol propanetriacrylate, glycerin propoxytriacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, penta Acrylate such as erythritol triacrylate, tetrahydrofurfuryl acrylate, trimethylpropan triacrylate, tripropylene glycol diacrylate; tetraethylene glycol dimethacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, allyl methacrylate, 1 , 3-butylene glycol dimethacrylate, benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxy Methacrylates such as ethyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate; diacetoneacrylamide, N, N-dimethylacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylate, methacrylicamide, N-methylolacrylamide, acryloylformolin , N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-phenylacrylamide , Acryloyl piperidine, (meth) acrylamide such as 2-hydroxyethyl acrylamide and the like. One of these acrylic monomers may be used alone, or two or more thereof may be used in combination. It is also possible to adjust the adhesive strength by using two or more kinds of acrylic monomers.

As the monomer forming the acrylic polymer, a vinyl monomer other than the acrylic monomer may be copolymerized together with the acrylic monomer.
Examples of vinyl-based monomers other than the acrylic monomer include styrene, α-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, maleic anhydride and the like.
When the vinyl-based monomer is copolymerized, the content of the acrylic-based monomer unit in the acrylic polymer is preferably 50 mol% or more and less than 100 mol%, and more preferably 70 mol% or more and 98 mol% or less. preferable. When the acrylic monomer unit content is at least the above lower limit value, the adhesiveness can be easily exhibited.
The content of the vinyl-based monomer unit in the acrylic polymer can be, for example, 2 mol% or more and 20 mol% or less.

When the acrylic polymer is used as an adhesive, the composition of the acrylic polymer is such that the glass transition temperature is preferably 80 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 0 ° C. or lower. Is preferable. Acrylic polymers having a glass transition temperature of more than 80 ° C. are preferably not included in the acrylic adhesive because they have low adhesiveness and adhesiveness. The glass transition temperature of the acrylic polymer is −80 ° C. or higher, and it is difficult to obtain one having a glass transition temperature lower than that. The glass transition temperature of the acrylic polymer can be determined by differential scanning calorimetry or dynamic viscoelasticity measurement.
Examples of the monomer capable of lowering the glass transition temperature of the acrylic polymer include ethyl acrylate, butyl acrylate (particularly n-butyl acrylate), 2-ethylhexyl acrylate and the like. In the acrylic polymer, the larger the proportion of the monomer units derived from these monomers, the lower the glass transition temperature.

The mass average molecular weight of the acrylic polymer is preferably 10,000 or more and 2 million or less, and more preferably 30,000 or more and 1 million or less. When the mass average molecular weight of the acrylic polymer is at least the above lower limit value, sufficient cohesive force can be secured, and cohesive failure of the conductive adhesive layer formed from the conductive polymer dispersion can be prevented. .. On the other hand, when the mass average molecular weight of the acrylic polymer is not more than the upper limit value, the adhesive strength can be further improved.

When the acrylic polymer has an acrylic monomer unit having a reactive functional group, it may be cured by reacting with a curing agent. When the acrylic polymer is cured, the cohesive force of the conductive adhesive layer formed from the conductive polymer dispersion can be improved and the strength can be improved. Further, by improving the cohesive force of the conductive adhesive layer, it is possible to obtain a removable adhesive layer capable of repeating adhesion and peeling.
Examples of the reactive functional group include a hydroxy group, a carboxy group, an amino group, an amide group, an epoxy group and the like. When reacting with a polyfunctional isocyanate described later, the reactive functional group is preferably a hydroxy group, a carboxy group or an amino group, and more preferably a hydroxy group.
Examples of the acrylic monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl acrylate. , 4-Hydroxybutyl methacrylate and the like.
Examples of the acrylic monomer having a carboxy group include acrylic acid, methacrylic acid, itaconic acid and the like.
Examples of the acrylic monomer having an amino group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate and the like.
Examples of the acrylic monomer having an amide group include acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide and the like.
Examples of the acrylic monomer having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
When a polyfunctional isocyanate is used as the curing agent, among the acrylic monomers having a reactive functional group, an acrylic monomer having a hydroxy group is preferable in consideration of curability and cost, 2-hydroxyethyl acrylate, 2-. Hydroxyethyl methacrylate is more preferred.
One type of acrylic monomer having a reactive functional group may be used alone, or two or more types may be used in combination.

In the conductive polymer dispersion of this embodiment, the solid content of the acrylic adhesive is preferably 1 part by mass or more and 100,000 parts by mass or less with respect to 100 parts by mass of the hydrophobic conductive composite. It is more preferably 10 parts by mass or more and 50,000 parts by mass or less, and further preferably 100 parts by mass or more and 10,000 parts by mass or less. When the solid content of the acrylic adhesive is not less than the lower limit value, the conductive adhesive layer can sufficiently exhibit the adhesiveness, and when it is not more than the upper limit value, the conductive adhesive is provided. Sufficient conductivity of the layer can be ensured.

(Hardener)
As described above, when the acrylic polymer has an acrylic monomer unit having a reactive functional group, the conductive polymer dispersion may contain a curing agent.
Examples of the curing agent include isocyanate-based curing agents such as polyfunctional isocyanate having two or more isocyanate groups in one molecule, and epoxy-based curing agents such as epoxy compounds having two or more epoxy groups in one molecule. Among these curing agents, polyfunctional isocyanate is preferable from the viewpoint of reactivity and availability. In particular, when the acrylic polymer has an acrylic monomer unit having a hydroxy group, the curing agent is preferably a polyfunctional isocyanate.

Examples of the polyfunctional isocyanate include an aliphatic polyfunctional isocyanate, an alicyclic polyfunctional isocyanate, and an aromatic polyfunctional isocyanate.
Specific examples of the polyfunctional isocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and polyphenylene. Polymethylene polyisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, p-phenylenediisocyanate, transcyclohexane 1,4-diisocyanate, 4,4'-dicyclomethane diisocyanate, 3,3 '-Dimethyl-4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, 1,5-naphthalenediisocyanate, 1,4-cyclohexanediisocyanate, lysine diisocyanate, lysine ester triisocyanate, tetramethyl Examples thereof include xylene diisocyanate, 1,6,11-undecantriisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptatriisocyanate, and trimethylhexamethylene diisocyanate.
The polyfunctional isocyanate may be a modified diisocyanate formed by modifying the diisocyanate from a modified polyfunctional isocyanate modified so that the NCO / OH molar ratio is 2/1 or more. Examples of the modified polyisocyanate include polyurethane polyisocyanate obtained by reacting the polyfunctional isocyanate with a polyhydric alcohol, polyisocyanate containing an isocyanurate ring obtained by polymerizing the polyfunctional isocyanate, and polyfunctional isocyanate. Examples thereof include polyisocyanate containing a bullet bond, which is obtained by reacting with water.
One type of curing agent may be used alone, or two or more types may be used in combination.

(Organic solvent)
Examples of the organic solvent used in this embodiment include alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents and the like. One type of organic solvent may be used alone, or two or more types may be used in combination.
Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, and propylene glycol monomethyl. Examples thereof include ether and ethylene glycol monomethyl ether.
Examples of the ether solvent include diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, propylene glycol dialkyl ether 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.
Examples of the nitrogen atom-containing compound solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.
Moreover, the above-mentioned acrylic monomer can also be used as an organic solvent. When an acrylic monomer is used as the organic solvent, it is preferable to further contain a radical polymerization initiator in order to polymerize the acrylic monomer when forming the conductive adhesive layer. As the radical polymerization initiator, a known thermal polymerization initiator or photopolymerization initiator can be used.

In this embodiment, since both the conductive composite and the acrylic adhesive can be easily dispersed, it is preferable to use an alcohol solvent, a ketone solvent, or an ester solvent as the organic solvent, and a ketone solvent is used. Is more preferable. Further, among the ketone solvents, methyl ethyl ketone is particularly preferable.
Further, in this embodiment, since water is used in the manufacturing process of the conductive composite, the conductive polymer dispersion liquid may contain a small amount of water. The content of water with respect to the total of the organic solvent and water is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 10% by mass or less. The conductive polymer dispersion may not contain water.

(High conductivity agent)
The conductive polymer dispersion may contain a highly conductive agent in order to further improve the conductivity.
Here, the above-mentioned π-conjugated conductive polymer, polyanion, and acrylic adhesive are not classified as highly conductive agents. Amine compounds, epoxy compounds and hardeners may also function as highly conductive agents.
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 highly conductive agent contained in the conductive polymer dispersion may be one kind or two or more kinds.
The content ratio of the high conductive agent is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, and 100 parts by mass with respect to 100 parts by mass of the conductive composite. It is more preferable that the amount is 2,500 parts by mass or less. When the content ratio of the high conductive agent is not less than the lower limit value, the effect of improving the conductivity by adding the high conductivity agent is sufficiently exhibited, and when it is not more than the upper limit value, the concentration of the π-conjugated conductive polymer is lowered. It is possible to prevent a decrease in conductivity due to the above.

(Other additives)
The conductive polymer dispersion may contain other known additives.
The additive is not particularly limited as long as the effect of the present invention can be obtained, and for example, a surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like can be used. However, the additive is composed of a compound other than the above-mentioned π-conjugated conductive polymer, polyanion, amine compound, epoxy compound, curing agent 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 an epoxy group, a vinyl group or an amino group.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, saccharides and the like.
Examples of 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 additive, the content ratio thereof is appropriately determined according to the type of the additive. For example, 0. The range may be 001 parts by mass or more and 5 parts by mass or less.

(First method for producing a conductive polymer dispersion)
The first method for producing the conductive polymer dispersion liquid of this embodiment for obtaining the conductive polymer dispersion liquid includes a precipitation step, a recovery step, and an adhesive addition step.

[Precipitation process]
The precipitation step is a step of adding an amine compound to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion, and precipitating the conductive complex to form a precipitate. In the precipitation step, an epoxy compound may be added.
When an amine compound is added to the aqueous dispersion, some of the polyanions constituting the conductive complex become anionic groups, specifically, anionic groups that do not participate in doping the π-conjugated conductive polymer. The amine compound is added and the anionic group disappears. This makes the conductive complex hydrophobic.
However, the amine compound may not be added to all the anion groups that are not involved in the doping of the π-conjugated conductive polymer, and some anion groups that are not involved in the doping may remain.
Since the hydrophobized conductive complex cannot be dispersed in the aqueous dispersion medium, it precipitates and becomes a precipitate.

The amount of the amine compound added is preferably 1 part by mass or more and 100,000 parts by mass or less, more preferably 10 parts by mass or more and 50,000 parts by mass or less, and 50 parts by mass with respect to 100 parts by mass of the conductive composite. It is more preferably 10,000 parts by mass or less. When the amount of the amine compound added is not less than the lower limit value, the hydrophobicity of the conductive complex can be sufficiently improved, and when it is not more than the upper limit value, the conductivity of the conductive adhesive layer is lowered. Can be prevented.

When the epoxy compound is added, the amount of the epoxy compound added is preferably 10 parts by mass or more and 10000 parts by mass or less, and 100 parts by mass or more and 5000 parts by mass or less with respect to 100 parts by mass of the conductive composite. Is more preferable, and more preferably 200 parts by mass or more and 500 parts by mass or less. When the amount of the epoxy compound added is at least the above lower limit value, the hydrophobicity of the conductive composite can be sufficiently improved, and when it is at least the above upper limit value, the conductivity of the conductive adhesive layer is lowered. Can be prevented.

In the precipitation step, the conductive polymer aqueous dispersion to which the amine compound is added is a dispersion in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is contained in the aqueous dispersion medium. Here, the aqueous dispersion medium may contain water and may contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents, and ester solvents. One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination.
The content of water in the aqueous dispersion medium is preferably 50% by mass or more, more preferably 80% by mass or more, and may be 100% by mass.
The conductive polymer aqueous dispersion is obtained, for example, by chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous solution of polyanion. Further, as the conductive polymer aqueous dispersion, a commercially available one may be used.
A known catalyst may be applied to the chemical oxidative polymerization. For example, catalysts and oxidizing agents can be used. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidant can restore the reduced catalyst to its original oxidized state.
The content of the conductive composite contained in the conductive polymer aqueous dispersion is preferably 0.1% by mass or more and 10% by mass or less, preferably 0.3% by mass, based on the total mass of the conductive polymer dispersion. % Or more and 5% by mass or less are preferable, and 0.5% by mass or more and 4% by mass or less are more preferable.

An organic solvent may be added before, at the same time as, or after the addition of the amine compound to the conductive polymer aqueous dispersion. As the organic solvent, a water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents, and ester solvents. When a water-soluble organic solvent is contained, one type may be used alone, or two or more types may be used in combination.

The amine compound may be heated before, during, or after the addition of the amine compound to the conductive polymer aqueous dispersion.

[Recovery process]
The recovery step is a step of recovering the precipitate composed of the hydrophobic conductive composite.
As a method for separating and recovering the precipitate from the aqueous dispersion medium, for example, a known separation method such as filtration, precipitation, or extraction can be applied. Among these preparative methods, filtration is preferable, and filtration is preferably performed using a filter having a coarse mesh so that the polyanion used for forming the conductive complex can pass through with the filtrate. According to this filtration method, the precipitate can be separated and the excess polyanion that does not form a conductive complex can be separated from the precipitate by leaving the excess polyanion on the filtrate side. By removing the excess polyanion, the conductivity of the precipitate can be enhanced.

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

The water content of the precipitate obtained by the recovery step is preferably as small as possible and most preferably does not contain any water, but from a practical point of view, the water content may be contained in the range of 10% by mass or less.
Examples of the method for reducing the amount of water include a method of washing away the precipitate with an organic solvent, a method of drying the precipitate, and the like.

[Adhesive addition process]
The adhesive adhesive addition step is a step of adding an acrylic adhesive to the recovered precipitate. The acrylic adhesive to be added to the precipitate may be a solid product containing the acrylic polymer, or a liquid product in which the acrylic polymer is dissolved or dispersed in an organic solvent.
The amount of solid content added to the acrylic adhesive is preferably 1 part by mass or more and 100,000 parts by mass or less with respect to 100 parts by mass of the hydrophobic conductive composite, and is 10 parts by mass or more and 50,000 parts by mass or less. Is more preferable, and more preferably 100 parts by mass or more and 10000 parts by mass or less. When the solid content addition amount of the acrylic adhesive is set to the lower limit value or more, the conductive adhesive layer can sufficiently exhibit the adhesiveness, and when it is set to the upper limit value or less, the conductive adhesive is provided. Sufficient conductivity of the layer can be ensured.

In the adhesive adhesive addition step, an organic solvent may be further added. The organic solvent may be added before the addition of the acrylic adhesive, after the addition of the acrylic adhesive, or at the same time as the addition of the acrylic adhesive.
The amount of the organic solvent added is preferably such that the content of the hydrophobic conductive composite is 0.1% by mass or more and 10% by mass or less with respect to 100% by mass of the conductive polymer dispersion. If an organic solvent is added so that the content of the hydrophobized conductive complex becomes equal to or higher than the lower limit, the conductivity of the conductive adhesive layer can be easily ensured from the conductive polymer dispersion. On the other hand, if an organic solvent is added so that the content of the hydrophobic conductive composite is equal to or less than the above upper limit value, the coatability of the conductive polymer dispersion liquid on the film substrate is improved, and the coating surface is coated. It becomes easy to apply evenly and evenly.

After adding the organic solvent to the precipitate, the obtained liquid may be stirred and dispersed. The stirring method is not particularly limited, and stirring may be performed with a weak shearing force such as a stirrer, or may be stirred using a disperser (homogenizer or the like) having a high shearing force. In the dispersion treatment, it is preferable to use a high-pressure homogenizer that can be pressurized because the dispersibility of the precipitate in the organic solvent can be improved.

When the acrylic polymer constituting the acrylic adhesive has a reactive functional group, a curing agent may be added together with the acrylic adhesive in the process of adding the adhesive.
The amount of the solid content added to the curing agent is preferably 0.1 part by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the acrylic polymer. preferable. When the solid content addition amount of the curing agent is at least the above lower limit value, the acrylic polymer can be sufficiently cured, and when it is at least the above upper limit value, gelation due to excessive curing can be suppressed.

[Addition of highly conductive agents and additives]
When a highly conductive agent, an additive, or the like is contained in the conductive polymer dispersion, the highly conductive agent, the additive, or the like may be added in the adhesive adhesive addition step.

(Second method for producing a conductive polymer dispersion)
The conductive polymer dispersion can also be produced by the second production method described below.
The second method for producing the conductive polymer dispersion liquid includes a drying step and a viscous adhesive addition step.

[Drying process]
The drying step is a step in which the conductive composite containing the π-conjugated conductive polymer and the polyanion dries the aqueous dispersion contained in the aqueous dispersion medium to obtain a dried product of the conductive composite.
As the drying method in the drying step, known methods such as freeze drying, vacuum drying, spray drying, air drying, warm air drying, and heat drying can be applied.
In freeze-drying, the water content in the conductive polymer aqueous dispersion is frozen and vacuum-dried.
The temperature during freeze-drying is preferably -60 to 60 ° C, more preferably -40 to 40 ° C. If the freeze-drying temperature is at least the lower limit value, the temperature can be easily adjusted, and if it is at least the upper limit value, the conductive polymer aqueous dispersion can be easily freeze-dried.
At the time of vacuum drying, in order to sufficiently volatilize the aqueous dispersion medium, it may be heated to, for example, 40 ° C. or higher after the freeze-drying temperature.
In spray drying, the conductive polymer aqueous dispersion is sprayed into a vacuum vessel to evaporate water and dry.
The temperature at the time of spray drying is preferably -20 to 40 ° C, more preferably 0 to 30 ° C. When the spray drying temperature is at least the lower limit value, the conductive polymer aqueous dispersion can be easily dried, and when it is at least the upper limit value, thermal deterioration of the conductive composite can be prevented.
The water content of the dried product obtained by the drying step is preferably as small as possible and most preferably does not contain any water, but from a practical point of view, the water content may be contained in the range of 10% by mass or less.
In order to reduce the amount of water, for example, the drying time may be long, the drying temperature may be high, and the degree of vacuum may be high.

[Adhesive addition process]
The adhesive adhesive addition step in the present production method is a step of adding an amine compound and an acrylic adhesive to the dried product.
In the adhesive adhesive addition step in the present production method, it is preferable to further add an organic solvent to the dried product. In the adhesive adhesive addition step, an epoxy compound may be added.
The order of addition of the amine compound and the organic solvent is not particularly limited, and the amine compound and the organic solvent may be added at the same time. Further, the organic solvent may be added before the amine compound, or the amine compound may be added before the organic solvent.
The order of addition of the acrylic adhesive and the organic solvent is not particularly limited, and the acrylic adhesive and the organic solvent may be added at the same time. Further, the organic solvent may be added before the acrylic adhesive, or the acrylic adhesive may be added before the organic solvent.
In this step, the amine compound can be added to the anion group of the polyanion by adding the amine compound to the dried product.

(Action effect)
The conductive composite contained in the conductive polymer dispersion of the present embodiment described above is a polymer-type conductive material, and the π-conjugated conductive polymer itself does not melt even when heated. , It is less likely to be altered by heat and has higher heat resistance than conductive materials such as surfactants, metal particles and ionic compounds.
In the conductive polymer dispersion of this embodiment, the anionic group of the polyanion that is not involved in doping the π-conjugated conductive polymer is hydrophobicized by the amine compound. Highly dispersibility in organic solvents.
In addition, the acrylic adhesive also has high hydrophobicity, has high dispersibility in organic solvents, and has high affinity with the hydrophobic conductive composite. Therefore, even if the acrylic adhesive contains the conductive composite, the conductive composite is unlikely to be separated or unevenly distributed, and the conductive composite has high dispersibility with respect to the acrylic adhesive layer. Sufficient conductivity can be exhibited. Therefore, a conductive adhesive layer having high conductivity and heat resistance can be easily formed from the conductive polymer dispersion liquid of this embodiment.
Further, since the hydrophobic conductive composite does not easily inhibit the adhesiveness of the acrylic adhesive, the conductive adhesiveness has sufficiently high adhesiveness.

<Conductive film>
The conductive film according to one aspect of the present invention includes a film base material and a conductive adhesive layer formed from the conductive polymer dispersion liquid on at least one surface of the film base material.

Examples of the film base material 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 and cellulose triacetate are preferable because they are inexpensive and have excellent mechanical strength.
The resin for a film base material may be amorphous or crystalline.
Further, the film base material may be unstretched or stretched.
Further, the film base material may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc. in order to further improve the adhesion of the conductive layer formed from the conductive polymer dispersion liquid.

The average thickness of the film substrate is preferably 10 μm or more and 500 μm or less, and more preferably 20 μm or more and 200 μm or less. If the average thickness of the film substrate is 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 of the member in the present specification is a value obtained by measuring the thickness at an arbitrary 10 points and averaging the measured values.

Further, a polarizing film can also be used as the film base material.
The polarizing film includes a pair of transparent films and a polarizing element arranged between the pair of transparent films.
Examples of the transparent resin constituting the transparent film include triacetyl cellulose, polyethylene terephthalate, polycarbonate, polycycloolefin, polystyrene, polyvinyl alcohol, acrylic resin and the like.
The thickness of the transparent film can be, for example, 10 μm or more and 500 μm or less, and is preferably 20 μm or more and 300 μm or less in terms of both thinning and strength.
Examples of the polarizer include those in which a dichroic substance is attached to a hydrophilic film and uniaxially stretched to orient the dichroic substance. Examples of the hydrophilic film include a polyvinyl alcohol film, a partially saponified film of an ethylene-vinyl acetate copolymer, and the like. Examples of the dichroic substance include iodine and a dichroic dye.
The thickness of the polarizer can be, for example, 10 μm or more and 500 μm or less, and is preferably 20 μm or more and 300 μm or less in terms of both thinning and polarization property.

When the conductive film is used for optical applications, it is preferable that the film base material is transparent. Specifically, the total light transmittance of the film substrate is preferably 65% or more, more preferably 70% or more, and further preferably 80% or more. The total light transmittance is a value measured according to JIS K7136.

The conductive adhesive layer in this embodiment is a formed layer. That is, the conductive adhesive layer contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, and an acrylic adhesive. Further, in the conductive composite contained in the conductive adhesive layer, the amine compound is added to a part of the anion groups of the polyanions. The acrylic adhesive may have a crosslinked structure formed by reaction with a curing agent.
The average thickness of the conductive adhesive layer is preferably 1 μm or more and 1000 μm or less, more preferably 5 μm or more and 500 μm or less, and further preferably 10 μm or more and 100 μm or less. When the average thickness of the conductive adhesive layer is not less than the lower limit value, sufficiently high adhesiveness can be exhibited, and when it is not more than the upper limit value, the conductive adhesive layer can be easily formed.

When the conductive film of this embodiment is used for an in-cell capacitive touch panel in which a touch panel is incorporated in a liquid crystal cell, if the conductivity of the conductive adhesive layer is too low, display defects due to liquid crystal molecular charging May occur. On the other hand, if the conductive adhesive layer has too high conductivity, it may adversely affect the detection of the change in capacitance of the touch panel. Therefore, it is preferable that the conductive adhesive layer has an appropriate conductivity, for example, ^{a surface resistance value of 1 × 10 7} Ω / □ or more and 1 × 10 ¹² Ω / □ or less.

(Manufacturing method of conductive film)
The method for producing a conductive film according to this embodiment is a step of forming a conductive adhesive layer by applying the conductive polymer dispersion liquid to at least one surface of a film base material to form a conductive adhesive layer. Has.

Examples of the method of applying the conductive polymer dispersion in the coating step include a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a knife coater, a fountain coater, a rod coater, and an air doctor. Apply coating methods using coaters such as coaters, knife coaters, blade coaters, cast coaters, screen coaters, spraying methods using atomizers such as air spray, airless spray, rotor dampening, dipping methods such as dips, etc. be able to.
Of the above coating methods, a bar coater may be used because coating can be performed easily. In the bar coater, the coating thickness differs depending on the type, and in the commercially available bar coater, a number is assigned to each type, and the larger the number, the thicker the coating can be performed.
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.}

After the coating step, there may be a drying step of drying the coating film composed of the coated conductive polymer dispersion liquid.
Examples of the method of drying in the drying step 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, and can be set to, for example, 50 ° C. or higher and 150 ° C. or lower. Here, the heating temperature is a set temperature of the drying device.

(Action effect)
Since the conductive adhesive layer constituting the conductive film of this embodiment is formed from the conductive polymer dispersion liquid, the dispersibility of the conductive composite in the conductive adhesive layer Is high. Further, the conductive composite is a polymer-type conductive material having a π-conjugated conductive polymer as a conductive material and having high heat resistance. Therefore, the conductive adhesive layer constituting the conductive film of this embodiment has high conductivity and heat resistance. Further, the conductive adhesive layer in this embodiment has sufficiently high adhesiveness.
The conductive adhesive layer in the present embodiment containing the π-conjugated conductive polymer can have higher conductivity than the conductive adhesive layer containing a surfactant. Since the π-conjugated conductive polymer has a larger molecular weight than the surfactant, it is unlikely to move in the conductive adhesive layer, and bleed-out to the layer surface is unlikely to occur. Therefore, when the conductive film of the present embodiment is adhered to the glass base material, the charging of the glass base material can be sufficiently prevented. Since the surfactant easily moves in the conductive adhesive layer and bleeds out and cannot fully exert its function as an antistatic agent, the glass substrate is sufficiently charged when it is adhered to the glass substrate. Cannot be prevented.
Further, the conductive adhesive layer in the present embodiment containing the π-conjugated conductive polymer can be made more transparent than the conductive adhesive layer containing metal particles. Therefore, the conductive film of this embodiment is suitable for an optical member. The conductive adhesive layer containing metal particles has low transparency and is not suitable for optical members.

<Conductive glass substrate>
The conductive glass base material according to one aspect of the present invention includes the conductive film and a glass base material adhered to the conductive adhesive layer of the conductive film. That is, as shown in FIG. 1, the conductive glass base material 1 of this embodiment has a film base material 11, a conductive adhesive layer 12 formed on one surface of the film base material 11, and a conductive adhesive layer 12. A glass base material 20 adhered to the adhesive layer 12 is provided. The film base material 11 and the conductive adhesive layer 12 form the conductive film 10.
Examples of the glass base material 20 include a non-alkali glass base material, a soda-lime glass base material, a borosilicate glass base material, a quartz glass base material, and the like. When the glass base material 20 contains an alkaline component, the conductivity of the conductive adhesive layer 12 tends to decrease. Therefore, among the glass base materials 20, a non-alkali glass base material is preferable. Here, the non-alkali glass is a glass composition having an alkali oxide content of 0.1% by mass or less.
The average thickness of the glass substrate 20 is preferably 100 μm or more and 3000 μm or less, and more preferably 100 μm or more and 1000 μm or less. If the average thickness of the glass base material 20 is at least the lower limit value, it is less likely to be damaged, and if it is at least the upper limit value, it can sufficiently contribute to thinning the member using the conductive glass base material 1.

The glass base material 20 may be a glass plate constituting the liquid crystal cell.
Here, the liquid crystal cell preferably includes a pair of glass plates, a pair of transparent electrode layers provided between the pair of glass plates, and a liquid crystal layer provided between the pair of transparent electrode layers. The liquid crystal layer is preferably a layer in which liquid crystal molecules are enclosed between a pair of oriented layers.
In the in-cell capacitive touch panel, it is preferable that the transparent conductive layer also serves as an electrode for applying a voltage to the liquid crystal molecules to change the orientation of the liquid crystal molecules and an electrode for the sensor of the touch panel.

(Manufacturing method of conductive glass base material)
As a method for producing the conductive glass base material 1 of the present embodiment, the conductive film for producing the conductive film 10 including the film base material 11 and the conductive adhesive layer 12 is produced by the method for producing the conductive film. Examples thereof include a method having a manufacturing step and an bonding step of adhering the conductive film 10 to the glass base material 20 by sticking the conductive adhesive layer 12 to the glass base material 20.
In the bonding step, it is preferable to press the conductive film with a pressure that does not damage the glass base material 20. Further, in the bonding step, heating may be performed if necessary. For example, when the acrylic adhesive contained in the conductive adhesive layer is a curable type, it is preferable to heat the acrylic adhesive during the bonding step to cure the adhesive.

Further, the glass base material 20 is coated with the conductive polymer dispersion liquid to form the conductive adhesive layer 12, and the film base material 11 is attached to the conductive adhesive layer 12. It is also possible to manufacture the conductive glass base material 1.

(Action effect)
Since the conductive adhesive layer constituting the conductive glass substrate of this embodiment is formed from the conductive polymer dispersion liquid, the conductive composite in the conductive adhesive layer Highly dispersive. The conductive composite is a polymer-type conductive material having high heat resistance. Therefore, the conductive glass substrate of this embodiment has high conductivity and heat resistance. The conductive glass base material having high conductivity has excellent antistatic properties and is hard to be charged.
Further, in the conductive glass base material of this embodiment, the conductive adhesive layer is adhered to the glass base material with a high adhesive force.

(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 to the solution at 80 ° C. for 12 hours. Stirred.
To the obtained sodium styrene sulfonate-containing solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, about 1000 ml of the polystyrene sulfonate-containing solution was removed by an ultrafiltration method, and 2000 ml of ion-exchanged water was added to the residual solution. , About 2000 ml of solution was removed by ultrafiltration. The above ultrafiltration operation was repeated 3 times. Further, about 2000 ml of ion-exchanged water was added to the obtained polystyrene sulfonic acid solution, and about 2000 ml of the solution was removed by an ultrafiltration method. This ultrafiltration operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.

(Manufacturing Example 2)
14.2 g of 3,4-ethylenedioxythiophene and a solution of 36.7 g of polystyrene sulfonic acid 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 solution was removed by an ultrafiltration method. This operation was repeated 3 times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the obtained solution, about 2000 ml of the solution was removed by an ultrafiltration method, and 2000 ml of ion-exchanged water was added thereto. About 2000 ml of the solution was removed by ultrafiltration. This operation was repeated 3 times.
Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed by an ultrafiltration method. This operation was repeated 5 times to obtain a 1.2% polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS aqueous dispersion) solution. The content of PSS with respect to the PEDOT-PSS solid content is 75% by mass.

(Manufacturing Example 3)
A mixed solution of 10.6 g of trioctylamine and 100 g of isopropanol was added to 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to precipitate a trioctylamine adduct of PEDOT-PSS. The precipitated PEDOT-PSS trioctylamine adduct was collected by filtration and washed with 100 g of water, and then washed with 100 g of acetone to remove the PEDOT-PSS trioctylamine adduct as a solid. 0.6 g of the obtained PEDOT-PSS trioctylamine adduct was added to 100 g of methyl ethyl ketone, dispersed using a high-pressure homogenizer, and the methyl ethyl ketone of the PEDOT-PSS trioctylamine adduct having a concentration of 0.6% by mass was added. A solution (conductive mixture) was obtained.

(Manufacturing Example 4)
A mixed solution of 8.08 g of trihexylamine and 100 g of isopropanol was added to 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to precipitate a trihexylamine adduct of PEDOT-PSS. The precipitated PEDOT-PSS trihexylamine adduct was collected by filtration and washed with 100 g of water, and then washed with 100 g of acetone to remove the PEDOT-PSS trihexylamine adduct as a solid. 0.6 g of the obtained PEDOT-PSS trihexylamine adduct was added to 100 g of methyl ethyl ketone, dispersed using a high-pressure homogenizer, and the methyl ethyl ketone of the PEDOT-PSS trihexylamine adduct having a concentration of 0.6% by mass was added. A solution (conductive mixed solution) was obtained.

(Example 1)
To 40 g of the conductive mixed solution obtained in Production Example 3, 60 g of an acrylic pressure-sensitive adhesive (SK Dyne 1499M manufactured by Soken Kagaku Co., Ltd., solid content concentration 35% by mass, ethyl acetate / butyl acetate mixed solution) and toluene as a curing agent 1.62 g of a diisocyanate-trimethylolpropane adduct (manufactured by Soken Kagaku Co., Ltd., L-45, solid content concentration 45% by mass, toluene / ethyl acetate mixed solution) was mixed to obtain a conductive polymer dispersion.

(Example 2)
To 60 g of the conductive mixed solution obtained in Production Example 3, 40 g of an acrylic pressure-sensitive adhesive (SK Dyne 1499M manufactured by Soken Kagaku Co., Ltd., solid content concentration 35% by mass, ethyl acetate / butyl acetate mixed solution) and toluene as a curing agent 1.08 g of a diisocyanate-trimethylolpropane adduct (manufactured by Soken Kagaku Co., Ltd., L-45, solid content concentration 45% by mass, toluene / ethyl acetate mixed solution) was mixed to obtain a conductive polymer dispersion.

(Example 3)
To 80 g of the conductive mixed solution obtained in Production Example 3, 20 g of an acrylic pressure-sensitive adhesive (SK Dyne 1499M manufactured by Soken Kagaku Co., Ltd., solid content concentration 35% by mass, ethyl acetate / butyl acetate mixed solution) and toluene as a curing agent 0.54 g of a diisocyanate-trimethylolpropane adduct (manufactured by Soken Kagaku Co., Ltd., L-45, solid content concentration 45% by mass, toluene / ethyl acetate mixed solution) was mixed to obtain a conductive polymer dispersion.

(Example 4)
The same as in Example 1 except that the type of acrylic pressure-sensitive adhesive was changed from SK Dyne 1499M manufactured by Soken Kagaku Co., Ltd. to SK Dyne 1498B (solid content concentration 35% by mass, mixed solution of ethyl acetate / methyl ethyl ketone) manufactured by Soken Kagaku Co., Ltd. A conductive polymer dispersion was obtained.

(Example 5)
A conductive polymer dispersion was obtained in the same manner as in Example 2 except that the type of acrylic pressure-sensitive adhesive was changed from SK Dyne 1499M manufactured by Soken Chemical Co., Ltd. to SK Dyne 1498B manufactured by Soken Chemical Co., Ltd.

(Example 6)
A conductive polymer dispersion was obtained in the same manner as in Example 3 except that the type of the acrylic pressure-sensitive adhesive was changed from SK Dyne 1499M manufactured by Soken Chemical Co., Ltd. to SK Dyne 1498B manufactured by Soken Chemical Co., Ltd.

(Example 7)
High conductivity as in Example 3 except that the type of acrylic pressure-sensitive adhesive was changed from SK Dyne 1499M manufactured by Soken Chemical Co., Ltd. to SK Dyne 1495 manufactured by Soken Chemical Co., Ltd. and the amount of curing agent was changed to 0.13 g. A molecular dispersion was obtained.

(Example 8)
The type of acrylic pressure-sensitive adhesive was changed from SK Dyne 1499M manufactured by Soken Kagaku Co., Ltd. to Nisetsu KP-1282 (solid content concentration 40% by mass, mixed solution of toluene / acetone) manufactured by Nippon Carbide Industries Co., Ltd., and the amount of curing agent was 0.4 g. A conductive polymer dispersion was obtained in the same manner as in Example 3 except that it was changed to.

(Example 9)
The type of acrylic pressure-sensitive adhesive was changed from SK Dyne 1499M manufactured by Soken Kagaku Co., Ltd. to Nisetsu KP-1410 (solid content concentration 40% by mass, mixed solution of toluene / ethyl acetate) manufactured by Nippon Carbide Industries Co., Ltd., and the curing agent was hexamethylene diisocyanate 0. A conductive polymer dispersion was obtained in the same manner as in Example 3 except that it was changed to .4 g.

(Example 10)
A conductive polymer dispersion was obtained in the same manner as in Example 3 except that the conductive mixed solution obtained in Production Example 3 was changed to the conductive mixed solution obtained in Production Example 4.

(Comparative Example 1)
A conductive polymer dispersion was obtained in the same manner as in Example 1 except that methyl ethyl ketone was used instead of the conductive mixed solution.

(Comparative Example 2)
A conductive polymer dispersion was obtained in the same manner as in Example 4 except that methyl ethyl ketone was used instead of the conductive mixed solution.

(Comparative Example 3)
A conductive polymer dispersion was obtained in the same manner as in Example 7 except that methyl ethyl ketone was used instead of the conductive mixed solution.

(Comparative Example 4)
A conductive polymer dispersion was obtained in the same manner as in Example 1 except that the conductive mixed solution obtained in Production Example 3 was changed to the conductive mixed solution obtained in Production Example 2. .. However, the study was stopped because the conductive polymer (PEDOT-PSS) and the acrylic pressure-sensitive adhesive were separated into two layers in the liquid.

<Evaluation>
[Surface resistance value]
The conductive polymer dispersions of each example were referred to as No. A polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror T60) was coated with 16 bar coaters and dried at 100 ° C. for 1 minute to form an adhesive layer to obtain an adhesive film. .. The surface resistance value of the adhesive layer of each example was measured using a resistivity meter (High Restor manufactured by Mitsubishi Chemical Analytical Co., Ltd.) under the condition of an applied voltage of 10 V. Table 1 shows the measurement results of the surface resistance value. In the table, "OVER" means that the measurable upper limit of the surface resistance value (1.0 × 10 ¹² Ω / □) has been exceeded.

[Peeling strength]
Polyethylene terephthalate was pressure-bonded to a part of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film, and a non-alkali glass plate (thickness 0.7 mm) was pressure-bonded to the rest, and cured at room temperature for 48 hours. Next, the crimped polyethylene terephthalate film was cut into strips having a width of 10 mm, and the peel strength at 180 ° peeling was measured according to JIS Z0237. Table 1 shows the measurement results of the peel strength. The higher the peel strength, the higher the adhesive strength.

[Voltage]
After the adhesive film was attached as described above and the non-alkali glass plate cured at room temperature for 48 hours was rubbed with a non-woven fabric to be charged, the surface potential of the non-alkali glass was digitally measured according to JIS C61340-2-2: 2006. The measurement was performed using a low potential measuring device (KSD-3000 manufactured by Kasuga Electric Co., Ltd.). This surface potential was defined as the voltage band on the non-alkali glass plate. Table 1 shows the measurement results of the band voltage. The lower the voltage band, the better the antistatic property.

<Result>
In Examples 1 to 10 using the conductive composite hydrophobicized with the amine compound, the surface resistance value of the adhesive layer was low, so that the voltage band was low and the antistatic property was excellent. It is presumed that this is because the conductive composite has high dispersibility in the acrylic pressure-sensitive adhesive, which is the main component of the adhesive layer, and the conductivity can be sufficiently exhibited. In addition, the adhesive layers in Examples 1 to 10 had sufficient adhesive strength.
In Comparative Examples 1 to 3 not containing the conductive composite, since the surface resistance value of the adhesive layer was high, the voltage band was also high and the antistatic property was not provided.

1 Conductive glass base material 10 Conductive film 11 Film base material 12 Conductive adhesive layer 20 Glass base material

Claims (8)

At least one amine compound selected from the group consisting of tertiary amines having an alkyl group having 4 to 12 carbon atoms is added to an aqueous dispersion of a conductive complex containing a π-conjugated conductive polymer and a polyanion. , A precipitation step of precipitating the conductive composite to form a precipitate, and
A recovery step for recovering the precipitate and
A method for producing a conductive polymer dispersion, which comprises a step of adding an acrylic adhesive to the recovered precipitate. Wherein the adhesive adding step, further adding an organic solvent to the precipitates, method for producing a conductive polymer dispersion of claim 1. The method for producing a conductive polymer dispersion according to claim 2, wherein the organic solvent is a ketone solvent. The method for producing a conductive polymer dispersion according to claim 3, wherein the organic solvent is methyl ethyl ketone. The method for producing a conductive polymer dispersion liquid according to any one of claims 1 to 4, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). The method for producing a conductive polymer dispersion according to any one of claims 1 to 5 , wherein the polyanion is polystyrene sulfonic acid. The method for producing a conductive polymer dispersion according to any one of claims 1 to 6, wherein the acrylic adhesive contains an acrylic polymer having a glass transition temperature of 0 ° C. or lower. The method for producing a conductive polymer dispersion according to any one of claims 1 to 7, wherein a polyfunctional isocyanate having two or more isocyanate groups in one molecule is further added in the adhesive adhesive addition step. ..

Images