JP6900308B2 - 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.

As a coating material for forming the conductive layer, a conductive polymer aqueous dispersion obtained by doping poly (3,4-ethylenedioxythiophene) with polystyrene sulfonic acid may be used.
Usually, the film base material on which the conductive layer is coated is often a hydrophobic plastic film. The conductive polymer aqueous dispersion, which is a water-based paint, tends to have a low affinity for a plastic film. Further, when the conductive polymer dispersion liquid is water-based, the dispersibility of the hydrophobic resin or the curable compound forming the hydrophobic resin becomes low, and it becomes difficult to use them as a binder component. Therefore, in the water-based conductive polymer dispersion, the types of binder components are limited.
Therefore, a conductive polymer organic solvent dispersion liquid in which water, which is a dispersion medium of the conductive polymer water dispersion liquid, is replaced with an organic solvent may be used.
As the conductive polymer organic solvent dispersion liquid, a conductive polymer aqueous dispersion containing a conductive composite composed of a π-conjugated conductive polymer and a polyanion is freeze-dried to obtain a dried product, and then the dried product is obtained. Is known to be obtained by adding an organic solvent and an amine compound to (Patent Document 1).
Further, a cyclic ether compound having at least one of an oxylan group and an oxetane group and an organic solvent are added to a conductive polymer aqueous dispersion containing a conductive composite composed of a π-conjugated conductive polymer and a polyanion. It is known to obtain a conductive polymer organic solvent dispersion (Patent Document 2). In the method described in Patent Document 2, the conductive composite is made organic by reacting an anionic group that is not doped with a π-conjugated conductive polymer with an oxylan group or an oxetane group of a cyclic ether compound to make it hydrophobic. Make it solvent dispersible.

Japanese Unexamined Patent Publication No. 2011-032382 International Publication No. 2014/125827

However, with the conventional conductive polymer organic solvent dispersion liquid, the light resistance of the conductive layer obtained from the dispersion may be lowered.
Therefore, 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 layer having high conductivity and light resistance even though an organic solvent is used as a dispersion medium. And. Another object of the present invention is to provide a conductive film provided with a conductive layer having high conductivity and light resistance, and a method for producing the same.

The present invention includes the following aspects.
[1] A conductive polymer dispersion liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, and a dispersion medium containing 85% by mass or more and 100% by mass or less of a diol compound.
[2] The conductive polymer dispersion liquid according to [1], wherein the content of water with respect to the total mass of the conductive polymer dispersion liquid is 0% by mass or more and 1.0% by mass or less.
[3] The conductive polymer dispersion according to [1] or [2], wherein the diol compound is a liquid at 25 ° C.
[4] The conductive polymer dispersion liquid according to any one of [1] to [3], wherein the diol compound has a boiling point of 250 ° C. or lower at standard atmospheric pressure.
[5] The conductivity according to any one of [1] to [4], wherein the diol compound is one or more selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol and butanediol. Polymer dispersion.
[6] The conductive polymer dispersion liquid according to any one of [1] to [5], wherein the conductive polymer dispersion liquid further contains a binder component.
[7] The conductive polymer dispersion liquid according to any one of [1] to [6], wherein the binder component is an organic solvent-soluble compound.
[8] The conductive polymer dispersion liquid according to [7], wherein the binder component is an active energy ray-curable acrylic compound.
[9] The conductive polymer dispersion according to any one of [1] to [8], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[10] A conductive polymer dispersion liquid according to any one of [1] to [9], wherein the polyanion is polystyrene sulfonic acid.
[11] A base material and a conductive layer formed by coating at least one surface of the base material with the conductive polymer dispersion liquid according to any one of [1] to [10]. , Conductive film.
[12] A step of removing water from a raw material water dispersion containing water and a conductive composite containing a π-conjugated conductive polymer and a polyanion to form a solid of the conductive composite, and the above-mentioned conductivity. It has a step of mixing the solid substance of the complex and the diol compound to obtain a conductive polymer dispersion, and the content of the diol compound in the dispersion medium contained in the conductive polymer dispersion is 85% by mass or more. A method for producing a conductive polymer dispersion, in which the solid substance of the conductive composite and the diol compound are mixed so as to be 100% by mass or less.
[13] The solid substance of the conductive complex and the diol compound are mixed, and then a dispersion treatment is performed on a mixed solution containing the solid substance of the conductive complex and the diol compound, according to [12]. A method for producing a conductive polymer dispersion.
[14] The method for producing a conductive polymer dispersion according to [12] or [13], wherein water is removed from the raw material water dispersion by freeze-drying the raw material water dispersion.
[15] A method for producing a conductive film, wherein the conductive polymer dispersion liquid according to any one of [1] to [10] is applied to at least one surface of a base material to form a conductive layer.

In the conductive polymer dispersion liquid of the present invention, a conductive layer having high conductivity and light resistance can be easily formed even though an organic solvent is used as a dispersion medium.
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 layer having high conductivity and light 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.

<Conductive polymer dispersion liquid>
One aspect of the conductive polymer dispersion liquid of the present invention will be described.
The conductive polymer dispersion liquid of this embodiment contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, and a dispersion medium containing a diol compound.
Further, in the conductive polymer dispersion liquid of this embodiment, the content of water with respect to the total mass of the conductive polymer dispersion liquid is 0% by mass or more and 1.0% by mass or less.

(Conductive complex)
The conductive complex in this embodiment includes a π-conjugated conductive polymer and a polyanion having an anion group. 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. The surplus anion group is a hydrophilic group.

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.

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.

Since the anionic group of the polyanion is hydrophilic and has a low affinity for an organic solvent, at least one of an amine compound and an epoxy compound may be reacted with the anionic group to form a hydrophobic substituent. However, in this embodiment, since the light resistance of the conductive layer formed from the conductive polymer dispersion becomes higher, it is preferable not to react at least one of the amine compound and the epoxy compound with the anionic group of the polyanion. Even when at least one of the amine compound and the epoxy compound is reacted with the anionic group of the polyanion, the amount of the amine compound and the epoxy compound added is preferably small.
Specifically, the amount of the amine compound added is preferably 0 parts by mass or more and 10 parts by mass or less, and more preferably 0 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the conductive composite. , 0 part by mass or more and 0.1 part by mass or less is more preferable. When the amount of the amine compound added is not more than the upper limit, the light resistance of the conductive layer formed from the conductive polymer dispersion can be further improved.
The amount of the epoxy compound added is preferably 0 parts by mass or more and 10 parts by mass or less, more preferably 0 parts by mass or more and 1 part by mass or less, and 0 parts by mass or more with respect to 100 parts by mass of the conductive composite. It is more preferably 0.1 parts by mass or less. When the amount of the epoxy compound added is not more than the upper limit value, the light resistance of the conductive layer formed from the conductive polymer dispersion can be further improved.

The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight of the polyanion is a mass-based molecular weight obtained by measuring the elution time using gel permeation chromatography (GPC) and obtaining it based on a calibration curve of elution time vs. molecular weight obtained in advance from a polystyrene standard substance having a known molecular weight. That is.

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.

In the conductive polymer dispersion liquid of this embodiment, the content of the conductive composite with respect to the total mass of the conductive polymer dispersion liquid is preferably 0.1% by mass or more and 20% by mass or less, preferably 0.5% by mass. It is more preferably% or more and 10% by mass or less, and further preferably 1.0% by mass or more and 5.0% by mass or less.

(Dispersion medium)
The dispersion medium in this embodiment contains a diol compound.
The diol compound is an organic compound having two hydroxy groups.
The diol compound is preferably a compound in which one of the hydrogen atoms of a linear aliphatic hydrocarbon having 2 to 8 carbon atoms is substituted with a hydroxy group. Further, the diol compound is preferably a liquid at 25 ° C. from the viewpoint of sufficiently fulfilling a role as a dispersion medium. Furthermore, since the diol compound is easily volatilized after coating and a conductive polymer dispersion is easily produced, the boiling point at standard air pressure (1013 hPa) is preferably 250 ° C. or lower. The boiling point of the diol compound at standard atmospheric pressure is preferably 100 ° C. or higher in terms of suppressing the volatilization of the diol compound.
Among the diol compounds, ethylene glycol, diethylene glycol, propylene glycol and butanediol (1,4-butanediol, 1,3-butanediol, 2,3-butanediol, etc. One or more selected from the group consisting of 1,2-butanediol) is preferable. Ethylene glycol, diethylene glycol, propylene glycol and butanediol are diol compounds that are liquid at 25 ° C and have a boiling point of 250 ° C or less at standard atmosphere.

The content ratio of the diol compound in the dispersion medium is 85% by mass or more and 100% by mass or less, preferably 90% by mass or more and 100% by mass or less, and 95% by mass or more and 100% by mass or less, based on 100% by mass of the dispersion medium. It is more preferably 99% by mass or more and 100% by mass or less. If the content ratio of the diol compound in the dispersion medium is less than the lower limit, the dispersibility of the conductive complex in the dispersion medium may decrease.

When the content ratio of the diol compound in the dispersion medium is not 100% by mass, the dispersion medium contains a dispersion medium other than the diol compound. Examples of the dispersion medium other than the diol compound include water and organic solvents other than the diol compound.
Examples of other organic solvents include alcohol solvents (excluding the diol compounds), ketone solvents, ester solvents, aromatic hydrocarbon solvents and the like. One type of other organic solvent may be used alone, or two or more types may be used in combination.
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.

In the conductive polymer dispersion liquid of this embodiment, the water content is 0% by mass or more and 1.0% by mass or less, and 0% by mass or more and 0% by mass, based on the total mass of the conductive polymer dispersion liquid. It is more preferably 5% by mass or less. The content of water in the conductive polymer dispersion liquid in this embodiment is a value measured by Karl Fischer titration.
When the water content in the conductive polymer dispersion is not more than the upper limit, the affinity of the conductive polymer dispersion with respect to the plastic film becomes higher. Further, when the water content in the conductive polymer dispersion is not more than the above upper limit value, when a hydrophobic resin or a curable compound forming a hydrophobic resin is blended as a binder component, the dispersibility of the binder component is high. It will be higher.

(Binder component)
The conductive polymer dispersion liquid of this embodiment may contain a binder component. The binder component is a component that can improve the mechanical strength and hardness of the conductive layer formed by applying the conductive polymer dispersion liquid.
As the binder component, a polymer other than the above-mentioned π-conjugated conductive polymer and polyanion or a compound forming the polymer is used. Specifically, 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, polyester resin, epoxy resin, oxetane resin, polyurethane resin, polyimide resin, melamine resin, silicone resin, vinyl acetate resin and the like.
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.
Since these binder components are easily dispersed or dissolved in the diol compound, it is preferably an organic solvent-soluble compound, that is, a hydrophobic resin or a curable compound that forms a hydrophobic resin.

Further, the binder component is preferably an active energy ray-curable acrylic compound. Here, the "active energy ray-curable" means a property of being radically polymerized and cured by irradiation with any one of ultraviolet rays, electron beams, and visible light.
If the binder component is an active energy ray-curable compound, the coatability of the conductive polymer dispersion is improved, and the conductive layer can be easily formed from the conductive polymer dispersion. Further, the active energy ray-curable compound is hydrophobic and has excellent solubility or dispersibility in a diol compound.
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, Glycerin propoxytriacrylate and the like can be mentioned.
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 acrylic compound may be an acrylate obtained by reacting an acrylic monomer with another compound such as epoxy acrylate, urethane acrylate, polyester acrylate, or polyacrylic acrylate.
The acrylic compound may be used alone or in combination of two or more.

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 more preferably 100 parts by mass or more and 10000 parts by mass or less with respect to 100 parts by mass of the conductive composite. It is preferably 500 parts by mass or more and 5000 parts by mass or less. When the solid content of the binder component is at least the above lower limit value, the strength and hardness of the conductive layer formed from the conductive polymer dispersion can be further improved.
When the solid content of the binder component is not more than the upper limit value, it is possible to suppress a decrease in the content of the conductive complex and ensure good conductivity.

When the binder component is active energy ray-curable, it is preferable that the conductive polymer dispersion further contains a photopolymerization initiator. Examples of the photopolymerization initiator include the Irgacure series manufactured by BASF.
When the binder component is thermosetting, it is preferable that the conductive polymer dispersion further contains a thermal polymerization initiator. As the thermal polymerization initiator, for example, a known inorganic peroxide or a known organic peroxide can be used.

(High conductivity agent)
The conductive polymer dispersion liquid of this embodiment may contain a highly conductive agent.
The high conductivity agent is a component that further improves the conductivity of the conductive layer. Here, the above-mentioned π-conjugated conductive polymer, polyanion, dispersion medium and binder component are not classified as high conductivity agents.
Highly conductive agents include saccharides, nitrogen-containing aromatic cyclic compounds, compounds having three 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 and a lactam compound.
The highly conductive agent contained in the conductive polymer dispersion medium may be one kind or two or more kinds.

When a high conductive agent is added, the content ratio of the high conductive agent in the conductive polymer dispersion is preferably 1 part by mass or more and 10000 parts by mass or less with respect to 100 parts by mass of the conductive composite. It is more preferably parts by mass or more and 5000 parts by mass or less, and further preferably 100 parts by mass or more and 2500 parts by mass or less. When the content ratio of the highly conductive agent in the conductive polymer dispersion is not less than the lower limit value, the effect of improving the conductivity by adding the highly conductive agent is sufficiently exhibited, and when it is not more than the upper limit value, the π-conjugated system It is possible to prevent a decrease in conductivity and a decrease in transparency due to a decrease in the concentration of the conductive polymer.

(Additive)
The conductive polymer dispersion liquid of this embodiment may contain an additive.
The additive is not particularly limited as long as it has the effect of the present invention, 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 π-conjugated conductive polymer, the polyanion, the diol compound, the binder component and the 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 polyvinyl alcohol or 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 resin 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, vitamins 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 of this embodiment contains the above additive, the content ratio thereof is appropriately determined depending on the type of the additive, and is, for example, with respect to 100 parts by mass of the solid content of the conductive composite. , 0.001 part by mass or more and 5 parts by mass or less.

(Manufacturing method of conductive polymer dispersion liquid)
The method for producing the conductive polymer dispersion liquid of this embodiment will be described.
The method for producing the conductive polymer dispersion liquid of this embodiment has the following first step and second step.

(First step)
The first step in this embodiment is a step of removing water contained in the raw material water dispersion liquid to obtain a solid substance of the conductive complex. Here, the raw material aqueous dispersion is an aqueous dispersion containing water and a conductive composite containing a π-conjugated conductive polymer and a polyanion. The content of the organic solvent in the raw material water dispersion is preferably 0% by mass or more and 50% by mass or less, and preferably 0% by mass or more and 30% by mass or less, from the viewpoint of enhancing the dispersibility of the conductive composite. More preferably, it is 0% by mass or more and 10% by mass or less.

Examples of the method for producing the raw material water dispersion include a method of chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous solution of a polyanion.
Further, as the raw material water dispersion liquid, a commercially available water dispersion liquid containing a conductive composite of a π-conjugated conductive polymer and a polyanion may be used.
A known catalyst may be applied to the chemical oxidative polymerization. For example, catalysts and oxidizing agents can be used. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate and 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 solid content concentration of the conductive composite contained in the raw material water dispersion is preferably 0.1% by mass or more and 10% by mass or less, and 0.3% by mass or more, based on the total mass of the raw material water dispersion. It is more preferably 5% by mass or less.

In the first step, as a method of removing water from the raw material water dispersion, for example, a method of freeze-drying the raw material water dispersion, a method of heating the raw material water dispersion to evaporate water, and a method of reducing the pressure of the raw material water dispersion. Then, a method of evaporating water, a method of heating the raw material water dispersion while reducing the pressure to evaporate the water, a method of removing water by film separation, and the like can be mentioned. Among the above-mentioned methods for removing water, a method of freeze-drying the raw material water dispersion is preferable because water can be sufficiently removed.
In the first step, water is removed until the content of water in the solid content of the obtained conductive composite is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more and 10% by mass. If the water content in the solid content of the conductive composite is set to the upper limit or less in the first step, the water content in the conductive polymer dispersion liquid of the present embodiment can be easily reduced to 1.0% by mass or less. it can.

(Second step)
The second step in this embodiment is a step of mixing the solid substance of the conductive composite with the diol compound to obtain a conductive polymer dispersion liquid.
In the second step, after mixing the solid substance of the conductive complex and the diol compound, it is preferable to perform a dispersion treatment on the mixed solution containing the solid substance of the conductive complex and the diol compound. If the mixed solution is subjected to a dispersion treatment, the dispersibility of the conductive composite in the conductive polymer dispersion is improved, so that the conductivity of the conductive layer obtained by coating the conductive polymer dispersion is further improved. be able to.
The dispersion treatment is a treatment in which a shearing force is applied to a mixed liquid containing a solid substance of a conductive composite and a diol compound to disperse each component.
In the dispersion processing, it is preferable to use a disperser. Examples of the disperser include a homogenizer, a high-pressure homogenizer, and a bead mill. Among the dispersers, a high-pressure homogenizer is preferable because the dispersibility of each component can be easily increased.
Examples of the high-pressure homogenizer include a device including a high-pressure generating portion that pressurizes the liquid to be treated to be dispersed, and an opposed collision portion, an orifice portion, or a slit portion that performs dispersion. As the high pressure generating part, a known high pressure pump such as a plunger pump is used. Specific examples of the high-pressure homogenizer include a product name nanomizer manufactured by Yoshida Kikai Kogyo Co., Ltd., a product name microfluidizer manufactured by Microfluidisk, and an ultimateizer manufactured by Sugino Machine Limited.

The amount of the diol compound added to the solid substance of the conductive composite is 90% by mass or more, with the content ratio of the diol compound in the dispersion medium of the conductive polymer dispersion being 85% by mass or more and 100% by mass or less. The amount is preferably 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and further preferably 99% by mass or more and 100% by mass or less. The content ratio of the diol compound is a ratio when the mass of the dispersion medium is 100% by mass. The content ratio of the diol compound in the dispersion medium can be determined by analysis using gas chromatography.
If the content ratio of the diol compound in the dispersion medium is less than the lower limit, the dispersibility of the conductive complex in the dispersion medium may decrease.

(Addition of other ingredients)
The binder component, the high conductivity agent, and the additive, which are optional components, may be added to the raw material water dispersion, respectively, or may be added to the solid material of the conductive complex together with the diol compound, or the diol compound. May be added to the solids of the conductive composite before or after the addition. The other organic solvent may be added to the solid of the conductive complex together with the diol compound, or may be added to the solid of the conductive complex before or after the addition of the diol compound.
From the viewpoint of further enhancing the light resistance of the conductive layer, it is preferable not to add at least one of the amine compound and the epoxy compound to the raw material aqueous dispersion. Even when at least one of the amine compound and the epoxy compound is added to the raw material water dispersion, the addition amount is preferably small.
Specifically, the amount of the amine compound added to the raw material water dispersion is preferably 0 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the conductive composite, and is 0 parts by mass or more and 1 part by mass or less. It is more preferably 0 parts by mass or more and 0.1 parts by mass or less. When the amount of the amine compound added is not more than the upper limit, the light resistance of the conductive layer formed from the conductive polymer dispersion can be further improved.
The amount of the epoxy compound added to the raw material water dispersion is preferably 0 parts by mass or more and 10 parts by mass or less, and more preferably 0 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the conductive composite. , 0 part by mass or more and 0.1 part by mass or less is more preferable. When the amount of the epoxy compound added is not more than the upper limit value, the light resistance of the conductive layer formed from the conductive polymer dispersion can be further improved.

(Action effect)
In this embodiment, the conductive complex is dispersed in a dispersion medium containing 85% by mass or more of a diol compound which is an organic solvent. Although the diol compound is an organic solvent, the conductive complex can be dispersed with high dispersibility. In particular, the diol compound can easily disperse the conductive complex without making the anionic group of the polyanion constituting the conductive complex hydrophobic with an amine compound, an epoxy compound or the like.
Further, according to the conductive polymer dispersion liquid of this embodiment in which the conductive composite is dispersed in a dispersion medium containing a diol compound, the conductivity and light resistance are high even though an organic solvent is used as the dispersion medium. An excellent conductive layer can be easily formed.

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

Examples of the base material include a resin film, a glass plate, a sheet obtained by making fibers, and the like. Since the conductive polymer dispersion used in this embodiment is solvent-based, a resin film having high hydrophobicity is suitable in this embodiment.
Examples of the resin constituting the resin film include polyolefin resin, ethylene-vinyl acetate copolymer resin, ethylene-methylmethacrylate copolymer resin, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. , Polyacrylate, polycarbonate, polyvinylidene fluoride, polyallylate, styrene-based elastomer, polyester-based elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate, etc. Be done. Examples of the polyolefin-based resin include polyethylene, polypropylene, ethylene-α-olefin copolymer resin, and propylene-α-olefin copolymer resin.
Further, the resin film may be unstretched or stretched.

The average thickness of the base material 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 base material 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 base material is a value obtained by measuring the thickness of any 10 or more points using an optical microscope or an electron microscope and averaging the measured values.

The conductive layer constituting the conductive film of the present embodiment is a layer formed by coating the conductive polymer dispersion liquid of the above embodiment. Therefore, the conductive layer in this embodiment contains at least a conductive complex and a diol compound that has not evaporated.
When the conductive polymer dispersion liquid contains a binder component, the conductive layer contains a binder resin. When the binder component contained in the conductive polymer dispersion is a curable compound, the cured product of the binder component becomes a binder resin. When the binder component contained in the conductive polymer dispersion is a resin, the binder component becomes the binder resin as it is.
Further, when the conductive polymer dispersion liquid further contains at least one of the high conductivity agent and the additive, the conductive layer also further contains at least one of the high conductivity agent and the additive.

The average thickness of the conductive layer is preferably 10 nm or more and 20000 nm or less, more preferably 20 nm or more and 10000 nm or less, and further preferably 30 nm or more and 5000 nm or less. If the average thickness of the conductive layer is at least the lower limit value, sufficiently high conductivity can be exhibited, and if it is at least the upper limit value, the conductive layer can be easily formed.
The thickness of the conductive layer is a value obtained by measuring the thickness of any 10 or more points using an optical microscope or an electron microscope and averaging the measured values.

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

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

Since the conductive layer constituting the conductive film of this embodiment is a layer formed from the conductive polymer dispersion liquid of the above embodiment, it is not only highly conductive but also excellent in light resistance.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.
In the following example, the water content of the conductive polymer dispersion was measured by Karl Fischer titration.

(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 20 minutes. Stirred for hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium styrene sulfonate-containing solution, and 1000 ml of the solvent of the polystyrene sulfonate-containing solution was removed by using an ultrafiltration method. 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of solvent was removed using an ultrafiltration method, and polystyrene sulfonic acid was washed with water. This ultrafiltration operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

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

(Manufacturing Example 3)
1000 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was freeze-dried to obtain a solid substance of 12 g of a conductive complex composed of a freeze-dried product.

(Manufacturing Example 4)
To 1000 g of isopropanol, 6.0 g of the solid substance of the conductive complex obtained in Production Example 3 and 5.25 g of trioctylamine were added and dispersed using a high-pressure homogenizer to disperse the isopropanol dispersion of the conductive complex. Got
In this example, the amino group of trioctylamine reacts with the anion group of the conductive complex to form a hydrophobic substituent.

(Manufacturing Example 5)
An attempt was made to prepare a propylene glycol dispersion of a conductive composite in the same manner except that isopropanol was changed to propylene glycol in Production Example 4, but the conductive composite and propylene glycol were separated and the dispersion could not be obtained. ..

(Manufacturing Example 6)
An attempt was made to prepare an ethylene glycol dispersion of a conductive composite in the same manner except that isopropanol was changed to ethylene glycol in Production Example 4, but the conductive composite and ethylene glycol were separated and a dispersion could not be obtained. ..

(Manufacturing Example 7)
An attempt was made to prepare a 1,4-butanediol dispersion of a conductive composite in the same manner except that isopropanol was changed to 1,4-butanediol in Production Example 4, but the conductive composite and 1,4-butanediol were prepared in the same manner. Butanediol was separated and a dispersion could not be obtained.

(Manufacturing Example 8)
An attempt was made to prepare a 1,2-butanediol dispersion of a conductive composite in the same manner except that isopropanol was changed to 1,2-butanediol in Production Example 4, but the conductive composite and 1,2-butanediol were prepared in the same manner. Butanediol was separated and a dispersion could not be obtained.

(Manufacturing Example 9)
An attempt was made to prepare a 1,3-butanediol dispersion of a conductive composite in the same manner except that isopropanol was changed to 1,3-butanediol in Production Example 4, but the conductive composite and 1,3-butanediol were prepared in the same manner. Butanediol was separated and a dispersion could not be obtained.

(Manufacturing Example 10)
An attempt was made to prepare a 2,3-butanediol dispersion of a conductive composite in the same manner except that isopropanol was changed to 2,3-butanediol in Production Example 4, but the conductive composite and 2,3-butanediol were prepared in the same manner. Butanediol was separated and a dispersion could not be obtained.

(Manufacturing Example 11)
To 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 300 g of methanol and 25 g of an epoxy compound (Epolite M-1230, C12, 13 mixed higher alcohol glycidyl ether manufactured by Kyoeisha Chemical Co., Ltd.) were added and heated at 60 ° C. for 4 hours. Stirred. As a result, the precipitated precipitate was collected by filtration to obtain 1.5 g of a conductive complex. Next, the conductive complex 1.5 was added to 198.5 g of methyl ethyl ketone and dispersed with a high-pressure homogenizer to obtain a methyl ethyl ketone dispersion of the conductive complex.
In this example, the epoxy group of the epoxy compound reacts with the anion group of the conductive complex to form a hydrophobic substituent.

(Manufacturing Example 12)
An attempt was made to prepare a propylene glycol dispersion of a conductive composite in the same manner except that methyl ethyl ketone was changed to propylene glycol in Production Example 11, but the conductive composite and propylene glycol were separated and a dispersion could not be obtained.

(Manufacturing Example 13)
An attempt was made to prepare an ethylene glycol dispersion of a conductive composite in the same manner except that methyl ethyl ketone was changed to ethylene glycol in Production Example 11, but the conductive composite and ethylene glycol were separated and a dispersion could not be obtained. ..

(Manufacturing Example 14)
An attempt was made to prepare a 1,4-butanediol dispersion of a conductive composite in the same manner except that the methyl ethyl ketone was changed to 1,4-butanediol in Production Example 11, but the conductive composite and 1,4-butanediol were prepared in the same manner. Butanediol was separated and a dispersion could not be obtained.

(Manufacturing Example 15)
An attempt was made to prepare a 1,2-butanediol dispersion of a conductive composite in the same manner except that the methyl ethyl ketone was changed to 1,2-butanediol in Production Example 11, but the conductive composite and 1,2-butanediol were prepared in the same manner. Butanediol was separated and a dispersion could not be obtained.

(Manufacturing Example 16)
An attempt was made to prepare a 1,3-butanediol dispersion of a conductive composite in the same manner except that the methyl ethyl ketone was changed to 1,3-butanediol in Production Example 11, but the conductive composite and 1,3-butanediol were prepared in the same manner. Butanediol was separated and a dispersion could not be obtained.

(Manufacturing Example 17)
An attempt was made to prepare a 2,3-butanediol dispersion of a conductive composite in the same manner except that the methyl ethyl ketone was changed to 2,3-butanediol in Production Example 11, but the conductive composite and 2,3-butanediol were prepared in the same manner. Butanediol was separated and a dispersion could not be obtained.

(Manufacturing Example 18)
100 g of methanol and 1.6 g of a photopolymerization initiator (Irgacure 127 manufactured by BASF) are added to 100 g of urethane acrylate (Art Resin UN-904M manufactured by Negami Kogyo Co., Ltd., solid content concentration 80% by mass, methyl ethyl ketone solution), and a binder component solution is added. Got

(Example 1)
99.4 g of propylene glycol (referred to as "PG" in the table) is added to 0.6 g of the solid material of the conductive complex obtained in Production Example 3, and dispersion treatment is performed using a high-pressure homogenizer to carry out conductivity. A polymer dispersion was obtained.
The obtained conductive polymer dispersion liquid was subjected to No. It was coated on a polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror T60) using the bar coater of No. 4 and dried at 150 ° C. for 1 minute. As a result, a conductive layer was formed to obtain a conductive film.

(Example 2)
A conductive film was obtained in the same manner as in Example 1 except that propylene glycol was changed to ethylene glycol (indicated as "EG" in the table).

(Example 3)
A conductive film was obtained in the same manner as in Example 1 except that propylene glycol was changed to 1,4-butanediol (indicated as "1,4-BD" in the table).

(Example 4)
A conductive film was obtained in the same manner as in Example 1 except that propylene glycol was changed to 1,2-butanediol (indicated as "1,2-BD" in the table).

(Example 5)
A conductive film was obtained in the same manner as in Example 1 except that propylene glycol was changed to 1,3-butanediol (indicated as "1,3-BD" in the table).

(Example 6)
A conductive film was obtained in the same manner as in Example 1 except that propylene glycol was changed to 2,3-butanediol (indicated as "2,3-BD" in the table).

(Comparative Example 1)
A conductive film was obtained in the same manner as in Example 1 except that 50 g of water was added to 50 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 to obtain a conductive polymer dispersion.

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

(Comparative Example 3)
A conductive film was obtained in the same manner as in Example 1 except that the conductive polymer dispersion was changed to the methyl ethyl ketone dispersion of the conductive composite obtained in Production Example 11.

(Example 7)
To 8 g of the conductive polymer dispersion liquid obtained in Example 1, 2 g of the binder component solution obtained in Production Example 18 was added to obtain a binder component-containing conductive polymer dispersion liquid.
The obtained conductive polymer dispersion liquid was subjected to No. It was applied onto a polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror T60) using a bar coater of No. 8, dried at 150 ° C. for 1 minute, and irradiated with ultraviolet rays of 400 mJ. As a result, the binder component was cured to form a conductive layer, and a conductive film was obtained.

(Example 8)
A conductive film was obtained in the same manner as in Example 7 except that the conductive polymer dispersion liquid obtained in Example 1 was changed to the conductive polymer dispersion liquid obtained in Example 2.

(Example 9)
A conductive film was obtained in the same manner as in Example 7 except that the conductive polymer dispersion liquid obtained in Example 1 was changed to the conductive polymer dispersion liquid obtained in Example 3.

(Example 10)
A conductive film was obtained in the same manner as in Example 7 except that the conductive polymer dispersion liquid obtained in Example 1 was changed to the conductive polymer dispersion liquid obtained in Example 4.

(Example 11)
A conductive film was obtained in the same manner as in Example 7 except that the conductive polymer dispersion liquid obtained in Example 1 was changed to the conductive polymer dispersion liquid obtained in Example 5.

(Example 12)
A conductive film was obtained in the same manner as in Example 7 except that the conductive polymer dispersion liquid obtained in Example 1 was changed to the conductive polymer dispersion liquid obtained in Example 6.

(Comparative Example 4)
A conductive polymer dispersion obtained by adding 50 g of water to 50 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was used as a conductive polymer dispersion, and the binder component solution obtained in Production Example 18 was added to the conductive polymer dispersion. A conductive film was obtained in the same manner as in Example 7 except that it was added.

(Comparative Example 5)
The conductive polymer dispersion was changed to the isopropanol dispersion of the conductive composite obtained in Production Example 4, and the binder component solution obtained in Production Example 18 was added to the isopropanol dispersion of the conductive composite obtained in Production Example 4. A conductive film was obtained in the same manner as in Example 7 except that it was added.

(Comparative Example 6)
The conductive polymer dispersion was changed to the methyl ethyl ketone dispersion of the conductive complex obtained in Production Example 11, and the binder component solution obtained in Production Example 18 was added to the methyl ethyl ketone dispersion of the conductive complex obtained in Production Example 11. A conductive film was obtained in the same manner as in Example 7 except that it was added.

(Comparative Example 7)
200 g of propylene glycol was added to 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, and water was removed using an evaporator to obtain 225 g of the conductive polymer dispersion. Using the obtained conductive polymer dispersion, a binder component-containing conductive polymer dispersion (diol content 77.4% by mass) was prepared, and a conductive film was obtained in the same manner as in Example 7. However, a large number of foreign substances were found in the coating film, and a uniform coating film could not be formed. Therefore, the production of the conductive film was discontinued.

<Evaluation>
The surface resistance value of the conductive layer of the conductive film 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 (indicated as "initial surface resistance value" in the table).
Further, using a carbon arc type light resistance tester, the conductive films of each example were irradiated with ultraviolet rays for 100 hours. After the irradiation with ultraviolet rays, the surface resistance value of the conductive film was measured in the same manner as described above. Table 1 shows the measurement results of the surface resistance value (indicated as "surface resistance value after the light resistance test" in the table). It should be noted that, in the table, "1.0 × 10 ⁸ <" means that it has exceeded the 1.0 × 10 ^8, that exceeds "1.0 × ^{10 12} <" is 1.0 × ^{10 12} means.

Table 1 shows the amount of increase in the surface resistance value after the light resistance test with respect to the initial surface resistance value (surface resistance value after the light resistance test / initial surface resistance value). The smaller the amount of increase, the better the light resistance. In the table, "5.0 × 10 ³ <" means that it exceeded 5.0 × 10 ³ , and “5.0 × 10 ² <” means that it exceeded ^{5.0 × 10 2.} meaning to, "5.0 × 10 ⁵ <" means that it has exceeded the 5.0 × 10 ^5, "2.5 × 10 ⁵ <" means that it has exceeded the 2.5 × 10 ⁵ ..

Table 1 shows the content ratio of the diol compound in the dispersion medium constituting the conductive polymer dispersion liquid.

<Result>
According to the conductive polymer dispersion of each example in which the content of the diol compound in the dispersion medium is 85% by mass or more and the water content is 1.0% by mass or less, the conductivity and light resistance are high. A conductive film having a layer could be produced.
In the conductive polymer dispersion of Comparative Example 1 in which the PEDOT-PSS aqueous dispersion was diluted with water, the light resistance of the conductive layer formed therein was low.
In the conductive polymer dispersions of Comparative Examples 2, 3, 5 and 6 in which the diol compound was not used as the dispersion medium, the light resistance of the conductive layer formed therein was low.
In addition, Examples 1 to 8 and Examples 10 to 12 are comparative examples.

Claims (10)

It contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, a dispersion medium containing 85% by mass or more and 100% by mass or less of a diol compound, and a binder component .
The π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
The polyanion is polystyrene sulfonic acid,
The diol compound is 1,4-butanediol.
A conductive polymer dispersion in which the binder component is an organic solvent-soluble active energy ray-curable acrylic compound. The conductive polymer dispersion liquid according to claim 1, wherein the content of water with respect to the total mass of the conductive polymer dispersion liquid is 0% by mass or more and 1.0% by mass or less. The conductive polymer dispersion liquid according to claim 1 or 2, wherein the content of water with respect to the total mass of the conductive polymer dispersion liquid is 0% by mass or more and 0.5% by mass or less. The conductive polymer dispersion liquid according to any one of claims 1 to 3, wherein the content of the diol compound with respect to the total mass of the dispersion medium is 95% by mass or more and 100% by mass or less. The conductive polymer dispersion liquid according to any one of claims 1 to 4, wherein the content of the diol compound with respect to the total mass of the dispersion medium is 99% by mass or more and 100% by mass or less. A conductive film comprising a base material and a conductive layer formed by coating at least one surface of the base material with the conductive polymer dispersion liquid according to any one of claims 1 to 5. .. The method for producing a conductive polymer dispersion according to any one of claims 1 to 5.
Forming a solid of the conductive composite to remove water from the raw material aqueous dispersion containing a conductive composite and water containing the π-conjugated conductive polymer and the polyanion,
Solids of the conductive composite, the diol compound, and mixing the binder component, has a step of obtaining the conductive polymer dispersion,
As the content of the diol compound in the dispersion medium contained in the conductive polymer dispersion is below 85 wt% to 100 wt%, solids of the conductive composite, the diol compound, and the binder component A method for producing a conductive polymer dispersion. The high conductivity according to claim 7 , wherein after mixing the solid substance of the conductive complex and the diol compound, a dispersion treatment is performed on a mixed solution containing the solid substance of the conductive complex and the diol compound. A method for producing a molecular dispersion. The method for producing a conductive polymer dispersion according to claim 7 or 8 , wherein water is removed from the raw material water dispersion by freeze-drying the raw material water dispersion. A method for producing a conductive film, wherein the conductive polymer dispersion liquid according to any one of claims 1 to 5 is applied to at least one surface of a base material to form a conductive layer.