JP7340955B2 - Conductive polymer-containing liquid and method for producing the same, and method for producing conductive film - Google Patents

Description

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

A π-conjugated conductive polymer whose main chain is composed of a π-conjugated system forms a conductive composite by doping with a polyanion having an anion group, and becomes dispersible in water. Manufacturing a conductive film with a conductive layer by coating a conductive polymer-containing liquid (sometimes called a conductive polymer dispersion) containing a conductive composite onto a film base material, etc. Can be done. However, the film base material to which the conductive polymer-containing liquid is applied is often a hydrophobic plastic film. Therefore, the wettability of a conductive polymer-containing liquid containing water to a film substrate, particularly a polypropylene film, is poor, and there has been a problem that the conductive film formed on the film substrate becomes non-uniform to the extent that it is difficult to function.

Therefore, water, which is a dispersion medium of the conductive composite, is sometimes replaced with an organic solvent. For example, it is known that a conductive composite dispersed in water is freeze-dried to obtain a dried body, and then an organic solvent and an amine compound are added to the dried body (Patent Document 1).
Furthermore, a method is known in which a conductive polymer is dispersed in an organic solvent by reacting a conductive composite dispersed in water with a cyclic ether compound having at least one of an oxirane group and an oxetane group to make it hydrophobic. (Patent Document 2).

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

However, in the methods described in Patent Documents 1 and 2, it is necessary to replace the dispersion medium of the conductive composite from water with an organic solvent, so it is difficult to sufficiently increase the production efficiency of the conductive polymer-containing liquid. There was a problem that I couldn't do it. In addition, after applying a conductive polymer-containing liquid containing only an organic solvent as a dispersion medium to a film base material, it sometimes dries too quickly, making it difficult to adjust the coating speed and coating thickness. .

The present invention relates to a conductive polymer-containing liquid that has excellent wettability to film substrates and a moderately fast drying speed after coating, a method for producing the conductive polymer-containing liquid with improved manufacturing efficiency, and a conductive film. Provides a manufacturing method.

[1] A conductive polymer-containing liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, water, an organic solvent, and a silicon-containing organic compound having a molecular weight of 1000 or less, The content of the organic solvent is 30% by mass or more and 90% by mass or less with respect to the total mass of the conductive composite, and the content of the silicon-containing organic compound is 100 parts by mass or more and 10,000 parts by mass with respect to 100 parts by mass of the conductive composite. A conductive polymer-containing liquid containing parts by mass or less.
[2] The conductive polymer-containing liquid according to [1], wherein the organic solvent contains alcohol.
[3] The conductive polymer-containing liquid according to [1] or [2], wherein the organic solvent contains at least one of methanol and ethanol.
[4] The conductive polymer-containing liquid according to any one of [1] to [3], wherein the silicon-containing organic compound contains an alkoxysilane.
[5] The conductive polymer-containing liquid according to any one of [1] to [4], wherein the silicon-containing organic compound contains trimethoxyvinylsilane.
[6] The conductive polymer-containing liquid according to any one of [1] to [5], wherein the silicon-containing organic compound contains tetraethoxysilane.
[7] The conductive polymer-containing liquid according to any one of [1] to [6], which further contains a binder component, and the binder component is a water-dispersible resin.
[8] The conductive polymer-containing liquid according to any one of [1] to [7], wherein the water-dispersible resin includes a water-dispersible polyester resin.
[9] The conductive polymer-containing liquid according to any one of [1] to [8], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene).
[10] The conductive polymer-containing liquid according to any one of [1] to [9], wherein the polyanion is polystyrene sulfonic acid.
[11] By mixing an organic silane solution in which a silicon-containing organic compound is dissolved in an organic solvent and a dispersion in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is dispersed in water, A method for producing a conductive polymer-containing liquid, wherein during the mixing, the content of the organic solvent is 30% by mass or more and 90% by mass or less based on the total mass of the conductive polymer-containing liquid, and A method for producing a conductive polymer-containing liquid, wherein the content of the silicon-containing organic compound is 100 parts by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of the conductive composite.
[12] The organic solvent contains at least one of methanol and ethanol, the silicon-containing organic compound contains an alkoxysilane, and the conductive composite contains poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid. The method for producing a conductive polymer-containing liquid according to [11].
[13] The conductive polymer-containing liquid according to any one of [1] to [10] is applied to at least one surface of a film base material, and the coating film formed on the film base material is A method of manufacturing a conductive film, the method comprising drying.
[14] The method for producing a conductive film according to [13], wherein the film base material is a film made of a polyolefin resin.
[15] The method for producing a conductive film according to [14], wherein the polyolefin resin includes a polypropylene resin.

Since the conductive polymer-containing liquid of the present invention contains a silicon-containing organic compound and an organic solvent in predetermined amounts, it has excellent wettability to a film base material.
According to the method for producing a conductive polymer-containing liquid of the present invention, by simply mixing an aqueous dispersion of a conductive composite and an organosilane solution containing a predetermined amount of a silicon-containing organic compound and an organic solvent, the desired result can be obtained. A conductive polymer-containing liquid is obtained. At this time, there is no need to replace water with an organic solvent as the dispersion medium of the conductive composite.
According to the method for producing a conductive film of the present invention, since the conductive polymer-containing liquid contains not only an organic solvent but also water, the coating film of the conductive polymer-containing liquid applied on the film base material dries appropriately. Therefore, a uniform and even conductive film can be easily formed.

≪Conductive polymer-containing liquid≫
The conductive polymer-containing liquid of the first aspect of the present invention contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, water, an organic solvent, and a silicon-containing organic compound with a molecular weight of 1000 or less. The content of the organic solvent is 30% by mass or more and 90% by mass or less based on the total mass of the conductive polymer-containing liquid, and the content of the organic solvent is 30% by mass or more and 90% by mass or less based on 100 parts by mass of the conductive composite. The content of the silicon organic compound is 100 parts by mass or more and 10,000 parts by mass or less.
In the conductive polymer-containing liquid of the present invention, the conductive composite may be in a dispersed state or in a dissolved state.

[Conductive composite]
The conductive composite in this embodiment includes a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive composite is doped into a π-conjugated conductive polymer to form a conductive composite having conductivity.

(π-conjugated conductive polymer)
The π-conjugated conductive polymer may be any organic polymer whose main chain is composed of a π-conjugated system, such as polypyrrole-based conductive polymers, polythiophene-based conductive polymers, and polyacetylene-based conductive polymers. Examples include polyphenylene conductive polymers, polyphenylene vinylene conductive polymers, polyaniline conductive polymers, polyacene conductive polymers, polythiophene vinylene conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferred, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferred.

Polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), 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-decyloxythiophene) ,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-carboxythiophene) butylthiophene).
Examples of polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), and poly(3-butylpyrrole). pyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-dibutylpyrrole) -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), and poly(3-methyl-4-hexyloxypyrrole).
Examples of polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-aniline sulfonic acid), and poly(3-aniline sulfonic acid).
Among these π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred in terms of conductivity, transparency, and heat resistance.
The number of types of π-conjugated conductive polymers contained in the conductive composite may be one or two or more types.

(Polyanion)
A polyanion is a polymer having two or more monomer units having anionic groups in its molecule. The anion group of this polyanion functions as a dopant for the π-conjugated conductive polymer to improve 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, polyallylsulfonic acid, polyacrylic ester having a sulfo group, polymethacrylic ester having a sulfo group (for example, poly(4-sulfobutyl methacrylate) , polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, and other polymers with sulfo groups, polyvinylcarboxylic acid, polystyrenecarboxylic acid, Polymers having carboxyl groups such as polyarylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), and polyisoprenecarboxylic acid are mentioned. may be a homopolymer obtained by polymerizing two or more types of monomers, or a copolymer obtained by polymerizing two or more types of monomers.
Among these polyanions, polymers having sulfo groups are preferred, and polystyrene sulfonic acid is more preferred, since it can further increase the conductivity.
The polyanions 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 1,000,000 or less, more preferably 100,000 or more and 500,000 or less. The mass average molecular weight is a mass-based average molecular weight measured using gel permeation chromatography and calculated in terms of polystyrene.

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, and 10 parts by mass or more and 700 parts by mass or less, based on 100 parts by mass of the π-conjugated conductive polymer. It is more preferable that it is, and it is even more preferable that it is in the range of 100 parts by mass or more and 500 parts by mass or less. If the content ratio of the polyanion is equal to or higher than the lower limit value, the doping effect on the π-conjugated conductive polymer tends to become stronger, and the conductivity becomes higher. On the other hand, if the content of the polyanion is below the upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

In the polyanion in the conductive composite, not all of the anion groups are doped into the π-conjugated conductive polymer, and there are surplus anion groups that do not participate in doping. This surplus anion group is a hydrophilic group, and the dispersibility of the conductive composite in which the anion group is not modified is high in an aqueous dispersion medium and low in an organic solvent.

[Silicon-containing organic compound]
The silicon-containing organic compound of this embodiment is an organic compound having a silicon atom and having a molecular weight of 1000 or less, and includes an organosilicon compound having a silicon-carbon bond and a silane compound having a silicon-hydrogen bond.
The silicon-containing organic compound of this embodiment is preferably one that functions as a binder component when cured, that is, a curable compound.
The molecular weight of the silicon-containing organic compound of this embodiment is 1000 or less, more preferably 500 or less, and even more preferably 200 or less, considering solubility in the conductive polymer-containing liquid. .

The silicon-containing organic compound, which is a curable compound, is preferably an organic compound in which one or more alkoxy groups are bonded to silicon, for example. Specifically, alkoxysilanes such as trialkoxysilane and tetraalkoxysilane are preferred.

Specific examples of trialkoxysilane include 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, and 3-(trimethoxysilyl acrylate). ) propyl, 3-(2-aminoethylamino)propyltriethoxysilane, (11-azidoundecyl)trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, 1,2-bis(trimethoxysilyl)ethane , [bicyclo[2.2.1]hept-5-en-2-yl]triethoxysilane, benzyltriethoxysilane, (3-bromopropyl)trimethoxysilane, 1,2-bis(triethoxysilyl)ethane , 1,6-bis(trimethoxysilyl)hexane, 3-trimethoxysilylpropyl chloride, 2-cyanoethyltriethoxysilane, (chloromethyl)triethoxysilane, cyclohexyltrimethoxysilane, (chloromethyl)trimethoxysilane, chloro Triethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, [3-(N,N-dimethylamino)propyl]trimethoxysilane, [3-(diethylamino)propyl]trimethoxysilane, decyltrimethoxysilane, 3- [(dimethylsilyl)oxy]-1,1,3,5,5-pentamethyltrisiloxane, triethoxyethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ethyltrimethoxysilane, 3- Glycidyloxypropyltrimethoxysilane, [8-(glycidyloxy)-n-octyl]trimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexadecyltrimethoxysilane, 3-(triethoxysilyl)propyl isocyanate, Tris[3-(trimethoxysilyl)propyl] isocyanurate, triethoxymethylsilane, trimethoxy(methyl)silane, 3-(trimethoxysilyl)propyl methacrylate, (3-mercaptopropyl)trimethoxysilane, 3-methacrylic acid [Tris(trimethylsilyloxy)silyl]propyl, (3-mercaptopropyl)triethoxysilane, octadecyltriethoxysilane, triethoxy-n-octylsilane, octadecyltrimethoxysilane, triethoxyphenylsilane, pentyltriethoxysilane, trimethoxyphenyl Silane, trimethoxy[3-(phenylamino)propyl]silane, 2-propynyl [3-(triethoxysilyl)propyl]carbamate, trimethoxysilane, triethoxysilane, 3-chloropropyltriethoxysilane, 3-aminopropyl Trimethoxysilane, triethoxyfluorosilane, triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane, trimethoxy(propyl)silane, 1-[3-(trimethoxysilyl)propyl]urea, (3 -isocyanatopropyl)trimethoxysilane, trimethyl[3-(triethoxysilyl)propyl]ammonium chloride, trimethoxy(p-tolyl)silane, triethoxy(3-glycidyloxypropyl)silane, 3-(triethoxysilyl) methacrylate Propyl, trimethoxy(3,3,3-trifluoropropyl)silane, trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, triethoxy(propyl) Silane, trimethoxy[3-(methylamino)propyl]silane, trimethoxy-n-octylsilane, triethoxy-1H,1H,2H,2H-heptadecafluorodecylsilane, trimethoxy(1H,1H,2H,2H-heptadecafluoro decyl)silane, trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, triethoxy(pentafluorophenyl)silane, trimethoxy(11-pentafluorophenoxyundecyl)silane, trimethoxy(4-vinylphenyl)silane, triethoxy [5,5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl]silane, 1-(trimethoxysilyl)naphthalene, trimethoxy(pentafluorophenyl)silane, trimethoxy (7-octen-1-yl)silane, [3-(trimethoxysilyl)propyl]succinic anhydride, trimethoxy(phenylethyl)silane, 1-[3-(triethoxysilyl)propyl]urea, vinyltrimethoxy Silane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, N-[2-(N-vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane hydrochloride, and the like.
Among the trialkoxysilanes, trialkoxysilanes having a vinyl group are preferred because they improve the dispersibility of the conductive composite and can easily form a uniform conductive film. Further, it is also preferable to use a trialkoxysilane having a vinyl group together with an alkoxysilane having no vinyl group. The alkoxysilane having no vinyl group is preferably one or more selected from trimethoxysilane, triethoxysilane, and tetraalkoxysilane described below.

Specific examples of tetraalkoxysilane include tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, tetrapropoxysilane, and tetraisopropoxysilane.
In addition, silicon-containing organic compounds include, for example, partial condensates of tetramethoxysilane (for example, methyl silicate 51, manufactured by Colcoat Co., Ltd.), partial condensates of tetraethoxysilane (for example, ethyl silicate 48, etc., manufactured by Colcoat Co., Ltd.), Specific examples of silicate compounds include .

The number of silicon-containing organic compounds contained in the conductive polymer-containing liquid of this embodiment may be one type or two or more types.
The total content of the silicon-containing organic compounds included in this embodiment is 100 parts by mass or more, preferably 200 parts by mass or more, and 300 parts by mass or more, based on 100 parts by mass of the conductive composite. The amount is more preferably 350 parts by mass or more, even more preferably 400 parts by mass or more.
When the content is at least the lower limit, the dispersibility of the conductive composite in the conductive polymer-containing liquid is improved, and a uniform and even conductive film can be formed on the film base material.
The upper limit of the above content is not particularly limited, but from the viewpoint of maintaining the strength and uniform film quality of the conductive film and obtaining sufficient conductivity, it is preferably 10,000 parts by mass or less, and preferably 5,000 parts by mass or less. More preferably, it is 1000 parts by mass or less.
That is, the above content is preferably 200 parts by mass or more and 10,000 parts by mass or less, more preferably 300 parts by mass or more and 5,000 parts by mass or less, and 400 parts by mass, based on 100 parts by mass of the conductive composite. More preferably, the amount is 1000 parts by mass or less.

(Organic solvent)
The organic solvent in this embodiment may be a water-soluble organic solvent, a water-insoluble organic solvent, or a mixed solvent of a water-soluble organic solvent and a water-insoluble organic solvent, but phase separation in a conductive polymer-containing liquid A water-soluble organic solvent is preferable from the viewpoint of suppressing this. Here, the water-soluble organic solvent is an organic solvent in which the amount dissolved in 100 g of water at 20° C. is 1 g or more, and the water-insoluble organic solvent is an organic solvent in which the amount dissolved in 100 g of water at 20° C. is less than 1 g.

Examples of the water-soluble organic solvent include alcohol solvents (alcohols), ether solvents, ketone solvents, and nitrogen atom-containing solvents.
Examples of alcoholic solvents include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, Examples include ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether.
Examples of the ether solvent include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, diethylene glycol diethyl 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 nitrogen atom-containing solvent include N-methylpyrrolidone, dimethylacetamide, and dimethylformamide.
One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination.
As the water-soluble organic solvent, alcohol-based solvents or ketone-based solvents are preferable because the coating properties of the conductive polymer-containing liquid on the film base material are improved. Moreover, since the solubility of the silicon-containing organic compound in the conductive polymer-containing liquid is improved, alcohol-based solvents are more preferable, and at least one of methanol and ethanol is even more preferable.

Examples of the water-insoluble organic solvent include hydrocarbon solvents. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents.
Examples of the aliphatic hydrocarbon solvent include hexane, cyclohexane, pentane, heptane, octane, nonane, decane, and dodecane.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, and isopropylbenzene.
One type of water-insoluble organic solvent may be used alone, or two or more types may be used in combination.
Among the water-insoluble organic solvents, aromatic hydrocarbon solvents are preferred, and toluene is more preferred, in that the conductive polymer-containing liquid in this embodiment can be easily produced.

From the viewpoint of increasing the solubility of the silicon-containing organic compound in the conductive polymer-containing liquid of this embodiment, the content of the organic solvent with respect to the total mass of the conductive polymer-containing liquid is 30% by mass or more. Further, from the viewpoint of increasing the dispersibility of the hydrophilic conductive composite, the content of the organic solvent with respect to the total mass of the conductive polymer-containing liquid is preferably 90% by mass or less, more preferably 60% by mass or less, More preferably, it is 40% by mass or less.
That is, the above content is preferably 30% by mass or more and 90% by mass or less, preferably 30% by mass or more and 60% by mass or less, and 30% by mass or more and 40% by mass or less, based on the total mass of the conductive polymer-containing liquid. is even more preferable.

(aqueous dispersion medium)
The solvent in this embodiment is an aqueous dispersion containing water and an organic solvent.
The content of water with respect to the total mass of the conductive polymer-containing liquid is not particularly limited as long as the content of the organic solvent is 30% by mass or more and can be adjusted to the above-mentioned suitable range, and is preferably 50% by mass or more, and 60% by mass or more. It is more preferably 65% by mass or more, and even more preferably 65% by mass or more.
The upper limit of the content is less than 70% by mass.

(Content of conductive composite)
The content of the conductive composite relative to the total mass of the conductive polymer-containing liquid is, for example, preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 5.0% by mass or less. , more preferably 0.6% by mass or more and 2.0% by mass or less.
When it is at least the lower limit of the above range, sufficient conductivity can be obtained from the conductive film formed using the conductive polymer-containing liquid of this embodiment. When it is below the upper limit of the above range, the dispersibility of the conductive composite in the conductive polymer-containing liquid of this embodiment can be improved.

(binder component)
The conductive polymer-containing liquid may contain a binder component other than the above-mentioned silicon-containing organic compound. The binder component is a resin other than the π-conjugated conductive polymer and the polyanion, or a precursor thereof, and is a thermoplastic resin, or a curable monomer or oligomer that hardens during formation of the conductive layer (conductive film). The thermoplastic resin becomes the binder resin as it is, and the resin formed by curing the curable monomer or oligomer becomes the binder resin.
One type of binder component may be used alone, or two or more types may be used in combination.

Specific examples of the binder resin derived from the binder component include acrylic resin (acrylic compound), polyester resin, polyurethane resin, polyimide resin, polyether resin, melamine resin, silicone, and the like.
Since the dispersion medium of the conductive polymer-containing liquid is an aqueous dispersion medium, the binder resin contained is preferably a water-dispersible resin, and more preferably a water-dispersible emulsion resin. The water-dispersible resin is an emulsion resin or a water-soluble resin.

Specific examples of water-dispersible emulsion resins include acrylic resins (acrylic compounds), polyester resins, polyurethane resins, polyimide resins, melamine resins, etc., which are made into emulsions with emulsifiers. Among these, polyester emulsions are preferred because the strength of the coating film (conductive film) obtained by applying a conductive polymer-containing liquid to a film base material is increased. In particular, when coating a polyester film base material, a polyester emulsion is preferred because the adhesiveness of the coating film to the film base material is high.

Specific examples of water-soluble resins include acrylic resins (acrylic compounds), polyester resins, polyurethane resins, polyimide resins, and melamine resins, which have acid groups such as carboxyl groups and sulfo groups, or salts thereof. Here, the water-soluble resin is preferably one that can dissolve in 100 g of distilled water at 25° C. 1 g or more, preferably 5 g or more, more preferably 10 g or more.

Acid groups such as carboxy groups and sulfo groups that the binder resin has may form salts with cations such as sodium ions and potassium ions.

The curable monomer or oligomer may be a thermosetting monomer or oligomer or a photocurable monomer or oligomer. Here, the oligomer refers to a polymer having a mass average molecular weight of less than 10,000. Note that a polymer having a mass average molecular weight of more than 10,000 does not have curability.
Examples of curable monomers include acrylic monomers (acrylic compounds) and epoxy monomers. Examples of curable oligomers include acrylic oligomers (acrylic compounds) and epoxy oligomers.
When an acrylic monomer or acrylic oligomer is used as the binder component, it can be easily cured by heating or light irradiation.

When containing a curable monomer or oligomer, it is preferable that a curing catalyst is further included. For example, when containing a thermosetting monomer or oligomer, it is preferable to include a thermal polymerization initiator that generates radicals when heated, and when containing a photocurable monomer or oligomer, generating radicals when irradiated with light. It is preferable that the photopolymerization initiator is included.

The content ratio of the binder component (however, the silicon-containing organic compound is not included) in the conductive polymer-containing liquid is preferably 100 parts by mass or more and 20,000 parts by mass or less with respect to 100 parts by mass of the conductive composite. , more preferably 100 parts by mass or more and 5000 parts by mass or less. When the content ratio of the binder component is equal to or higher than the lower limit value, film formability and film strength when applying the conductive polymer-containing liquid to a film base material can be improved. If the content ratio of the binder component is below the above-mentioned upper limit value, it is possible to suppress a decrease in conductivity due to a decrease in the content ratio of the conductive composite.

(High conductivity agent)
The conductive polymer-containing liquid may contain a high conductivity agent in order to further improve conductivity.
High conductivity agents include sugars, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxy groups, compounds having two or more carboxyl groups, one or more hydroxy groups, and one or more carboxyl groups. The compound is preferably at least one compound selected from the group consisting of a compound having an amide group, a compound having an imide group, a lactam compound, and a compound having a glycidyl group.
However, the high conductivity agent is a compound other than the aforementioned π-conjugated conductive polymer and polyanion, the organic solvent, the silicon-containing organic compound, and the binder component.
Among the high conductivity agents, glycol, which is a linear compound having two hydroxyl groups, is preferred, and propylene glycol is more preferred, since it has a high effect of improving conductivity.
The number of highly conductive agents contained in the conductive polymer-containing liquid may be one, or two or more.

The content ratio of the high conductivity agent is preferably 1 part by mass or more and 10,000 parts by mass or less, more preferably 10 parts by mass or more and 5,000 parts by mass or less, and 100 parts by mass or less, based on 100 parts by mass of the conductive composite. It is more preferably 1 part or more and 2500 parts by mass or less. If the content ratio of the high conductivity agent is above the lower limit value, the conductivity improvement effect by adding the high conductivity agent will be fully exhibited, and if it is below the upper limit value, the concentration of π-conjugated conductive polymer will be reduced. It is possible to prevent a decrease in conductivity caused by

(Other additives)
The conductive polymer-containing liquid may also contain other additives.
The additives are not particularly limited as long as the effects of the present invention can be obtained, and for example, surfactants, inorganic conductive agents, antifoaming agents, antioxidants, ultraviolet absorbers, etc. can be used.
However, the additives are other than the above-mentioned π-conjugated conductive polymer, polyanion, dispersion medium, silicon-containing organic compound, binder component, and high conductivity agent.
Examples of the surfactant include nonionic, anionic, and cationic surfactants, and nonionic surfactants are preferred from the viewpoint of storage stability. Additionally, a polymeric surfactant such as polyvinylpyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions, conductive carbon, and the like. Note that metal ions can be generated by dissolving metal salts in water.
Examples of antifoaming agents include silicone resins, polydimethylsiloxanes, silicone oils, and the like.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, sugars, and the like.
Examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, benzoate UV absorbers, etc. can be mentioned.

When the conductive polymer-containing liquid contains the additive, the content ratio is appropriately determined depending on the type of additive, but for example, 0.001 parts by mass per 100 parts by mass of the conductive composite. The content may be in a range of 5 parts by mass or less.

≪Method for producing conductive polymer-containing liquid≫
The second aspect of the present invention is a method for producing the conductive polymer-containing liquid of the first aspect.
The conductive polymer-containing liquid of the first embodiment can be easily produced by the method described below.
That is, an organic silane solution in which a silicon-containing organic compound is dissolved in an organic solvent, and a dispersion (referred to as a conductive polymer aqueous dispersion) in which a conductive composite containing a π-conjugated conductive polymer and a polyanion are dispersed in water. This is a method of mixing the following. During the mixing, the content of the organic solvent with respect to the total mass of the conductive polymer-containing liquid is 30% by mass or more and 90% by mass or less, and the content of the silicon-containing organic compound with respect to 100 parts by mass of the conductive composite. The content is 100 parts by mass or more and 10,000 parts by mass or less.

Since the concentration of the silicon-containing organic compound dissolved in the organic silane solution is diluted by mixing with the conductive polymer aqueous dispersion, it is set in consideration of this dilution. For example, it is preferable to dissolve the silicon-containing organic compound in an amount of preferably 1 to 10 g, more preferably 3 to 6 g, per 100 g of the alcoholic solvent.
If the lower limit is above, the silicon-containing organic compound may be contained in a predetermined proportion to 100 parts by mass of the conductive composite contained in the conductive polymer-containing liquid to improve the dispersibility of the conductive composite. becomes easier.
When it is below the above upper limit, the solubility of the silicon-containing organic compound in the conductive polymer-containing liquid becomes good, and precipitation of the silicon-containing organic compound can be suppressed.

A dispersion in which a conductive composite is dispersed in water (sometimes referred to as a conductive polymer aqueous dispersion) is produced by, for example, adding monomers constituting a π-conjugated conductive polymer to an aqueous polyanion dispersion. It can be obtained by oxidative polymerization. Furthermore, a commercially available aqueous conductive polymer dispersion may be used.

The content of the conductive composite relative to the total mass of the conductive polymer aqueous dispersion is, for example, preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and 1 It is more preferably .0% by mass or more and 5.0% by mass or less.
Within the above range, the content of the conductive composite relative to the total mass of the conductive polymer-containing liquid can be easily adjusted to the above-mentioned suitable range.

By adjusting the mixing ratio of the organic silane solution and the conductive polymer aqueous dispersion, the content of the organic solvent and the content of the silicon-containing organic compound relative to the total mass of the conductive polymer-containing liquid can be adjusted. Let the amount be a predetermined ratio.
Although the mixing method is not particularly limited, it is preferable to add the conductive polymer aqueous dispersion to the organic silane solution to which ion-exchanged water has been added first to dilute the organic solvent concentration, and to stir the mixture. With this method, it is possible to prevent the silicon-containing organic compound in the organic silane solution from precipitating immediately after mixing.
By the above manufacturing method, the desired conductive polymer-containing liquid can be obtained.

<Method for manufacturing conductive film>
The method for producing a conductive film according to the third aspect of the present invention includes applying the conductive polymer-containing liquid according to the first aspect to at least one surface of a film base material, and forming a coating film on the film base material. including drying.

(Film base material)
Examples of the film base material include plastic films.
Examples of film base resins constituting plastic films include ethylene-methyl methacrylate 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 elastomer, polyester elastomer, polyether sulfone, polyetherimide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio Examples include Nate. Among these film base resins, polyethylene terephthalate is preferred because it is inexpensive and has excellent mechanical strength.
Furthermore, since the conductive polymer-containing liquid of the present invention has good wettability when applied, the film base material is preferably a film made of polyolefin resin.
The type of the polyolefin resin is not particularly limited, and any known polyolefin resin can be used. Among these, it is preferable that the film base material contains a polypropylene resin since the above-mentioned wettability is good.

The resin for the film base material may be amorphous or crystalline.
The film base material may be unstretched or stretched.
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-containing liquid.

The average thickness of the film base material is preferably 5 μm or more and 500 μm or less, more preferably 20 μm or more and 200 μm or less. If the average thickness of the film base material is greater than or equal to the lower limit, it will be difficult to break, and if it is less than or equal to the upper limit, sufficient flexibility can be ensured as a film.
The thickness of a member in this specification is a value obtained by measuring the thickness at arbitrary 10 locations and averaging the measured values.

A known polarizing film can also be used as the film base material.
As a polarizing film, for example, one including a pair of transparent films and a polarizing layer disposed between them is known.
Examples of the transparent resin constituting the transparent film include triacetyl cellulose, polyethylene terephthalate, polycarbonate, polycycloolefin, polystyrene, polyvinyl alcohol, and acrylic resin.
The thickness of the transparent film can be, for example, 10 μm or more and 500 μm or less, and preferably 20 μm or more and 300 μm or less in terms of achieving both thinness and strength.
Examples of the polarizing layer 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 and a partially saponified film of ethylene/vinyl acetate copolymer. Examples of dichroic substances include iodine and dichroic dyes.
The thickness of the polarizing layer can be, for example, 10 μm or more and 500 μm or less, and preferably 20 μm or more and 300 μm or less in terms of achieving both thinness and polarization.

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

Examples of methods for coating (applying) a conductive polymer-containing liquid onto a film base material 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, Apply a method using a coater such as an air doctor coater, knife coater, blade coater, cast coater, or screen coater, a method using a sprayer such as air spray, airless spray, or rotor dampening, or an immersion method such as dipping. I can do it.
Commercially available bar coaters are numbered according to the coating thickness, and the higher the number, the thicker the coating can be applied.
The amount of the conductive polymer-containing liquid to be applied to the film base material is not particularly limited, but in consideration of uniform and even application, conductivity and film strength, the solid content should be 0.01 g/m ² It is preferably in the range of 10.0 g/m ² or less.

A conductive film on which a conductive layer (conductive film) is formed can be obtained by drying a coating film made of a conductive polymer-containing liquid applied onto a film base material and removing the dispersion medium.
Examples of methods for drying the coating film include heating drying, vacuum drying, and the like. For heating and drying, for example, a conventional method such as hot air heating or infrared heating can be used.
When heat drying is applied, the heating temperature is appropriately set depending on the dispersion medium used, but is usually within the range of 50°C or higher and 150°C or lower. Here, the heating temperature is the set temperature of the drying device.

When the applied conductive polymer-containing liquid contains a thermosetting monomer or oligomer as a binder component, the conductive layer is formed by heating the coating film and curing the binder component. You can get the film.
When the applied conductive polymer-containing liquid contains a photocurable monomer or oligomer as a binder component, the conductive layer can be cured by irradiating the coating film with ultraviolet rays or electron beams to harden the binder component. A formed conductive film can be obtained.

≪Conductive film≫
The conductive film produced according to the third aspect of the present invention includes a conductive composite containing a π-conjugated conductive polymer and a polyanion on at least one surface of a film base material, and a cured product of the silicon-containing organic compound. A conductive film is provided with a conductive layer comprising:

(conductive layer)
The average thickness of the conductive layer provided on at least one surface of the film base material is, for example, preferably 10 nm or more and 5000 nm or less, more preferably 20 nm or more and 1000 nm or less, and 30 nm or more and 500 nm or less. It is even more preferable.
If the average thickness of the conductive layer is equal to or greater than the lower limit, sufficiently high conductivity can be exhibited, and if the average thickness is equal to or less than the upper limit, the conductive layer can be easily formed.

The conductive layer of the conductive film of this embodiment preferably has a surface resistance value of, for example, 1×10 ² Ω/□ or more and 1×10 ¹⁰ Ω/□ or less, as a measure of good conductivity. It is more preferable to have a surface resistance value of ² Ω/□ or more and 1×10 ⁴ Ω/□ or less, and more preferably a surface resistance value of 1×10 ² Ω/□ or more and 1×10 ³ Ω/□ or less.

<Effect>
Since the conductive polymer-containing liquid of the present invention contains a silicon-containing organic compound and an organic solvent in predetermined amounts, it has excellent wettability to a film base material. At first glance, the dispersibility of the hydrophilic conductive composite seems to be unstable in the presence of organic solvents, but by including silicon-containing organic compounds, it becomes conductive even in the presence of organic solvents. The dispersibility of the sex complex is well maintained. Further, the silicon-containing organic compound itself will precipitate in the presence of water unless the concentration of the organic solvent is at least a predetermined level (see Comparative Example below). As described above, it has conventionally been difficult to stably disperse a hydrophilic conductive composite in a dispersion medium containing an organic solvent and water, but in the present invention, a silicon-containing organic compound is dispersed in a predetermined amount of an organic solvent. By including the hydrophilic conductive composite in a dispersion medium containing an organic solvent and water, the hydrophilic conductive composite can be stably dispersed in a dispersion medium containing an organic solvent and water.

(Production Example 1) Production of polystyrene sulfonic acid Dissolve 206 g of sodium styrene sulfonate in 1000 ml of ion-exchanged water, and while stirring at 80°C, add 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water. The solution was added dropwise for 20 minutes and stirred for 12 hours.
1,000 ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium polystyrene sulfonate-containing solution, and about 1,000 ml of the solvent in the obtained polystyrene sulfonic acid-containing solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by ultrafiltration, and the polystyrene sulfonic acid was washed with water. This water washing operation was repeated three times.
Water in the resulting solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Production Example 2) Production of a conductive polymer-containing liquid containing an aqueous dispersion medium (conductive polymer aqueous dispersion medium) 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid were added to 2000 ml. and a solution dissolved in ion-exchanged water were mixed at 20°C.
The resulting mixed solution was kept at 20°C, and while stirring, 29.64 g of ammonium persulfate and 8.0 g of ferric sulfate oxidation catalyst solution dissolved in 200 ml of ion-exchanged water were slowly added, and the mixture was stirred for 3 hours. The mixture was stirred and reacted.
2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated three 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 by ultrafiltration. 2000 ml of ion-exchanged water was added to the residual liquid, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated three times.
Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated 5 times to obtain a conductive polymer aqueous dispersion medium in which polystyrene sulfonic acid-doped poly(3,4-ethylenedioxythiophene) (PEDOT-PSS) with a concentration of 1.2% by mass was dispersed in the aqueous dispersion medium. Ta. Note that the content of PSS in the PEDOT-PSS solid content is 75% by mass.

In each of the following examples, conductive polymer-containing liquids were prepared and attempts were made to produce conductive films. The film formation test results of the conductive film were evaluated based on the following criteria.
A: A good conductive film was formed.
B: A functional conductive film was formed although there was some unevenness.
C: A non-uniform film with severe unevenness and difficult to function as a conductive film was formed.
D: Precipitates were formed in the conductive polymer-containing liquid, making it difficult to apply.

(Example 1)
0.75 g of trimethoxyvinylsilane was dissolved in 30 g of methanol, 15 g of ion-exchanged water was added, and the mixture was stirred at room temperature for 10 minutes. Thereafter, 50 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 (PEDOT-PSS solid content 0.6 g) was added and stirred at room temperature for 30 minutes to obtain a conductive polymer-containing liquid.
The obtained conductive polymer-containing liquid was transferred to No. It was coated on a polypropylene film (PP film) using a No. 12 bar coater and dried at 120°C for 2 minutes to obtain a conductive film.
The film formation test result of the conductive film was B.

(Example 2)
A conductive polymer-containing liquid was prepared in the same manner as in Example 1, except that 1.5 g of trimethoxyvinylsilane was dissolved in 30 g of methanol, and this was applied to a PP film in the same manner as in Example 1. After drying for a few minutes, an attempt was made to prepare a conductive film. In the same manner as in Example 1, the above conductive polymer-containing liquid was applied to a PP film and dried at 120° C. for 2 minutes to obtain a conductive film.
The film formation test result of the conductive film was A.

(Example 3)
1.5 g of trimethoxyvinylsilane and 1 g of tetraethoxysilane were dissolved in 30 g of methanol, 15 g of ion-exchanged water was added, and the mixture was stirred at room temperature for 10 minutes. Thereafter, 50 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was added and stirred at room temperature for 30 minutes to obtain a conductive polymer-containing liquid.
In the same manner as in Example 1, the above conductive polymer-containing liquid was applied to a PP film and dried at 120° C. for 2 minutes to obtain a conductive film.
The film formation test result of the conductive film was A.

(Example 4)
1.5 g of trimethoxyvinylsilane and 1 g of tetraethoxysilane were dissolved in a mixed solvent of 5 g of ethanol and 25 g of methanol, 15 g of ion-exchanged water was added, and the mixture was stirred at room temperature for 10 minutes. Thereafter, 50 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 was added and stirred at room temperature for 30 minutes to obtain a conductive polymer-containing liquid.
In the same manner as in Example 1, the above conductive polymer-containing liquid was applied to a PP film and dried at 120° C. for 2 minutes to obtain a conductive film.
The film formation test result of the conductive film was A.

(Example 5)
1.5 g of trimethoxyvinylsilane and 1 g of tetraethoxysilane were dissolved in 30 g of methanol, 15 g of ion-exchanged water was added, and the mixture was stirred at room temperature for 10 minutes. Thereafter, 50 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 and 2 g of water-dispersed polyester resin (manufactured by Gooh Kagaku Kogyo Co., Ltd., Plus Coat RZ-105 (solid content concentration 25%)) were added and stirred at room temperature for 30 minutes. In this way, a conductive polymer-containing liquid was obtained.
In the same manner as in Example 1, the above conductive polymer-containing liquid was applied to a PP film and dried at 120° C. for 2 minutes to obtain a conductive film.
The film formation test result of the conductive film was A.

(Example 6)
A conductive film was obtained in the same manner as in Example 1, except that the PP film was changed to a polyethylene terephthalate film (Toray Industries, Inc., Lumirror T60).
The film formation test result of the conductive film was B.

(Example 7)
A conductive film was obtained in the same manner as in Example 2, except that the PP film was changed to a polyethylene terephthalate film (Toray Industries, Ltd., Lumirror T60).
The film formation test result of the conductive film was A.

(Example 8)
A conductive film was obtained in the same manner as in Example 3, except that the PP film was changed to a polyethylene terephthalate film (Toray Industries, Inc., Lumirror T60).
The film formation test result of the conductive film was A.

(Example 9)
A conductive film was obtained in the same manner as in Example 4, except that the PP film was changed to a polyethylene terephthalate film (Toray Industries, Inc., Lumirror T60).
The film formation test result of the conductive film was A.

(Example 10)
A conductive film was obtained in the same manner as in Example 5, except that the PP film was changed to a polyethylene terephthalate film (Toray Industries, Inc., Lumirror T60).
The film formation test result of the conductive film was A.

(Comparative example 1)
A conductive polymer-containing liquid was prepared in the same manner as in Example 1, except that trimethoxyvinylsilane was not added, and this was applied to a PP film in the same manner as in Example 1. It was dried at 120°C for 2 minutes to form a conductive film. I tried to make it. However, because the conductive polymer-containing liquid had poor wettability with respect to the PP film, it was not possible to form a uniform conductive film. In other words, the film formation test result of the conductive film was C.

(Comparative example 2)
An attempt was made to prepare a conductive polymer-containing liquid in the same manner as in Example 1, except that 1.5 g of trimethoxyvinylsilane was dissolved in 20 g of methanol. However, since trimethoxyvinylsilane was precipitated in the conductive polymer-containing liquid to the extent that it could be visually confirmed, coating on the film was not performed. In other words, the film formation test result of the conductive film was D.

(Comparative example 3)
A conductive polymer-containing liquid was prepared in the same manner as in Example 1, except that 0.5 g of trimethoxyvinylsilane was dissolved in 30 g of methanol, and this was applied to a PP film in the same manner as in Example 1. After drying for a few minutes, an attempt was made to prepare a conductive film. However, because the conductive polymer-containing liquid had poor wettability with respect to the PP film, it was not possible to form a uniform conductive film. In other words, the film formation test result of the conductive film was C.

(Comparative example 4)
An attempt was made to prepare a conductive polymer-containing liquid in the same manner as in Example 2, except that 1.5 g of trimethoxyvinylsilane and 1 g of tetraethoxysilane were added to 20 g of methanol. However, trimethoxyvinylsilane and tetraethoxysilane were precipitated in the conductive polymer-containing liquid to the extent that they could be visually confirmed, so coating on the film was not performed. In other words, the film formation test result of the conductive film was D.

(Comparative example 5)
A conductive polymer-containing liquid was prepared in the same manner as in Example 2, except that 0.4 g of trimethoxyvinylsilane and 0.1 g of tetraethoxysilane were dissolved in 30 g of methanol, and this was applied to a PP film in the same manner as in Example 1. It was coated and dried at 120° C. for 2 minutes in an attempt to produce a conductive film. However, because the conductive polymer-containing liquid had poor wettability with respect to the PP film, it was not possible to form a uniform conductive film. In other words, the film formation test result of the conductive film was C.

(Comparative example 6)
An attempt was made to prepare a conductive polymer-containing liquid in the same manner as in Example 3, except that 1.5 g of trimethoxyvinylsilane and 1 g of tetraethoxysilane were added to 5 g of ethanol and 15 g of methanol. However, trimethoxyvinylsilane and tetraethoxysilane were precipitated in the dispersion liquid to the extent that they could be visually confirmed, so coating on the film was not performed. In other words, the film formation test result of the conductive film was D.

(Comparative example 7)
A conductive film was obtained in the same manner as in Comparative Example 1, except that the PP film was changed to a polyethylene terephthalate film (Toray Industries, Inc., Lumirror T60).
The film formation test result of the conductive film was B.

(Comparative example 8)
A conductive film was obtained in the same manner as in Comparative Example 3, except that the PP film was changed to a polyethylene terephthalate film (Toray Industries, Inc., Lumirror T60).
The film formation test result of the conductive film was B.

(Comparative example 9)
A conductive film was obtained in the same manner as in Comparative Example 5, except that the PP film was changed to a polyethylene terephthalate film (Toray Industries, Inc., Lumirror T60).
The film formation test result of the conductive film was B.

<Evaluation of conductivity>
Table 1 shows the results of measuring the surface resistance value of the conductive film for each example. During the measurement, a resistivity meter (Hiresta, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used, and the applied voltage was 10V. In addition, "Ω/□" in the table means ohm per square.
The smaller the surface resistance value (unit: Ω/□), the higher the conductivity.

<Evaluation of adhesion>
The adhesion of the formed conductive film to each film was determined by measuring the squares that did not peel off against a total of 100 squares of 1 mm square according to the grid tape peeling test in JIS K 5600:1999. Evaluated by. The results are shown in Table 1.
The results in Table 1 indicate that the larger the number of molecules (the number of squares that were not peeled off), the greater the adhesion of the conductive film to each film.

From the results in Table 1, it is clear that by using the conductive polymer-containing liquids of Examples 1 to 10 according to the present invention, a more uniform and even conductive film can be formed on the film base material than in the comparative example. . In Examples 2 to 5 and Examples 7 to 10, by containing more silicon-containing organic compounds than in Examples 1 and 6, the dispersibility of the conductive composite was improved in the presence of an organic solvent and water. As a result, a good conductive film could be formed.
On the other hand, when using the conductive polymer-containing liquids of Comparative Example 1, which does not contain a silicon-containing organic compound, and Comparative Examples 3 and 5, which have an insufficient content of a silicon-containing organic compound, there is non-uniformity and severe unevenness. A conductive film was formed. This result shows that even if an organic solvent is contained, if the silicon-containing organic compound is not contained or its concentration is low, the dispersibility of the hydrophilic conductive composite is reduced.
Further, in the conductive polymer-containing liquids of Comparative Examples 2 and 4, which had a low concentration of organic solvent, the silicon-containing organic compound precipitated and could not be applied to the film base material. This result shows that the organic solvent not only improves the wettability to the film base material but also improves the solubility of the silicon-containing organic compound.
In Comparative Examples 7 to 9, it was possible to form a conductive film on the PET film that allowed the surface resistance value to be measured, but the adhesion of the conductive film to the PET film was extremely low, making it impractical for practical use. I know it's not suitable.
Note that Examples 1 to 4 and Examples 6 to 9 are comparative examples.

Claims (10)

A conductive polymer-containing liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, water, an organic solvent, a silicon-containing organic compound with a molecular weight of 1000 or less, and a water-dispersible polyester resin. can be,
The content of the organic solvent with respect to the total mass of the conductive polymer-containing liquid is 30% by mass or more and 90% by mass or less,
The content of the silicon-containing organic compound relative to 100 parts by mass of the conductive composite is 100 parts by mass or more and 10,000 parts by mass or less,
The content ratio of the water-dispersible polyester resin is 0.5 g or more and 120 g or less with respect to 0.6 g of the conductive composite,
A conductive polymer-containing liquid, wherein the silicon-containing organic compound includes trimethoxyvinylsilane . The conductive polymer-containing liquid according to claim 1, wherein the organic solvent contains alcohol. The conductive polymer-containing liquid according to claim 1 or 2, wherein the organic solvent contains at least one of methanol and ethanol. The conductive polymer-containing liquid according to any one of claims 1 to 3 , wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). The conductive polymer-containing liquid according to any one of claims 1 to 4 , wherein the polyanion is polystyrene sulfonic acid. an organic silane solution in which a silicon-containing organic compound is dissolved in an organic solvent;
A method for producing a conductive polymer-containing liquid by mixing a dispersion of a conductive composite containing a π-conjugated conductive polymer and a polyanion in water and a water-dispersible polyester resin. hand,
During the mixing, the content of the organic solvent with respect to the total mass of the conductive polymer-containing liquid is 30% by mass or more and 90% by mass or less, and
The content of the silicon-containing organic compound with respect to 100 parts by mass of the conductive composite is 100 parts by mass or more and 10,000 parts by mass or less, and
A method for producing a conductive polymer-containing liquid, wherein the content ratio of the water-dispersible polyester resin is 0.5 g or more and 120 g or less with respect to 0.6 g of the conductive composite. The organic solvent contains at least one of methanol and ethanol,
the silicon-containing organic compound contains an alkoxysilane,
The method for producing a conductive polymer-containing liquid according to claim 6 , wherein the conductive composite contains poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid. Coating the conductive polymer-containing liquid according to any one of claims 1 to 5 on at least one surface of a film base material, and drying the coating film formed on the film base material. , a method for producing a conductive film. The method for producing a conductive film according to claim 8 , wherein the film base material is a film made of polyolefin resin. The method for manufacturing a conductive film according to claim 9 , wherein the polyolefin resin includes a polypropylene resin.