JP7002224B2 - Method for manufacturing conductive polymer dispersion - Google Patents

Description

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

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 substrate to which the conductive layer is applied is made of a hydrophobic plastic film. Therefore, the conductive polymer aqueous dispersion, which is a water-based paint, tends to have low adhesion to the film substrate. Further, since the conductive polymer aqueous dispersion has a long drying time, the productivity of forming the conductive layer tends to be low.
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 water dispersion liquid 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. It is known that it is obtained by adding an organic solvent and an amine compound to (Patent Document 1).
However, the conductive layer formed from the conductive polymer organic solvent dispersion liquid containing the amine compound has problems such as lower conductivity and change in color tone than the conductive layer formed from the conductive polymer water dispersion liquid. May occur. Further, when the addition-curable silicone is blended in the conductive polymer organic solvent dispersion in order to develop the releasability in the conductive layer, the addition-curable silicone may cause curing inhibition due to the presence of the amine compound. Therefore, the conductive polymer organic solvent dispersion using the amine compound could not exhibit sufficient releasability in the conductive layer.

As a countermeasure to the above problem, a cyclic ether compound having at least one of an oxylan group and an oxetane group is 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 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, even in the method described in Patent Document 2, the dispersibility of the conductive composite with respect to the organic solvent may be insufficient, and in particular, a low-polarity organic solvent such as a hydrocarbon-based organic solvent is used as the organic solvent. In some cases, the dispersibility of the conductive composite may be low. Further, in the conductive layer formed from the conductive polymer organic solvent dispersion liquid described in Patent Document 2, the adhesiveness and conductivity with the film substrate may be lowered.
Therefore, in the present invention, although the organic solvent is used as the dispersion medium, the conductive layer having high dispersibility of the conductive composite and sufficiently high adhesion to the film substrate and conductivity can be easily formed. It is an object of the present invention to provide a conductive polymer dispersion liquid and a method for producing the same. Another object of the present invention is to provide a method for producing a conductive film capable of easily forming a conductive layer having high adhesion and conductivity to a film substrate.

The present invention includes the following aspects.
[1] A conductive composite containing a π-conjugated conductive polymer and a polyanion and an organic solvent are contained, and the polyanion is a reaction between a part of the anion group and the first epoxy group-containing compound together with the anion group. A conductive polymer dispersion further having a substituent (B) formed by reacting the substituent (A) formed by the above with a compound containing a second epoxy group.
[2] The conductive polymer dispersion liquid according to [1], wherein the organic solvent contains a hydrocarbon solvent.
[3] The conductive polymer dispersion liquid according to [2], wherein the content of the hydrocarbon solvent in the organic solvent is 50% by mass or more.
[4] The conductive polymer dispersion liquid according to [2] or [3], wherein the hydrocarbon solvent is at least one of heptane and toluene.
[5] The conductive polymer dispersion liquid according to any one of [1] to [4], wherein the organic solvent contains methyl ethyl ketone.
[6] The conductive polymer dispersion liquid according to any one of [1] to [5], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[7] The conductive polymer dispersion liquid according to any one of [1] to [6], wherein the polyanion is polystyrene sulfonic acid.
[8] The conductive polymer dispersion liquid according to any one of [1] to [7], which further contains a binder component.
[9] The conductive polymer dispersion liquid according to [8], wherein the binder component is a silicone compound.
[10] The conductive polymer dispersion liquid according to [9], wherein the silicone compound is an addition-curable silicone compound.

[11] A conductive composite containing a π-conjugated conductive polymer and a polyanion is precipitated by adding a first epoxy group-containing compound to an aqueous dispersion contained in an aqueous dispersion medium to precipitate the conductive composite. A precipitation recovery step of recovering the precipitate after obtaining the product, and addition of a second epoxy group-containing compound to obtain a first preparation liquid by adding a first organic solvent and a second epoxy group-containing compound to the recovered precipitate. A method for producing a conductive polymer dispersion liquid, which comprises a step.
[12] Further, there is a cleaning step of cleaning the precipitate with a cleaning organic solvent containing an organic solvent having no hydroxy group between the precipitation recovery step and the second epoxy group-containing compound addition step. 11] The method for producing a conductive polymer dispersion.
[13] The method for producing a conductive polymer dispersion liquid according to [11] or [12], wherein the first organic solvent is methyl ethyl ketone.
[14] A drying step of drying an aqueous dispersion in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium to obtain a dried product of the conductive composite.
Highly conductive, comprising a first preparation liquid preparation step of adding a first epoxy group-containing compound and a first organic solvent to the dried product, and further adding a second epoxy group-containing compound to obtain a first preparation liquid. A method for producing a molecular dispersion.
[15] The method for producing a conductive polymer dispersion liquid according to any one of [11] to [14], further comprising a binder component addition step of adding a binder component to the first preparation liquid.
[16] The high conductivity according to any one of [11] to [15], further comprising a second organic solvent addition step of adding a second organic solvent to the first preparation liquid to obtain a second preparation liquid. A method for producing a molecular dispersion.
[17] The method for producing a conductive polymer dispersion liquid according to [16], wherein the second organic solvent is a hydrocarbon solvent.
[18] The method for producing a conductive polymer dispersion liquid according to [16] or [17], further comprising a binder component addition step of adding a binder component to the second preparation liquid.
[19] A coating step of applying the conductive polymer dispersion liquid according to any one of [1] to [10] onto at least one surface of the film substrate, and the coated conductive polymer dispersion. A method for producing a conductive film, which comprises a drying step of drying the liquid.

Although the conductive polymer dispersion liquid of the present invention uses an organic solvent as a dispersion medium, the conductive layer has high dispersibility of the conductive composite, and has sufficiently high adhesion and conductivity to the film substrate. Can be easily formed.
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.
According to the method for producing a conductive film of the present invention, a conductive layer having high adhesion and conductivity to a film substrate can be easily formed.

<Conductive polymer dispersion liquid>
The conductive polymer dispersion liquid of one aspect of the present invention contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, and an organic solvent.

(Pi-conjugated conductive polymer)
The π-conjugated conductive polymer is not particularly limited as long as it is an organic polymer whose main chain is composed of a π-conjugated system, as long as it has the effect of the present invention. Conductive polymer, polyacetylene-based conductive polymer, polyphenylene-based conductive polymer, polyphenylene vinylene-based conductive polymer, polyaniline-based conductive polymer, polyacene-based conductive polymer, polythiophene vinylene-based conductive polymer, and Examples thereof include these copolymers. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-hexylthiophene). , Poly (3-heptylthiophene), Poly (3-octylthiophene), Poly (3-decylthiophene), Poly (3-dodecylthiophene), Poly (3-octadecylthiophene), Poly (3-bromothiophene), Poly (3-Chlorothiophene), Poly (3-iodothiophene), Poly (3-cyanothiophene), Poly (3-phenylthiophene), Poly (3,4-dimethylthiophene), Poly (3,4-dibutylthiophene) , Poly (3-hydroxythiophene), Poly (3-methoxythiophene), Poly (3-ethoxythiophene), Poly (3-butoxythiophene), Poly (3-hexyloxythiophene), Poly (3-Heptyloxythiophene) , Poly (3-octyloxythiophene), Poly (3-decyloxythiophene), Poly (3-dodecyloxythiophene), Poly (3-octadecyloxythiophene), Poly (3,4-dihydroxythiophene), Poly (3) , 4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene) , Poly (3,4-diheptyloxythiophene), Poly (3,4-dioctyloxythiophene), Poly (3,4-didecyloxythiophene), Poly (3,4-didodecyloxythiophene), Poly (3,4-didodecyloxythiophene) 3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3- Methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxyphene) Butylthiophene).
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 above-mentioned π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity, transparency and heat resistance.
The π-conjugated conductive polymer contained in the conductive composite may be of one type or two or more types.

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

Polyanions form a conductive complex by doping the π-conjugated conductive polymer. However, in the polyanion, all the anion groups do not dope the π-conjugated conductive polymer and have a surplus anion group that does not participate in the doping. Since this excess anionic group is a hydrophilic group, the conductive composite has high water dispersibility and low organic solvent dispersibility before being reacted with the epoxy group-containing compound as described later.

The polyanion used in this embodiment has an anionic group and a substituent (A) formed by the reaction of a part of the anion group with the first epoxy group-containing compound, which is different from the first epoxy group-containing compound. It has a substituent (B) formed by reacting an epoxy group-containing compound.
Although detailed analysis of the conductive complex is not always easy, the substituent (A) is a group represented by the following chemical formula (A), and the substituent (B) is a group represented by the following chemical formula (B). It is presumed. That is, in this embodiment, it is presumed that the protons in some of the anion groups of the polyanion are replaced with the substituent (B).

R ¹ and R ² in the chemical formula (A) and the chemical formula (B) are arbitrary substituents, respectively. The hydroxy group in the chemical formula (A) is a group formed by opening the ring of the epoxy group of the epoxy group-containing compound, and R ¹ is a substituent derived from the first epoxy group-containing compound described later. R ² in the chemical formula (B) is a substituent derived from the second epoxy group-containing compound described later.
The substituent (A) and the substituent (B) are each bonded to the oxygen atom of the anion group.

The first epoxy group-containing compound and the second epoxy group-containing compound are compounds having one or more epoxy groups in one molecule. From the viewpoint of preventing aggregation or gelation, the epoxy group-containing compound is preferably a compound having one epoxy group in one molecule.
As the first epoxy group-containing compound and the second epoxy group-containing compound, one type may be used alone, or two or more types may be used in combination.
The first epoxy group-containing compound and the second epoxy group-containing compound may be the same compound or may be different compounds.

Examples of the monofunctional epoxy group-containing compound having one epoxy group in one molecule include propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, and 1, 2-Epoxide heptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monooxide, 1,2-epoxytetradecane, glycidylmethyl ether, 1,2-epoxide Octadecan, 1,2-epoxide hexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeikosan, 2- (chloromethyl) -1,2-epoxide propane, glycidol, epichlorohydrin, epi Bromohydrin, butyl glycidyl ether, 1,2-epoxide hexane, 1,2-epoxide-9-decane, 2- (chloromethyl) -1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2-epoxide -1H, 1H, 2H, 2H, 3H, 3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidylmethacrylate, 1,2-epoxide cyclododecane, 1 -Methyl-1,2-epoxide cyclohexane, 1,2-epoxide cyclopentadecane, 1,2-epoxide cyclopentane, 1,2-epoxide cyclohexane, 1,2-epoxide-1H, 1H, 2H, 2H, 3H, 3H -Heptadecafluorobutane, 3,4-epoxide tetrahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzyl Glysidyl ether, diethoxy (3-glycidyloxypropyl) methylsilane, 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxide propane, 1,1,1,3,5,5,5-heptamethyl-3 -(3-Glysidyloxypropyl) trisiloxane, 9,10-epoxide-1,5-cyclododecadien, 4-tert-butyl glycidyl benzoate, 2,2-bis (4-glycidyloxyphenyl) propane, 2- tert-butyl-2- [2- (4-chlorophenyl)] ethyl oki Silane, styrene oxide, glycidyltrityl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylprepylene oxide, cholesterol-5α, 6α-epoxide, stillbenoxide, glycidyl p-toluenesulfonate, 3 -Ethyl methyl-3-phenylglycidate, N-propyl-N- (2,3-epoxypropyl) perfluoro-n-octylsulfonic acid, (2S, 3S) -1,2-epoxy-3- (tert-) Butoxycarbonylamino) -4-phenylbutane, 3-nitrobenzene sulfonic acid (R) -glycidyl, 3-nitrobenzene sulfonic acid-glycidyl, parthenolide, N-glycidyl phthalimide, endolin, dyrdoline, 4-glycidyl oxycarbazole, 7,7- Examples thereof include dimethyloctanoic acid [oxylanylmethyl], 1,2-epoxy-4-vinylcyclohexane, C12 and C13 mixed higher alcohol glycidyl ether, and one-ended epoxy-modified silicone.

Examples of the polyfunctional epoxy group-containing compound having two or more epoxy groups in one molecule include 1,6-hexanediol diglycidyl ether, 1,7-octadiendiepoxide, neopentyl glycol diglycidyl ether, and 4-. Butanediol diglycidyl ether, 1,2: 3,4-diepoxide butane, 1,2-cyclohexanedicarboxylate diglycidyl, triglycidyl isocyanurate neopentyl glycol diglycidyl ether, 1,2: 3,4-diepoxide butane, Polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether , Trimethylol propane triglycidyl ether, trimethylol propane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol system Examples thereof include polyglycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate, double-ended epoxy-modified silicone, and side-chain epoxy-modified silicone.

The first epoxy group-containing compound and the second epoxy group-containing compound preferably have a molecular weight of 50 or more and 2,000 or less because they have high solubility in an organic solvent.
When an organic epoxy compound containing no silicon atom is used as the first epoxy group-containing compound and the second epoxy group-containing compound, the first epoxy group is contained in that the solubility in a low-polarity organic solvent is higher. The carbon number of each of the compound and the second epoxy group-containing compound is preferably 10 or more. On the other hand, practically, the epoxy group-containing compound preferably has 25 or less carbon atoms.
When an epoxy-modified silicone containing a silicon atom is used as at least one of the first epoxy group-containing compound and the second epoxy group-containing compound, the first epoxy is more soluble in a low-polarity organic solvent. The total number of carbon atoms and the number of silicon of each of the group-containing compound and the second epoxy group-containing compound is preferably 10 or more. On the other hand, practically, the epoxy group-containing compound preferably has 50 or less carbon atoms.

When an organic epoxy compound containing no silicon atom is used as the first epoxy group-containing compound and the second epoxy group-containing compound, the total carbon number of the substituent (B) is preferably 15 or more, preferably 20 or more. It is more preferable to have it, and it is more preferable to have 22 or more. When the total carbon number of the substituent (B) is at least the above lower limit value, the dispersibility of the conductive complex with respect to the organic solvent can be further improved. The total carbon number of the substituent (B) is preferably 50 or less from the viewpoint that the epoxy group-containing compound to be used is easily available.
When an epoxy-modified silicone containing a silicon atom is used as at least one of the first epoxy group-containing compound and the second epoxy group-containing compound, the total number of carbon atoms and the number of silicon of the substituent (B) shall be 15 or more. Is preferable, 20 or more is more preferable, and 22 or more is more preferable. When the total number of carbon atoms and the number of silicon of the substituent (B) is at least the above lower limit value, the dispersibility of the conductive complex with respect to the organic solvent can be further improved. The total number of carbon atoms and the number of silicon of the substituent (B) is preferably 100 or less from the viewpoint that the epoxy group-containing compound to be used is easily available.

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, the amount of the anion group not involved in the doping is appropriately suppressed, and the anion group can be easily converted to hydrophobic when the first epoxy group-containing compound is reacted. ..

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

(Organic solvent)
Examples of the organic solvent used in this embodiment include a hydrocarbon solvent, a ketone solvent, an alcohol solvent, an ester solvent, a nitrogen atom-containing compound solvent and the like. One type of organic solvent may be used alone, or two or more types may be used in combination.
Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent. Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane and the like. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene 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 alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, allyl alcohol and the like.
Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate and the like.
Examples of the nitrogen atom-containing compound solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.

Among the above organic solvents, hydrocarbon solvents are preferable in that the wettability of the conductive polymer dispersion with respect to the plastic film substrate is high and the low-polarity binder component can be easily solubilized. Further, among the hydrocarbon solvents, at least one of heptane and toluene is preferable, and heptane is more preferable, because it is versatile. When a silicone compound is used as the binder component, at least one of heptane and toluene is preferable because of its excellent silicone solubility.
When the organic solvent used in this embodiment contains a hydrocarbon solvent, the content thereof is preferably 50% by mass or more, preferably 60% by mass when the total amount of the organic solvent is 100% by mass. The above is more preferable. All of the organic solvents may be hydrocarbon solvents. When a solvent other than the hydrocarbon solvent is contained, the content of the hydrocarbon solvent is preferably 90% by mass or less, and preferably 80% by mass or less.
In the organic solvent used in this embodiment, it is preferable to contain methyl ethyl ketone because the dispersibility of the conductive complex becomes higher.
When heptane is used as the organic solvent, a solvent other than heptane may be used in combination. As the organic solvent used in combination with heptane, methyl ethyl ketone, toluene, ethyl acetate, butyl acetate, xylene, methyl isobutyl ketone and cyclohexane are preferable.
When the organic solvent contains heptane and a solvent other than heptane, the content of heptane is preferably 10% by mass or more and 90% by mass or less, preferably 30% by mass or more and 60% by mass or less when the total amount of the organic solvent is 100% by mass. It is more preferably mass% or less.

(Binder component)
The conductive polymer dispersion liquid of this embodiment may contain a binder component in order to improve the film-forming property of the obtained conductive layer.
Since the conductive polymer dispersion liquid of this embodiment uses an organic solvent as the dispersion medium, a low-polarity silicone compound can be preferably used as the binder component.

Examples of the silicone compound include curable silicone. When the binder component is a curable silicone, the conductive layer can be releasable by curing the curable silicone.
The curable silicone may be either an addition curable silicone or a condensation curable silicone. In this embodiment, even if addition-curable silicone is used, curing inhibition is unlikely to occur, which is preferable.
Examples of the addition-curable silicone include linear polymers having a siloxane bond, which have a polydimethylsiloxane having a vinyl group at both ends of the straight chain and a hydrogensilane. Such an addition-curable silicone forms a three-dimensional crosslinked structure by an addition reaction and is cured. A platinum-based curing catalyst may be used to accelerate the curing.
Specific examples of the addition-curable silicone include KS-3703T, KS-847T, KM-3951, X-52-151, X-52-6068, X-52-6069 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. ..
As the addition-curable silicone, those dissolved or dispersed in an organic solvent are preferably used.

As the binder component, a thermoplastic resin (for example, polyester, etc.), a thermosetting compound (for example, a polyfunctional epoxy compound, etc.), and an active energy ray-curable compound (for example, an acrylic compound, etc.) other than the silicone compound are used. May be good. When a thermosetting compound is used, it is preferable to further contain a thermopolymerization initiator, and when an active energy ray-curable compound is used, it is preferable to further contain a photopolymerization initiator.

The content ratio of the binder component is preferably 1000 parts by mass or more and 100,000 parts by mass or less, and more preferably 3000 parts by mass or more and 50,000 parts by mass or less with respect to 100 parts by mass of the conductive composite. When the content ratio of the binder component is not less than the lower limit value, the strength and hardness of the obtained conductive layer can be sufficiently improved, and when it is not more than the upper limit value, sufficient conductivity can be ensured.

(Highly conductive agent)
The conductive polymer dispersion liquid may contain a highly conductive agent in order to further improve the conductivity.
Here, the above-mentioned π-conjugated conductive polymer, polyanion, and binder component are not classified as high conductivity agents. However, the epoxy group-containing compound and the organic solvent may correspond to the highly conductive agent described here.
The high conductivity agent is a saccharide, a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxy groups, a compound having one or more hydroxy groups and one or more carboxy groups, a compound having an amide group, and the like. It is preferably at least one compound selected from the group consisting of a compound having an imide group, a lactam compound, and a compound having a glycidyl group.
The highly conductive agent contained in the conductive polymer dispersion may be one kind or two or more kinds.
The content ratio of the highly conductive agent is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, with respect to 100 parts by mass of the conductive composite. It is more preferably more than parts by mass and not more than 2500 parts by mass.
When the content ratio of the high conductive agent is not less than the lower limit value, the effect of improving the conductivity by adding the high conductivity agent is sufficiently exhibited, and when it is not more than the upper limit value, the concentration of the π-conjugated conductive polymer is lowered. It is possible to prevent a decrease in conductivity due to the above.

(Other additives)
The conductive polymer dispersion may contain other known additives.
The additive is not particularly limited as long as the effect of the present invention can be obtained, and for example, a surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like can be used. However, the additive is composed of a compound other than the above-mentioned π-conjugated conductive polymer, polyanion, epoxy group-containing compound, binder component and high conductivity agent.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferable from the viewpoint of storage stability. Further, a polymer-based surfactant such as polyvinylpyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving the metal salt in water.
Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the coupling agent include a silane coupling agent having a vinyl group or an amino group.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, etc. Can be mentioned.
When the conductive polymer dispersion liquid contains the above additive, the content ratio thereof is appropriately determined depending on the type of the additive. For example, 0. The range may be 001 parts by mass or more and 5 parts by mass or less.

(Manufacturing method of conductive polymer dispersion liquid)
[First manufacturing method]
The first method for producing the conductive polymer dispersion liquid of this embodiment for obtaining the conductive polymer dispersion liquid includes a precipitation recovery step and a second epoxy group-containing compound addition step.
Further, the first method for producing the conductive polymer dispersion liquid of this embodiment may further include a cleaning step between the precipitation recovery step and the second epoxy group-containing compound addition step. Further, after the second epoxy group-containing compound addition step, at least one of the second organic solvent addition step and the binder component addition step may be further provided.

[Precipitation recovery process]
The precipitation recovery step is a step of adding a first epoxy group-containing compound to a conductive polymer aqueous dispersion, precipitating a conductive composite to obtain a precipitate, and then recovering the precipitate by filtration.
When the first epoxy group-containing compound is added to the conductive polymer aqueous dispersion, at least a part of the epoxy groups of the first epoxy group-containing compound reacts with some anion groups of the polyanion. As a result, the substituent (A) is formed and the conductive complex becomes hydrophobic, which makes it difficult to stably disperse in the aqueous dispersion, and precipitates to form a precipitate.
The amount of the first epoxy group-containing compound added is preferably 0.1 or more and 1000 or less, and more preferably 1.0 or more and 100 or less in terms of mass ratio with respect to the polyanion. When the amount of the first epoxy group-containing compound added is not less than the lower limit, the hydrophobicity of the conductive complex becomes sufficiently high, and when it is not more than the upper limit, the conductivity of the unreacted first epoxy group-containing compound is increased. It is possible to prevent deterioration of sex.
An organic solvent may be added before, simultaneously with, or after the addition of the epoxy group-containing compound to the conductive polymer aqueous dispersion. As the organic solvent, a water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include alcohol-based solvents, ketone-based solvents, and ester-based solvents. When a water-soluble organic solvent is contained, one type may be used alone, or two or more types may be used in combination.

The conductive polymer aqueous dispersion to which the first epoxy group-containing compound is added is a dispersion in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is contained in the aqueous dispersion medium. Here, the aqueous dispersion medium contains water and may contain a water-soluble organic solvent. The content of water in the aqueous dispersion medium is preferably 20% by mass or more, more preferably 50% by mass or more, and may be 100% by mass.
The conductive polymer aqueous dispersion can be obtained, for example, by chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous solution of a polyanion. Further, a commercially available conductive polymer aqueous dispersion 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 ferric 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 water content of the precipitate obtained by the precipitation recovery step is preferably as small as possible, and most preferably it does not contain any water, but from a practical point of view, the water content may be contained in the range of 10% by mass or less.
Examples of the method for reducing the amount of water include a method of washing away the precipitate with an organic solvent, a method of drying the precipitate, and the like.

[Washing process]
The cleaning step between the precipitation recovery step and the second epoxy group-containing compound addition step is a step of cleaning the precipitate with a cleaning organic solvent. By this washing step, residual water, an unreacted first epoxy group-containing compound, and a hydrolyzate of the first epoxy group-containing compound are removed.
The cleaning organic solvent contains an organic solvent having no hydroxy group. The organic solvent having a hydroxy group may react with the first epoxy group-containing compound to form a useless ester. Further, if the organic solvent having a hydroxy group remains in the precipitate, it may react with the second epoxy group-containing compound used in the next step. Therefore, the cleaning organic solvent used in the cleaning step contains an organic solvent that does not have a hydroxy group and has low reactivity with an epoxy group-containing compound. The organic solvent for cleaning may contain an organic solvent having a hydroxy group. Organic solvents with hydroxy groups are suitable for removing water. When an organic solvent having a hydroxy group is used as the organic solvent for cleaning, the residue may react with the compound containing the second epoxy group. Therefore, after cleaning the precipitate with the organic solvent having a hydroxy group. Is preferably washed with an organic solvent having no hydroxy group.
Further, as the cleaning organic solvent, a solvent that can be washed without dissolving the precipitate is preferably used. Therefore, as the cleaning organic solvent, a ketone solvent, an ester solvent, and a nitrogen atom-containing compound solvent are preferable. One type of organic solvent for cleaning may be used alone, or two or more types may be used in combination.
The cleaning method is not particularly limited. For example, the organic solvent for cleaning may be poured over the precipitate to clean the precipitate, or the precipitate may be stirred in the organic solvent for cleaning to clean the precipitate. You may.

[Second epoxy group-containing compound addition step]
The second epoxy group-containing compound addition step is a step of adding a first organic solvent and a second epoxy group-containing compound to the precipitate to obtain a first preparation liquid.
The first organic solvent and the second epoxy group-containing compound may be added to the precipitate at the same time, or the second epoxy group-containing compound may be added after the first organic solvent is added.
By adding the second epoxy group-containing compound to the precipitate, the second epoxy group-containing compound can be reacted with the substituent (A) formed by the reaction between the anionic group and the first epoxy group-containing compound. When the second epoxy group-containing compound is reacted with the substituent (A), the substituent (B) is formed, and the hydrophobicity of the conductive complex becomes higher.
Further, in this step, an organic solvent is used as the dispersion medium, and water is absent or scarce. Therefore, since the epoxy group can be maintained without adding water to the epoxy group of the second epoxy group-containing compound, its reactivity is not easily impaired, and it is presumed that the substituent (B) can be easily formed.
The amount of the second epoxy group-containing compound added is preferably 0.1 or more and 100 or less, and more preferably 1 or more and 20 or less in terms of mass ratio with respect to the polyanion. When the amount of the second epoxy group-containing compound added is not less than the lower limit, the hydrophobicity of the conductive complex becomes sufficiently high, and when it is not more than the upper limit, the conductivity of the unreacted second epoxy group-containing compound is increased. It is possible to prevent deterioration of sex.
In the step of adding the second epoxy group-containing compound, it is preferable to heat the compound in order to promote the reactivity of the second epoxy group-containing compound. The heating temperature is preferably 40 ° C. or higher and 100 ° C. or lower.

As the first organic solvent, the above-mentioned organic solvent can be used, but when the second organic solvent addition step described later is carried out, it is preferable to use methyl ethyl ketone as the first organic solvent. When methyl ethyl ketone is used as the first organic solvent, the dispersibility of the precipitate can be enhanced in the first preparation liquid, and the dispersibility of the conductive composite in the conductive polymer dispersion obtained by adding the second organic solvent. Can be further improved.

After adding the first organic solvent and the second epoxy group-containing compound to the precipitate, the first preparation liquid may be stirred and subjected to the dispersion treatment. In particular, when the present production method does not include the second organic solvent addition step, it is preferable to perform a dispersion treatment on the first preparation liquid. The stirring method is not particularly limited, and stirring may be performed with a weak shearing force such as a stirrer, or may be stirred using a disperser (homogenizer or the like) having a high shearing force.

When the first method for producing the conductive polymer dispersion liquid of this embodiment does not include the second organic solvent addition step, the first preparation liquid obtained in the second epoxy group-containing compound addition step has high conductivity. It becomes a molecular dispersion liquid.

[Second organic solvent addition step]
The second organic solvent addition step is a step of adding a second organic solvent different from the first organic solvent to the first preparation liquid to obtain a second preparation liquid. After adding the second organic solvent to the first preparation liquid, it is preferable to stir the second preparation liquid for dispersion treatment. The stirring method is not particularly limited, and stirring may be performed with a weak shearing force such as a stirrer, or may be stirred using a disperser (homogenizer or the like) having a high shearing force.
When methyl ethyl ketone is used as the first organic solvent, it is preferable to use a hydrocarbon solvent which is a low polar solvent as the second organic solvent, and since it is highly versatile, at least one of heptane and toluene is used. It is more preferable to use.
When the first method for producing the conductive polymer dispersion liquid of this embodiment has a second organic solvent addition step, the second preparation liquid obtained in the second organic solvent addition step is the conductive polymer dispersion liquid. Become.

[Binder component addition process]
The binder component addition step is a step of adding the binder component to the first preparation liquid or the second preparation liquid. When the second organic solvent addition step is not provided, it is preferable to add the binder component to the first preparation liquid, and when the second organic solvent addition step is provided, the binder component is added to the second preparation liquid. Is preferable.
After adding the binder component to the first preparation liquid or the second preparation liquid, it is preferable to stir to enhance the dispersibility of the binder component.
When the binder component is an addition-curable silicone, it is preferable to add the platinum-based curing catalyst at the same time as or after the addition of the binder component.

[Addition of highly conductive agents and additives]
When a highly conductive agent, an additive, or the like is contained in the conductive polymer dispersion, one or more of the second epoxy group-containing compound addition step, the second organic solvent addition step, and the binder component addition step. In, a highly conductive agent, an additive, or the like may be added.

[Second manufacturing method]
The second method for producing the conductive polymer dispersion liquid of this embodiment for obtaining the conductive polymer dispersion liquid includes a drying step and a first preparation liquid preparation step.
Further, the second method for producing the conductive polymer dispersion liquid of this embodiment may further include a cleaning step between the drying step and the first preparation liquid preparation step. Further, after the first preparation liquid preparation step, at least one of the second organic solvent addition step and the binder component addition step may be further performed. The cleaning step, the second organic solvent addition step, and the binder component addition step in the second manufacturing method are the same as the cleaning step, the second organic solvent addition step, and the binder component addition step in the first manufacturing method.
In the present production method, when the highly conductive agent, the additive, etc. are contained in the conductive polymer dispersion, any one of the first preparation liquid preparation step, the second organic solvent addition step, and the binder component addition step. In the above steps, a highly conductive agent, an additive, or the like may be added.

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

[First preparation liquid preparation step]
The first preparation liquid preparation step is a step of adding a first epoxy group-containing compound and a first organic solvent to the dried product, and further adding a second epoxy group-containing compound to obtain a first preparation liquid.
As the first organic solvent, the above-mentioned organic solvent can be used without particular limitation. In particular, in this production method, since the dried product contains almost no water, a low-polarity solvent such as a hydrocarbon solvent can be used as the first organic solvent, and at least one of heptane and toluene can be preferably used.
The addition of the second epoxy group-containing compound is preferable after the addition of the first epoxy group-containing compound and the first organic solvent because it facilitates the reaction with the first epoxy group-containing compound.
In this step, by adding the first epoxy group-containing compound to the dried product, the anionic group of the polyanion and the first epoxy group-containing compound can be reacted to form the substituent (A). Further, after that, by adding the second epoxy group-containing compound, the substituent (A) and the second epoxy group-containing compound can be reacted to form the substituent (B). When the first epoxy group-containing compound and the second epoxy group-containing compound are added, they may be heated to promote the reaction. The heating temperature is preferably 40 ° C. or higher and 100 ° C. or lower.
In the second production method, the first preparation liquid may be used as a conductive polymer dispersion liquid, or the second preparation liquid obtained in the second organic solvent addition step may be used as a conductive polymer dispersion liquid.

(Action effect)
Since the substituent (A) formed by reacting the anionic group of the polyanion with the first epoxy group-containing compound as described in Patent Document 2 is presumed to have a hydroxy group, it is more hydrophilic than the anionic group. The sex is low, but not low enough. Therefore, the dispersibility of the conductive complex was insufficient for a low-polarity organic solvent such as heptane. In this embodiment, since the substituent (A) is reacted with the second epoxy group-containing compound to form the substituent (B), the hydrophilicity becomes lower and the lipophilicity (hydrophobicity) can be further improved. .. The reason is not clear, but when the substituent (A) is reacted with the second epoxy group-containing compound, the hydroxy group of the substituent (A) is reacted with the epoxy group of the second epoxy group-containing compound. It is presumed to form a substituent (B). Since the formed substituent (B) has a larger number of carbon atoms and a longer chain length than the substituent (A), it is presumed that the lipophilicity is improved.
Therefore, according to the conductive polymer dispersion liquid of this embodiment, the dispersibility of the conductive composite with respect to the organic solvent, particularly the dispersibility of the conductive composite with respect to a low-polarity organic solvent such as heptane can be improved. In the conductive layer formed from such a conductive polymer dispersion liquid, the dispersibility of the conductive composite is high, so that the conductivity is sufficiently improved even though an organic solvent is used as the dispersion medium. be able to. In particular, even if a low-polarity organic solvent such as heptane is used, the conductivity can be sufficiently improved.
Further, since the conductive polymer dispersion liquid of this embodiment has high lipophilicity and high wettability to the film substrate, it is possible to improve the adhesion of the conductive layer formed from the conductive polymer dispersion liquid.
Further, the conductive polymer dispersion liquid of this embodiment can easily dissolve or disperse a binder component, particularly a low-polarity organic solvent such as a silicone compound, and can improve the dispersibility of the binder component. When a silicone compound is used as a binder component in order to develop releasability in the conductive layer, the releasability is improved because the silicone dispersibility in the conductive layer formed from the conductive polymer dispersion is high. Can be made to.

<Manufacturing method of conductive film>
The method for producing a conductive film according to this embodiment is a coating film comprising a coating step of applying the above-mentioned conductive polymer dispersion liquid to at least one surface of a film base material and a coated conductive polymer dispersion liquid. It is a method having a drying step of drying (conductive layer).

(Conductive film)
The conductive film obtained by the production method of this embodiment includes a film base material and a conductive layer formed on at least one surface of the film base material. The conductive layer contains a conductive composite containing a π-conjugated conductive polymer and a polyanion. The hydrogen atom of a part of the anion group of the polyanion contained in the conductive layer is substituted with the substituent (B).
When the conductive polymer dispersion liquid contains a binder component, the conductive layer contains a binder component or a cured product obtained by curing the binder component.
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. When the average thickness of the conductive layer is not less than the lower limit value, sufficiently high conductivity can be exhibited, and when it is not more than the upper limit value, the conductive layer can be easily formed.

Examples of the film base material used in the production method of this embodiment include plastic films and paper.
Examples of the resin for the film base material constituting the plastic film include ethylene-methylmethacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, and polybutylene terephthalate. , Polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene-based elastomer, polyester-based elastomer, polyether sulfone, polyetherimide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio Examples include Nate. Among these resins for film substrates, polyethylene terephthalate and cellulose triacetate are preferable because they are inexpensive and have excellent mechanical strength.
The resin for a film base material may be amorphous or crystalline.
Further, the film substrate may be unstretched or stretched.
Further, the film substrate may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc. in order to further improve the adhesion of the conductive layer formed from the conductive polymer dispersion liquid.

The average thickness of the film substrate is preferably 10 μm or more and 500 μm or less, and more preferably 20 μm or more and 200 μm or less. When the average thickness of the film substrate is at least the lower limit value, it is difficult to break, and when it is at least the upper limit value, sufficient flexibility as a film can be ensured.
The thickness of the member in the present specification is a value obtained by measuring the thickness at any 10 points and averaging the measured values.

(Coating process)
As a method of applying the conductive polymer dispersion liquid in the coating process, for example, a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a knife coater, a fountain coater, a rod coater, and an air doctor. Apply coating methods using coaters such as coaters, knife coaters, blade coaters, cast coaters, screen coaters, spraying methods using atomizers such as air spray, airless spray, rotor dampening, dipping methods such as dips, etc. be able to.
Of the above, a bar coater may be used because it 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.
The amount of the conductive polymer dispersion liquid applied to the film substrate is not particularly limited, but the solid content is preferably in the range of 0.1 g / m ² or more and 10.0 g / m ² or less.

(Drying process)
Examples of the drying method in the drying step include heat drying and vacuum drying. As the heat drying, for example, a usual method such as hot air heating or infrared heating can be adopted. When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium used, and can be set to, for example, 50 ° C. or higher and 150 ° C. or lower. Here, the heating temperature is a set temperature of the drying device.
When the conductive polymer dispersion liquid contains an active energy ray-curable binder component, an active energy ray irradiation step of irradiating the dried conductive polymer coating film with active energy rays is performed after the drying step. You may also have more. When the active energy ray irradiation step is provided, the formation speed of the conductive layer can be increased, and the productivity of the conductive film is improved.
When the active energy ray irradiation step is provided, examples of the active energy ray used include ultraviolet rays, electron beams, and visible light. As the light source of ultraviolet rays, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used.
The illuminance in ultraviolet irradiation is preferably 100 mW / cm ² or more. If the illuminance is less than 100 mW / cm ² , the active energy ray-curable binder component may not be sufficiently cured. Further, the integrated light amount is preferably 50 mJ / cm ² or more. If the integrated light intensity is less than 50 mJ / cm ² , the cross-linking may not be sufficient. In addition, the illuminance and the integrated light amount in this specification use the UVR-T1 (industrial UV checker, receiver; UD-T36, measurement wavelength range; 300 nm or more and 390 nm or less, peak sensitivity wavelength; about 355 nm) manufactured by Topcon. It is a measured value.

(Action effect)
In the method for producing a conductive film of this embodiment, since the conductive polymer dispersion liquid of the above aspect having high oil resistance is applied to the film base material, the conductive layer formed from the conductive polymer dispersion liquid is a film base material. High adhesion to.
Further, in the conductive polymer dispersion liquid of the above aspect, since the conductive composite is highly dispersed in the organic solvent, the conductive composite is also contained in the conductive layer formed from the conductive polymer dispersion liquid. Can be contained in a high dispersion. Therefore, the conductivity of the conductive layer can be sufficiently increased.
Further, when the conductive polymer dispersion liquid contains a silicone compound, the silicone compound is highly dispersed in the conductive polymer dispersion liquid, so that the silicone in the conductive layer formed from the conductive polymer dispersion liquid is formed. The compound dispersibility can be increased. Therefore, the releasability of the conductive layer expressed by the silicone compound can be sufficiently increased.

(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 at 80 ° C. for 20 minutes, and this solution was added dropwise for 12 hours. Stirred.
1000 ml of sulfuric acid diluted to 10% by mass is added to the obtained sodium styrene sulfonate-containing solution, about 1000 ml of the polystyrene sulfonate-containing solution is removed by an ultrafiltration method, and 2000 ml of ion-exchanged water is added to the residual solution. , About 2000 ml of solution was removed by ultrafiltration. The above ultrafiltration operation was repeated 3 times. Further, about 2000 ml of ion-exchanged water was added to the obtained polystyrene sulfonic acid solution, and about 2000 ml of the solution was removed by an ultrafiltration method. This ultrafiltration operation was repeated 3 times.
Water in the obtained solution was removed under reduced pressure to obtain 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 in 2000 ml of ion-exchanged water were mixed at 20 ° C.
The mixed solution thus obtained was kept at 20 ° C., and while stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of a ferric sulfate oxidation catalyst solution were slowly added. The reaction was carried out with stirring for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solution was removed by an ultrafiltration method. This operation was repeated 3 times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the obtained solution, about 2000 ml of the solution is removed by an ultrafiltration method, and 2000 ml of ion-exchanged water is added thereto. About 2000 ml of the solution was removed by ultrafiltration. This operation was repeated 3 times.
Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed by an ultrafiltration method. This operation was repeated 5 times to obtain a 1.2% polystyrene sulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS aqueous dispersion) solution. The content of PSS with respect to the PEDOT-PSS solid content is 75% by mass.

(Manufacturing Example 3)
To 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 25 g of a higher alcohol glycidyl ether (Epolite M-1230 manufactured by Kyoeisha Chemical Co., Ltd.) mixed with 300 g of methanol and C12 and C13 is added, and the mixture is heated and stirred at 60 ° C. for 4 hours. did. As a result, a precipitate of a conductive composite formed from a π-conjugated conductive polymer, a polyanion, and an epoxy group-containing compound was obtained. The precipitate was collected by filtration and washed with 100 g of methanol and then 100 g of ethyl acetate to obtain 1.6 g of a conductive complex.

(Manufacturing Example 4)
To 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 300 g of methanol and 25 g of 1,2-epoxydecane were added, and the mixture was heated and stirred at 60 ° C. for 4 hours. As a result, a precipitate of a conductive composite formed from a π-conjugated conductive polymer, a polyanion, and an epoxy group-containing compound was obtained. The precipitate was collected by filtration and washed with 100 g of methanol and then 100 g of ethyl acetate to obtain a conductive composite of 1.5 g.

(Manufacturing Example 5)
Additive curable silicone (KS-3703T, manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration 30% by mass, toluene solution) 1.5 g, toluene 25.5 g, methyl ethyl ketone 58.5 g, and platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., 0.03 g of CAT-PL-50T) was mixed to obtain a silicone solution (solid content concentration 0.53% by mass).

(Example 1)
To 1.6 g of the conductive composite obtained in Production Example 3, 100 g of methyl ethyl ketone and 2.0 g of a higher alcohol glycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., Epolite M-1230) mixed with C12 and C13 were mixed, and the temperature was 80 ° C. for 4 hours. The reaction was carried out while refluxing using a cooling tube. Then, 200 g of heptane was added, and the mixture was stirred for 1 hour, returned to room temperature, and stirred for 16 hours. The prepared solution thus obtained was subjected to dispersion treatment using a high-pressure homogenizer to obtain a conductive polymer dispersion.
The obtained conductive polymer dispersion liquid was subjected to No. Using 12 bar coaters, the film was applied to a polyethylene terephthalate film (Toray Industries, Inc., Lumirer T60) and dried at 100 ° C. for 1 minute to form a non-release conductive layer to obtain a conductive film.
Further, 14.3 g of the silicone solution obtained in Production Example 5 was mixed with 2.95 g of the obtained conductive polymer dispersion liquid to obtain a silicone-containing conductive polymer dispersion liquid.
The obtained silicone-containing conductive polymer dispersion liquid was subjected to No. Using 14 bar coaters, it was applied to a polyethylene terephthalate film (Toray Industries, Inc., Lumirer T60) and dried at 150 ° C. for 1 minute to form a release conductive layer to obtain a conductive release film. ..

(Example 2)
C12, C13 mixed higher alcohol glycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., Epolite M-1230) was changed to one-ended epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-173BX, epoxy equivalent 2500 g / mol). A conductive film and a conductive release film were obtained in the same manner as in Example 1 except for the above.

(Example 3)
C12, C13 mixed higher alcohol glycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., Epolite M-1230) was changed to one-ended epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-173DX, epoxy equivalent 4600 g / mol). A conductive film and a conductive release film were obtained in the same manner except for the above.

(Example 4)
The conductive film and the conductive release film were obtained in the same manner as in Example 1 except that 1.6 g of the conductive composite obtained in Production Example 3 was changed to 1.5 g of the conductive composite obtained in Production Example 4. Got

(Example 5)
To 1.6 g of the conductive composite obtained in Production Example 3, 100 g of methyl ethyl ketone and 10.0 g of a higher alcohol glycidyl ether mixed with C12 and C13 (Epolite M-1230 manufactured by Kyoeisha Chemical Co., Ltd.) were mixed, and the temperature was 80 ° C. for 4 hours. The reaction was carried out while refluxing using a cooling tube. Then, 200 g of heptane was added, and the mixture was stirred for 1 hour, returned to room temperature, and stirred for 16 hours. The prepared solution thus obtained was filtered to separate the conductive complex, and 100 g of methanol and then 100 g of ethyl acetate were poured and washed to obtain 2.0 g of the conductive complex. To this 2.0 g of the conductive composite, 100 g of methyl ethyl ketone and 200 g of heptane were added and dispersed using a high-pressure homogenizer to obtain a conductive polymer solution. A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that the conductive polymer dispersion was used.

(Comparative Example 1)
To 1.6 g of the conductive composite obtained in Production Example 3, 100 g of methyl ethyl ketone and 200 g of heptane were added and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion. A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that the conductive polymer dispersion was used.

(Comparative Example 2)
To 1.5 g of the conductive composite obtained in Production Example 4, 100 g of methyl ethyl ketone and 200 g of heptane were added and dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion. A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that the conductive polymer dispersion was used.

<Evaluation>
[Measurement of surface resistance value]
For the conductive film and the conductive release film of each example, the surface resistance value of the conductive layer was measured using a resistivity meter (High Restor manufactured by Mitsubishi Chemical Analytical Corporation) under the condition of an applied voltage of 10 V. The measurement results are shown in Table 1. In the table, "OVER" means that the measurable upper limit of the surface resistance value (1.0 × 10 ¹² Ω / □) has been exceeded.
[Measurement of peeling force]
The release force of the conductive layer of the conductive mold release film of each example was measured by the following method to evaluate the mold release property.
A 25 mm wide polyester adhesive tape (Nitto Denko Corporation, No. 31B) was placed on the surface of the conductive layer of the conductive release film of each example, and a load of 1976 Pa was placed on the adhesive tape for 20 hours at 25 ° C. Heat-treated. Next, according to JIS Z0237, the adhesive tape attached to the conductive layer is peeled off at an angle of 180 ° (peeling speed 0.3 m / min) using a tensile tester to obtain a peeling force (unit: N). It was measured. The measurement results are shown in Table 1. The smaller the peeling force, the higher the releasability of the conductive layer.

The conductive film and the conductive release film of each example had a small surface resistance value and had high conductivity. In addition, the conductive mold release film of each example had a small peeling force and had high mold release properties.
The conductive film and the conductive release film of each comparative example had a large surface resistance value and low conductivity. In addition, the conductive mold release film of each comparative example had a large peeling force and a low mold release property.
In the examples, the polyanion of the conductive composite was reacted with the first epoxy group-containing compound, and further reacted with the second epoxy group-containing compound, whereby the hydrophobicity of the conductive composite was improved and in an organic solvent. It is presumed that the dispersibility of the conductive composite of the above was increased. It is presumed that the increased dispersibility of the conductive complex in the organic solvent increased the dispersibility of the conductive complex in the conductive layer, resulting in higher conductivity. Further, it is presumed that the releasability of the conductive layer is improved because the dispersibility of the low-polarity addition-curable silicone can be increased in the conductive polymer dispersion liquid of the example.
On the other hand, in the comparative example, since the first epoxy group-containing compound was reacted with the polyanion of the conductive composite and then the second epoxy group-containing compound was not reacted, the hydrophobicity of the conductive composite became insufficient and it was organic. It is presumed that the dispersibility of the conductive composite in the solvent was not sufficiently high. In the conductive layer of the comparative example formed from the conductive polymer dispersion having low dispersibility of the conductive composite in the organic solvent, the dispersibility of the conductive composite in the layer was low and the conductivity was low. Guessed. Further, it is presumed that the releasability of the conductive layer was lowered because the dispersibility of the addition-curable silicone was also low in the conductive polymer dispersion liquid of the comparative example.

Claims (9)

The first epoxy group-containing compound is added to the aqueous dispersion containing poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid in the aqueous dispersion medium to precipitate the conductive complex. After obtaining a precipitate, a precipitation recovery step of recovering the precipitate and a precipitation recovery step,
A method for producing a conductive polymer dispersion, which comprises a step of adding a second epoxy group-containing compound to obtain a first preparation liquid by adding a first organic solvent and a second epoxy group-containing compound to the recovered precipitate. hand,
A method for producing a conductive polymer dispersion, wherein the first epoxy group-containing compound and the second epoxy group-containing compound are independently described in (i) below or (ii) below.
(I) Organic epoxy compound having 10 or more and 25 or less carbon atoms and containing no silicon atom (ii) Epoxy-modified silicone having 10 or more and 50 or less carbon atoms containing silicon atom The first aspect of the present invention further comprises a cleaning step of cleaning the precipitate with a cleaning organic solvent containing an organic solvent having no hydroxy group between the precipitation recovery step and the second epoxy group-containing compound addition step. The method for producing a conductive polymer dispersion according to the above method. The method for producing a conductive polymer dispersion according to claim 1 or 2, wherein the first organic solvent is methyl ethyl ketone. It has a second organic solvent addition step of adding heptane to the first preparation liquid to obtain a second preparation liquid.
The method for producing a conductive polymer dispersion liquid according to claim 3, wherein the content of heptane is 60% by mass or more with respect to 100% by mass of the total amount of the organic solvent contained in the second preparation liquid. The method for producing a conductive polymer dispersion liquid according to claim 4, wherein an addition-curable silicone compound is further added to the second preparation liquid. A drying step of drying an aqueous dispersion in which a conductive complex containing poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is contained in an aqueous dispersion medium to obtain a dried product of the conductive complex, and a drying step.
Highly conductive, comprising a first preparation liquid preparation step of adding a first epoxy group-containing compound and a first organic solvent to the dried product, and further adding a second epoxy group-containing compound to obtain a first preparation liquid. It is a method for producing a molecular dispersion liquid.
A method for producing a conductive polymer dispersion, wherein the first epoxy group-containing compound and the second epoxy group-containing compound are independently described in (i) below or (ii) below.
(I) Organic epoxy compound having 10 or more and 25 or less carbon atoms and containing no silicon atom (ii) Epoxy-modified silicone having 10 or more and 50 or less carbon atoms containing silicon atom The method for producing a conductive polymer dispersion according to claim 6, wherein the first organic solvent is methyl ethyl ketone. It has a second organic solvent addition step of adding heptane to the first preparation liquid to obtain a second preparation liquid.
The method for producing a conductive polymer dispersion liquid according to claim 7, wherein the content of heptane is 60% by mass or more with respect to 100% by mass of the total amount of the organic solvent contained in the second preparation liquid. The method for producing a conductive polymer dispersion liquid according to claim 8, wherein an addition-curable silicone compound is further added to the second preparation liquid.