JP2021105072A - Method for manufacturing high conductive composite, method for manufacturing aqueous dispersion of high conductive composite, method for manufacturing organic solvent dispersion of high conductive composite, conductive film and method for manufacturing the same - Google Patents

Abstract

To provide: a method for manufacturing a high conductive composite, capable of forming a conductive layer excellent in conductivity; a method for manufacturing the aqueous dispersion of the high conductive composite; a method for manufacturing the organic solvent dispersion of the high conductive composite; a conductive film; and a method for manufacturing the conductive film.SOLUTION: (1) A method for manufacturing a high conductive composite includes: obtaining a mixed-solution obtained by mixing a preparation liquid comprising a conductive composite including a π conjugated system conductive polymer and a polyanion, transition metal ions and an aqueous dispersion medium with an organic solvent to deposit a high conductive composite in the mixed-solution; and fractionating the deposited high conductive composite. (2) A method for manufacturing a high conductive composite includes: obtaining the mixed-solution obtained by mixing the preparation liquid including the conductive composite, the transition metal ions and the aqueous dispersion medium with the organic solvent to deposit the high conductive composite in the mixed-solution; and adding an amine compound to the mixed solution including the high conductive composite; and fractionating the high conductive composite having the added amine compound.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a highly conductive composite, a method for producing an aqueous dispersion of a highly conductive composite, a method for producing an organic solvent dispersion of a highly conductive composite, a conductive film and a method for producing the same.

As a coating material for forming a conductive layer on a plastic film, a conductive polymer-containing liquid containing a conductive composite in which poly (3,4-ethylenedioxythiophene) is doped with polystyrene sulfonic acid may be used. ..
Patent Document 1 proposes a method of adding an amine compound to an anionic group of a conductive composite to make the conductive composite hydrophobic in order to improve the wettability of the conductive polymer-containing liquid with respect to a plastic film. Has been done.

Japanese Unexamined Patent Publication No. 2018-53191

However, the conductivity of the conductive layer formed by applying the amine adduct of the conductive complex is not always satisfactory, and further improvement in conductivity is required.
The present invention relates to a method for producing a highly conductive composite capable of forming a conductive layer having excellent conductivity, a method for producing an aqueous dispersion of a highly conductive composite, and an organic solvent dispersion of a highly conductive composite. A method for producing a conductive film and a method for producing the same.

[1] A mixed solution obtained by mixing an organic solvent with a prepared solution containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a transition metal ion, and an aqueous dispersion medium is obtained in the mixed solution. A method for producing a highly conductive composite, which comprises depositing a highly conductive composite in a solvent and separating the precipitated highly conductive composite.
[2] The method for producing a highly conductive composite according to [1], wherein the content of the organic solvent contained in the mixed solution is 50% by mass or more with respect to the total mass of the mixed solution.
[3] The method for producing a highly conductive composite according to [1] or [2], wherein the organic solvent contains at least one of a ketone solvent and an alcohol solvent.
[4] The method for producing a highly conductive complex according to [3], wherein the organic solvent contains a ketone solvent and the ketone solvent contains a methyl ethyl ketone.
[5] The method for producing a highly conductive composite according to [3], wherein the organic solvent contains an alcohol solvent and the alcohol solvent contains methanol.
[6] The method for producing a highly conductive complex according to [1] or [2], wherein the organic solvent contains methyl ethyl ketone and methanol.
[7] The method for producing a highly conductive complex according to [1] or [2], wherein the organic solvent contains isopropanol and ethyl acetate.
[8] The method for producing a highly conductive complex according to [7], wherein the organic solvent further contains methyl ethyl ketone.
[9] When the highly conductive composite precipitated in the mixed solution is separated, the transition metal ion contained in the mixed solution and the highly conductive composite are separated from each other [1] to [8]. The method for producing a highly conductive composite according to any one of the above.
[10] Of [1] to [9], when the highly conductive composite is precipitated in the mixed solution, the mixed solution contains at least one of the counter anion of the transition metal ion and the oxidizing agent. The method for producing a highly conductive composite according to any one of the above.
[11] The highly conductive complex according to any one of [1] to [10], wherein the method for separating the highly conductive complex precipitated in the mixed solution is filtration or decantation. Manufacturing method.
[12] The method for producing a highly conductive composite according to any one of [1] to [11], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[13] The method for producing a highly conductive complex according to any one of [1] to [12], wherein the polyanion is polystyrene sulfonic acid.
[14] A mixed solution obtained by mixing an organic solvent with a prepared solution containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a transition metal ion, and an aqueous dispersion medium is obtained in the mixed solution. After precipitating the highly conductive composite in, an amine compound is added to the mixed solution containing the highly conductive composite, and the highly conductive composite to which the amine compound is added is separated. A method for producing a conductive composite.
[15] A highly conductive composite comprising mixing a highly conductive composite obtained by the production method according to any one of [1] to [13] with a water-containing aqueous solvent. A method for producing an aqueous dispersion.
[16] The method for producing an aqueous dispersion of a highly conductive complex according to [15], which further comprises mixing a binder component.
[17] A highly conductive composite comprising mixing a highly conductive composite obtained by the production method according to any one of [1] to [13], an organic solvent, and an amine compound. A method for producing an organic solvent dispersion.
[18] A method for producing an organic solvent dispersion of a highly conductive complex, which comprises mixing the highly conductive complex obtained by the production method according to [14] with an organic solvent.
[19] The method for producing an organic solvent dispersion of a highly conductive complex according to [17] or [18], which further comprises mixing a binder component.
[20] The method for producing an organic solvent dispersion of a highly conductive composite according to [19], wherein the binder component is a compound that forms an acrylic resin after curing.
[21] An aqueous dispersion of a highly conductive composite obtained by the production method according to [15] or [16], or any of [17] to [20] on at least one surface of the film substrate. A method for producing a conductive film, which comprises applying an organic solvent dispersion of a highly conductive composite obtained by the production method according to item 1 and drying the formed coating film.
[22] On at least one surface of the film substrate, a conductive layer composed of a cured layer of an aqueous dispersion of a highly conductive composite obtained by the production method according to [15] or [16], or [17]. A conductive film provided with a conductive layer composed of a cured layer of an organic solvent dispersion of a highly conductive composite obtained by the production method according to any one of [20].

According to the method for producing a highly conductive complex of the present invention, the highly conductive complex can be easily separated without requiring a reaction for hydrophobizing the anion group of the highly conductive complex. Since the separated highly conductive complex is hydrophilic, it can be easily dispersed in water. Further, if necessary, it is easy to add an amine compound to the highly conductive complex to make it hydrophobic. Therefore, the hydrophobized highly conductive complex can be easily dispersed in an organic solvent. Surprisingly, when the highly conductive composite obtained by the present invention is used, it is possible to form a conductive layer having excellent conductivity as compared with the case where a conventional conductive composite is used.

≪Manufacturing method of highly conductive composite≫
In the first aspect of the present invention, a mixed solution obtained by mixing an organic solvent with a prepared solution containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a transition metal ion, and an aqueous dispersion medium is obtained. , A method for producing a highly conductive composite, which comprises precipitating a highly conductive composite in the mixed solution and separating the precipitated highly conductive composite.

[Preparation solution]
The preparation liquid used in this embodiment contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, a transition metal ion, and an aqueous dispersion medium. This preparation liquid may contain an organic solvent as long as the conductive complex in the liquid is in a dispersed state.

As the preparation liquid used in this embodiment, the reaction liquid prepared for oxidative polymerization of the monomer of the π-conjugated conductive polymer can be applied as it is. The preparation liquid may contain an oxidizing agent used for oxidatively polymerizing the monomer. The preparation liquid may contain a transition metal ion and a counter anion of the transition metal ion as a catalyst for promoting oxidative polymerization.
In the method for producing a highly conductive composite of this embodiment, even if the prepared liquid contains an oxidizing agent and a catalyst, a mixed liquid obtained by mixing an organic solvent with the prepared liquid is obtained and the highly conductive composite is precipitated. The highly conductive composite can be easily separated from the oxidizing agent and the catalyst by separating the highly conductive composite.

(Conductive complex)
The polyanion is doped with a π-conjugated conductive polymer to form a conductive composite having conductivity. In the polyanion, only a part of the anion groups are doped in the π-conjugated conductive polymer, and the polyanion has a surplus anion group that does not participate in the doping. Since the excess anionic group is a hydrophilic group, the conductive complex has dispersibility in water.

In the preparation liquid used in this embodiment, the conductive complex is in a dispersed state. The distinction between the dispersed state and the precipitated state can be easily visually performed. The dispersion liquid in the dispersed state is highly transparent, and no solid suspended matter is found in the prepared liquid. On the other hand, the transparency of the prepared liquid in the precipitated state is low, and solid suspended matter is observed in the liquid. Normally, the conductive composite in a dispersed state does not easily precipitate, and even if it is allowed to stand for 12 hours, for example, precipitation is unlikely to occur. On the other hand, the suspended matter in the liquid in the precipitated state is likely to settle, and for example, by allowing it to stand for about 12 hours, precipitation is likely to occur.

When the preparation liquid used in this embodiment is passed through a filter having a reserved particle size of 7 μm, the conductive composite in a dispersed state passes through the filter together with the dispersion medium. On the other hand, the conductive complex in the precipitated state can be captured by the filter.
Here, the reserved particle size of the filter paper is a guideline for the roughness of the mesh, and is obtained from the leaked particle size when barium sulfate or the like specified in JIS P 3801 [filter paper (for chemical analysis)] is naturally filtered.

(Π-conjugated conductive polymer)
The π-conjugated conductive polymer may be an organic polymer whose main chain is composed of a π-conjugated system. For example, a polypyrrole-based conductive polymer, a polythiophene-based conductive polymer, or a polyacetylene-based conductive polymer has high conductivity. Examples thereof include molecules, polyphenylene-based conductive polymers, polyphenylene vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophenine vinylene-based conductive polymers, and copolymers thereof. 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 these π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity, transparency, and heat resistance.
The π-conjugated conductive polymer contained in the conductive complex may be of one type or two or more types.

(Polyanion)
A 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 acid ester having a sulfo group, and polymethacrylic acid ester having a sulfo group (for example, poly (4-sulfobutyl methacrylate). , Polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprenesulfonic acid and other polymers with sulfo groups, polyvinylcarboxylic acid, polystyrenecarboxylic acid, etc. Examples thereof include polymers having a carboxy group such as polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), and polyisoprenecarboxylic acid. The polyanion is a single monomer. It may be a homopolymer obtained by polymerizing the above, or it may be a copolymer obtained by polymerizing two or more kinds of monomers.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be made higher.
The polyanion may be used alone or in combination of two or more.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less. The mass average molecular weight is a mass-based average molecular weight measured by gel permeation chromatography and determined 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 with respect to 100 parts by mass of the π-conjugated conductive polymer, and is 10 parts by mass or more and 700 parts by mass or less. It is more preferable that the amount is 100 parts by mass or more and 500 parts by mass or less. When the content ratio of the polyanion is at least the above lower limit value, the doping effect on the π-conjugated conductive polymer tends to be strong, and the conductivity becomes higher. On the other hand, when the content of the polyanion is not more than the upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

<Manufacturing method of preparation liquid>
The conductive composite containing the π-conjugated conductive polymer and the polyanion can be obtained, for example, by chemically oxidatively polymerizing a monomer forming the π-conjugated conductive polymer in an aqueous solution of the polyanion. The reaction solution of this chemical oxidation polymerization can be used as it is as the preparation solution of this embodiment.

The chemical oxidative polymerization can be carried out using a known catalyst and an oxidizing agent. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidant can restore the reduced catalyst to its original oxidized state.

The content of the conductive complex contained in the preparation liquid of this embodiment is preferably 0.1% by mass or more and 20% by mass or less, and 0.5% by mass or more and 10% by mass, based on the total mass of the preparation liquid. % Or less is preferable, and 1.0% by mass or more and 5.0% by mass or less is more preferable.
When it is at least the lower limit of the above range, precipitation of the highly conductive complex after the addition of the organic solvent becomes easy. When it is not more than the upper limit of the above range, the dispersibility of the conductive complex in the preparation liquid is enhanced, so that unintended aggregation during storage of the preparation liquid is prevented and the quality of the highly conductive complex precipitated after the addition of the organic solvent Can be made uniform.

The preparation liquid used in this embodiment may contain an organic solvent as long as the conductive complex is in a dispersed state. The smaller the content of the organic solvent, the more preferable, and it is more preferable that the organic solvent is not substantially contained. Is even more preferable.
The organic solvent that may be contained in the preparation liquid used in this embodiment is preferably one that is highly miscible with water, and examples thereof include alcoholic solvents described later.

[Mixture]
Examples of the method of mixing the preparation liquid with the organic solvent to obtain the mixed liquid include a method of adding the organic solvent to the preparation liquid, a method of adding the preparation liquid to the organic solvent, and the like. A preferred embodiment includes a method of gradually adding an organic solvent while stirring the preparation liquid. With this addition method, it is possible to prevent the concentration of the organic solvent in the preparation liquid from rising locally, and to gently precipitate the highly conductive complex. Sudden increases in organic solvent concentration can result in inhomogeneous agglomerates of highly conductive complexes.

The content of the organic solvent contained in the mixed solution is preferably 50% by mass or more and less than 100% by mass, more preferably 55% by mass or more and 90% by mass or less, and 60% by mass, based on the total mass of the mixed solution. More than 85% by mass is more preferable, and 65% by mass or more and 80% by mass or less is particularly preferable. Here, the content of the organic solvent is an amount containing the organic solvent contained in the preparation liquid before mixing.
When it is at least the lower limit of the above range, the precipitation of the highly conductive complex becomes easier, and the yield of the highly conductive complex is improved.
When it is not more than the upper limit of the above range, the amount of the prepared liquid contained in the mixed liquid can be relatively increased, so that the amount of the highly conductive complex to be sorted can be increased.

The appearance after mixing the prepared liquid and the organic solvent and allowing the obtained mixed liquid to stand may be such that the water and the organic solvent are completely compatible with each other or separated from each other. However, from the viewpoint of facilitating the precipitation of the highly conductive composite, it is preferable that they are sufficiently compatible with each other.

(Organic solvent)
As the organic solvent constituting the mixed liquid of this embodiment, a water-soluble organic solvent is preferable. Here, the water-soluble organic solvent is an organic solvent having a dissolution amount of 1 g or more with respect to 100 g of water at a temperature of 20 ° C.
Examples of the water-soluble organic solvent include alcohol-based solvents, ketone-based solvents, and ester-based solvents.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, allyl alcohol and the like.
Examples of the ketone solvent include methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diethyl ketone, diisopropyl ketone, acetone, diacetone alcohol and the like.
Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate and the like.
One type of organic solvent may be used alone, or two or more types may be used in combination.

The organic solvent constituting the mixed solution of this embodiment preferably contains at least one of a ketone solvent and an alcohol solvent.
It is preferable to contain methyl ethyl ketone as the ketone solvent.
As the alcohol solvent, methanol or isopropanol is preferable.
When the above-mentioned suitable organic solvent is contained, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.

In the mixed solution of this embodiment, methyl ethyl ketone is preferably contained in combination with methanol or isopropanol. In this case, the content of methanol or isopropanol with respect to 100 parts by mass of methyl ethyl ketone is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 3 parts by mass or more and 50 parts by mass or less, and further preferably 6 parts by mass or more and 20 parts by mass or less. ..
When the above-mentioned suitable combination of organic solvents is contained, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.
When the organic solvent is contained in the above-mentioned preferable range, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.

In the mixed solution of this embodiment, isopropanol is preferably contained in combination with methyl acetate or ethyl acetate. In this case, the content of methyl acetate or ethyl acetate with respect to 100 parts by mass of isopropanol is preferably 10 parts by mass or more and 300 parts by mass or less, more preferably 30 parts by mass or more and 200 parts by mass or less, and 60 parts by mass or more and 100 parts by mass or less. More preferred.
When the above-mentioned suitable combination of organic solvents is contained, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.
When the organic solvent is contained in the above-mentioned preferable range, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.

In the mixed solution of this embodiment, it is preferable that methyl ethyl ketone, isopropanol, and methyl acetate or ethyl acetate are contained in combination. In this case, the content of methyl acetate or ethyl acetate with respect to 100 parts by mass of isopropanol is preferably 10 parts by mass or more and 300 parts by mass or less, more preferably 30 parts by mass or more and 200 parts by mass or less, and 60 parts by mass or more and 100 parts by mass or less. More preferred. The content of methyl ethyl ketone with respect to 100 parts by mass of isopropanol is preferably 100 parts by mass or more and 3000 parts by mass or less, more preferably 200 parts by mass or more and 2000 parts by mass or less, and further preferably 500 parts by mass or more and 1000 parts by mass or less.
When the above-mentioned suitable combination of organic solvents is contained, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.
When the organic solvent is contained in the above-mentioned preferable range, the highly conductive composite can be more easily precipitated in the mixed solution, and the yield can be further improved.

The content of the acid or base other than the polyanion in the mixed solution of this embodiment is preferably 0.1% by mass or less, preferably 0.01% by mass or less, based on the total mass of the mixed solution. It is more preferable that it is present, and it is most preferable that it is not substantially contained.
Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as paratoluene sulfonic acid and naphthalene sulfonic acid.
Examples of the base include inorganic bases such as sodium hydroxide and sodium carbonate, and organic bases such as trioctylamine and octylamine.
The above-mentioned acid or base can be a cause of inhibiting the precipitation of the highly conductive complex in the mixed solution of this embodiment.

The mixed solution of this embodiment contains one or more of the transition metal ions derived from the prepared solution.
Examples of the transition metal ion include cations of the first transition element such as iron and copper.
Examples of the counter anion of the transition metal ion include anions such as chlorine, bromine, sulfuric acid, and nitric acid.
When the transition metal ions are derived from a catalyst for oxidatively polymerizing a monomer of a π-conjugated conductive polymer, the amount of the transition metal ions in the preparation liquid is, for example, relative to the total mass of the preparation liquid. It is contained as a guideline of 0.001% by mass or more and 0.5% by mass or less, preferably 0.005% by mass or more and 0.25% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
Since the mixed solution is obtained by diluting the prepared solution with the organic solvent, the amount of transition metal ions contained in the mixed solution is, for example, 0.0001% by mass or more with respect to the total mass of the mixed solution. As a guide, 0.4% by mass or less, preferably 0.0005% by mass or more and 0.1% by mass or less, more preferably 0.001% by mass or more and 0.05% by mass or less.

The mixed solution of this embodiment may contain one or more kinds of oxidizing agents derived from the prepared solution. Examples of the oxidizing agent include those used for oxidatively polymerizing a monomer of a π-conjugated conductive polymer.
When the oxidizing agent is an oxidizing agent for oxidatively polymerizing a monomer of a π-conjugated conductive polymer, the amount of the oxidizing agent in the preparation liquid is, for example, 0. 1% by mass or more and 5% by mass or less, preferably 0.5% by mass or more and 3% by mass or less, more preferably 1% by mass or more and 2% by mass or less is included as a guide.
Since the mixed solution is obtained by diluting the prepared solution with the organic solvent, the amount of the oxidizing agent contained in the mixed solution is, for example, 0.01% by mass or more with respect to the total mass of the mixed solution. 4% by mass or less is mentioned, preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.2% by mass or more and 1% by mass or less as a guide.

[Precipitation of highly conductive complex]
The method for precipitating the highly conductive complex in the prepared mixed solution is not particularly limited, and the mixed solution can be precipitated even by allowing the mixed solution to stand still. Further, it is not necessary to allow the mixture to stand completely, and the precipitate may be precipitated with gentle stirring.

When precipitating the highly conductive composite in the mixed solution, it is preferable to heat the mixed solution. The heating temperature is preferably 40 ° C. or higher, more preferably 50 ° C. or higher and 100 ° C. or lower, and even more preferably 60 ° C. or higher and 80 ° C. or lower. The heating time at the above-mentioned suitable heating temperature can be, for example, 1 hour or more and 10 hours or less.
When the mixed solution is heated, the highly conductive complex can be easily precipitated in the mixed solution, and the yield of the conductive complex can be improved.

[Separation of highly conductive composite]
The method for separating (recovering) the highly conductive complex precipitated in the mixed solution is not particularly limited, and examples thereof include filtration, decantation, centrifugation, vacuum drying, freeze drying, and spray drying.
Of these, filtration or decantation is preferable because it is easy to separate the components other than the highly conductive complex contained in the mixed solution from the highly conductive complex. Here, filtration is an operation of capturing a highly conductive composite in a filter through which a mixed solution has passed. Further, decantation is an operation of precipitating the precipitated highly conductive complex and removing the supernatant liquid.
Decantation is easier to sort because it is necessary to deal with clogging of the filter when sorting by filtration. Further, since the solid substance of the highly conductive complex is compressed by the filtration pressure on the filter, the highly conductive complex separated by filtration tends to be in a harder state than when separated by decantation. Since the highly conductive composite obtained by decantation is obtained in a relatively soft powder state, it can be easily dispersed later in a dispersion medium. Therefore, it is more preferable to separate the highly conductive complex by decantation.

The separated highly conductive composite is preferably washed with an organic solvent in which the highly conductive composite is difficult to dissolve. Specifically, for example, an organic solvent may be poured over a filter that captures the highly conductive composite, or the organic solvent is added to the highly conductive composite remaining at the bottom of the container after decantation and stirred. After that, it may be sorted again by decantation or the like.
A dried body of the highly conductive composite can be obtained by drying and removing the organic solvent or the like adhering to the separated highly conductive composite.

<Effect>
According to the method for producing a highly conductive composite of the present invention, 90 to 100 parts by mass of a highly conductive composite is recovered as a precipitate with respect to 100 parts by mass of the conductive composite contained in the mixed solution. Can be done. That is, the method for producing a highly conductive composite of this embodiment can exhibit a high yield of 90 to 100% by mass.
In the method for producing a highly conductive composite of the present invention, it is presumed that the reason why the highly conductive composite is precipitated in the mixed liquid containing an organic solvent is that the highly conductive composite is difficult to dissolve in the organic solvent. NS.
Surprisingly, the use of the highly conductive composite precipitated in the production method of the present invention is more than the use of a conventional conductive complex (for example, a conductive complex obtained by freeze-drying a raw material). , A conductive layer having excellent conductivity can be formed (see Examples and Comparative Examples described later). The difference in chemical composition between the highly conductive composite after precipitation and the conventional conductive composite is considered to be the presence or absence of a very small amount of organic solvent adhering to the highly conductive composite at the molecular level, if any. Be done. It is considered that the difference in physicochemical properties rather than the chemical composition influences the difference in conductivity. By using the highly conductive composite obtained by the production method of the present invention, a highly conductive composite having a particle size smaller than that of the conventional conductive composite can be dispersed in the coating material. As a result, it is presumed that the conductivity of the conductive layer formed from the coating film of the paint is increased.

In the method for producing a highly conductive complex of the present invention, an oxidizing agent and a catalyst may be contained in the mixed liquid for precipitating the highly conductive complex. Therefore, it is not necessary to remove the oxidizing agent and the catalyst from the preparation liquid which is the raw material of the mixed liquid in advance. As the preparation liquid, a reaction liquid subjected to oxidative polymerization for forming a π-conjugated conductive polymer can be used, so that the production efficiency of the highly conductive composite is very high. If the oxidizing agent and the catalyst are removed from the prepared liquid in advance, there is a problem that the manufacturing cost increases because the prepared liquid needs to be treated by ion exchange, gel filtration, ultrafiltration, or the like. On the other hand, in the production method of the present invention, it is not necessary to carry out these treatments, and a highly conductive composite having improved conductivity is separated through precipitation, and an oxidizing agent and a catalyst unnecessary for the subsequent steps are mixed. Since it can be easily separated by leaving it inside, the manufacturing cost can be reduced.

≪Manufacturing method of aqueous dispersion of highly conductive complex≫
A second aspect of the present invention is the production of an aqueous dispersion of a highly conductive composite, which comprises mixing the highly conductive composite obtained by the production method of the first aspect with an aqueous dispersion medium containing water. The method.
Since the highly conductive composite obtained in the first aspect has high dispersibility in water, it can be easily dispersed in an aqueous dispersion medium containing water.
The highly conductive composite used in this embodiment may be separated by the production method of the first aspect and then dried and stored, or may be used immediately without storage.

The aqueous dispersion medium of this embodiment may contain an organic solvent. As the organic solvent, a water-soluble organic solvent is preferable. Here, the water-soluble organic solvent is an organic solvent having a dissolution amount of 1 g or more with respect to 100 g of water at 20 ° C.
Examples of the water-soluble organic solvent include alcohol-based solvents, ketone-based solvents, and ester-based solvents, and alcohol-based solvents are preferable. A specific example of the water-soluble organic solvent will be omitted because it is the same as the description of the first aspect.

The content ratio of water to the total mass of the aqueous dispersion medium of this embodiment can be, for example, 5% by mass or more and 100% by mass or less, preferably 50% by mass or more and 100% by mass or less, and 70% by mass or more and 100% by mass or less. The following is more preferable.

In this embodiment, the method of mixing the highly conductive composite and the aqueous dispersion medium is not particularly limited, and for example, (1) a method of adding the aqueous dispersion medium to the highly conductive composite and stirring, (2) high. Examples thereof include a method in which water is added to the conductive composite to obtain an aqueous dispersion of the highly conductive composite, and then an organic solvent is further added as needed and the mixture is stirred.
Since the dispersibility of the highly conductive composite in water is very high, the method (2) is preferable from the viewpoint of preventing the particles from becoming larger in diameter due to the aggregation of the highly conductive composite.

After mixing the highly conductive composite and the aqueous dispersion medium, the mixed solution may be stirred to perform the 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.

In the aqueous dispersion of the highly conductive complex of this embodiment, the particle size distribution of the dispersed highly conductive complex is not particularly limited, but is preferably 300 nm or less, more preferably 250 nm or less, and more preferably 200 nm or less. Is more preferable. Since the highly conductive composite contains a polymer, the lower limit is 1 nm or more as a guide, considering the molecular radius of the polymer.
The smaller the particle size distribution, the better the conductivity of the conductive layer formed by applying the aqueous dispersion of the highly conductive complex of this embodiment.
Here, the particle size distribution is a value obtained by measuring the average particle size of cumulant by a dynamic light scattering method.

The content of the highly conductive composite with respect to the total mass of the aqueous dispersion of the highly conductive composite of this embodiment is, for example, preferably 0.1% by mass or more and 20% by mass or less, and 0.5% by mass or more and 10%. More preferably, it is 1.0% by mass or more and 5.0% by mass or less.
Within the above range, the highly conductive composite can be dispersed more stably.

(Binder component)
The aqueous dispersion of the highly conductive complex of this embodiment may contain a binder component. 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 cures when a conductive layer (conductive film) is formed. The thermoplastic resin becomes a binder resin as it is, and the curable monomer or oligomer is a binder resin formed by curing.
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, polyacrylamide resin, silicone and the like.
As the binder resin contained in the aqueous dispersion of the highly conductive composite of this embodiment, a water-dispersible resin is preferable, and a water-dispersible emulsion resin is more preferable. The water-dispersible resin is an emulsion resin or a water-soluble resin.

Specific examples of the water-dispersible emulsion resin include acrylic resin (acrylic compound), polyester resin, polyurethane resin, polyimide resin, melamine resin, and the like, which are emulsified with an emulsifier. Of these, a polyester emulsion is preferable because the strength of the coating film (conductive film) obtained by applying the aqueous dispersion of the highly conductive composite of this embodiment to the film substrate is high. In particular, when coating on a polyester film base material, a polyester emulsion is preferable because the adhesion of the coating film to the film base material is high.

Specific examples of the water-soluble resin include acrylic resin (acrylic compound), polyester resin, polyurethane resin, polyimide resin, and melamine resin, which have an acid group such as a carboxy group or a sulfo group or a salt thereof. Here, the water-soluble resin preferably dissolves in 100 g of distilled water at 25 ° C. in an amount of 1 g or more, preferably 5 g or more, and more preferably 10 g or more.

The acid group such as the carboxy group and the sulfo group contained in the binder resin may form a salt with a cation such as a sodium ion or a potassium ion.

The curable monomer or oligomer may be a thermosetting monomer or oligomer, or may be a photocurable monomer or oligomer. Here, the oligomer is a polymer having a mass average molecular weight of less than 10,000.
Examples of the curable monomer include an acrylic monomer (acrylic compound) and an epoxy monomer. Examples of the curable oligomer include an acrylic oligomer (acrylic compound) and an epoxy oligomer.
When an acrylic monomer or an acrylic oligomer is used as the binder component, it can be easily cured by heating or light irradiation.

When a curable monomer or oligomer is contained, it is preferable to further contain a curing catalyst. For example, when a thermosetting monomer or oligomer is contained, it is preferable to contain a thermosetting initiator that generates radicals by heating, and when a photocurable monomer or oligomer is contained, radicals are generated by light irradiation. It is preferable to include a photopolymerization initiator to be allowed to be used.

The content ratio of the binder component in the aqueous dispersion of the highly conductive composite of this embodiment is preferably 100 parts by mass or more and 20000 parts by mass or less, and 500 parts by mass or more, with respect to 100 parts by mass of the highly conductive composite. It is more preferably 5000 parts by mass or less. When the content ratio of the binder component is at least the above lower limit value, the film-forming property and the film strength when the aqueous dispersion of the highly conductive composite of this embodiment is applied to the film substrate can be improved. When the content ratio of the binder component is not more than the upper limit value, it is possible to suppress the decrease in conductivity due to the decrease in the content ratio of the highly conductive composite.

≪Manufacturing method of organic solvent dispersion liquid of highly conductive composite≫
A third aspect of the present invention is the production of an organic solvent dispersion of a highly conductive composite, which comprises mixing the highly conductive composite obtained by the production method of the first aspect, an organic solvent, and an amine compound. The method.
The highly conductive composite obtained in the first aspect has high dispersibility in water and low dispersibility in organic solvents. Therefore, an amine compound is added to the highly conductive composite together with an organic solvent, and the amine compound is added to the anionic group of the polyanion constituting the highly conductive composite to make the highly conductive composite hydrophobic. The highly conductive composite can be dispersed in an organic solvent.
The highly conductive composite used in this embodiment may be separated by the production method of the first aspect and then dried and stored, or may be used immediately without storage.

(Amine compound)
The amine compound is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. One type of amine compound may be used alone, or two or more types may be used in combination.
Examples of the primary amine include aniline, toluidine, benzylamine, ethanolamine and the like.
Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, trinaphthylamine and the like.
Among the amine compounds, a tertiary amine is preferable, and at least one of trioctylamine and tributylamine is more preferable because the highly conductive complex can be easily hydrophobized.

Since the amine compound has high dispersibility in a low-polarity organic solvent, the amine compound preferably has a substituent having 6 or more carbon atoms on the nitrogen atom, and has a substituent having 8 or more carbon atoms on the nitrogen atom. It is more preferable to have.

The organic solvent dispersion liquid of the highly conductive composite contains the above-mentioned highly conductive composite, an amine compound added thereto, and an organic solvent. Since the organic solvent can disperse or dissolve the highly conductive composite, it can be called a dispersion medium or a solvent. In the present specification, it may be simply referred to as dispersion without distinguishing between dispersion and dissolution, and may be simply referred to as a dispersion medium without distinguishing between a dispersion medium and a solvent.

(Organic solvent)
Examples of the organic solvent used in the production method of this embodiment include hydrocarbon solvents, ketone solvents, alcohol solvents, ester solvents, nitrogen atom-containing compound solvents and the like. One type of organic solvent may be used alone, or two or more types may be used in combination.
Examples of the 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-mentioned organic solvents, an alcohol-based solvent has a high wettability of the organic solvent dispersion liquid of a highly conductive composite with respect to a plastic film base material, and can easily solubilize a relatively highly polar binder component. Is preferable. Further, among the alcohol solvents, isopropanol is preferable because the highly conductive complex to which the amine compound is added has good dispersibility.

The content ratio of the organic solvent is preferably 50% by mass or more and 99.5% by mass or less, and more preferably 70% by mass or more and 99% by mass or less, based on the total mass of the organic solvent dispersion liquid of the highly conductive composite. When the content ratio of the organic solvent is within the above range, the dispersibility of the highly conductive composite can be enhanced.

In this embodiment, the method of mixing the highly conductive composite, the organic solvent and the amine compound is not particularly limited, and for example, (A) the method of adding the organic solvent and the amine compound to the highly conductive composite and stirring the mixture. (B) Examples thereof include a method in which an amine compound is added to the highly conductive composite to obtain a hydrophobic high conductive composite, and then an organic solvent is further added and stirred.
The method (A) is preferable from the viewpoint of increasing the efficiency of the addition reaction of the amine compound to the polyanion of the highly conductive complex.

In this embodiment, as a method of mixing the highly conductive composite, the organic solvent, and the amine compound, a method of mixing them and dispersing them while mixing them with a high-pressure homogenizer is preferable.

When the amine compound and the organic solvent are mixed with the highly conductive composite, the amine compound is added to the highly conductive composite, and the highly conductive composite is hydrophobized. Although the hydrophobized highly conductive complex is dispersed in this mixture, the mixture may be continuously stirred to further disperse the mixture. The stirring method is not particularly limited, and stirring may be performed with a weak shearing force such as a stirrer, or may be stirred using a disperser (homogenizer or the like) having a high shearing force.

In the organic solvent dispersion liquid obtained by the production method of this embodiment, the highly conductive composite to which the amine compound is added is in a dispersed state.
The particle size distribution of the dispersed highly conductive composite is not particularly limited, but is preferably 300 nm or less, more preferably 250 nm or less, and further preferably 200 nm or less. Since the highly conductive composite contains a polymer, the lower limit is 1 nm or more as a guide, considering the molecular radius of the polymer.
The smaller the particle size distribution, the better the conductivity of the conductive layer formed by applying the organic solvent dispersion liquid of the highly conductive composite of this embodiment.
Here, the particle size distribution is a value obtained by measuring the average particle size of cumulant by a dynamic light scattering method.

The content of the highly conductive composite with respect to the total mass of the organic solvent dispersion liquid of the highly conductive composite of this embodiment is, for example, preferably 0.01% by mass or more and 10% by mass or less, and 0.1% by mass or more. 5% by mass or less is more preferable, and 0.2% by mass or more and 1.0% by mass or less is further preferable.
Within the above range, the highly conductive composite can be dispersed more stably.

(Binder component)
The organic solvent dispersion liquid of the highly conductive composite of this embodiment may contain a binder component. 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 cures when a conductive layer (conductive film) is formed. The thermoplastic resin becomes a binder resin as it is, and the curable monomer or oligomer is a binder resin formed by curing.
One type of binder component may be used alone, or two or more types may be used in combination.

The curable monomer or oligomer may be a thermosetting monomer or oligomer, or may be a photocurable monomer or oligomer. Here, the oligomer is a polymer having a mass average molecular weight of less than 10,000.
Examples of the curable monomer include an acrylic monomer (acrylic compound) and an epoxy monomer. Examples of the curable oligomer include an acrylic oligomer (acrylic compound) and an epoxy oligomer.
When an acrylic monomer or an acrylic oligomer is used as the binder component, it can be easily cured by heating or light irradiation.

When a curable monomer or oligomer is contained, it is preferable to further contain a curing catalyst. For example, when a thermosetting monomer or oligomer is contained, it is preferable to contain a thermosetting initiator that generates radicals by heating, and when a photocurable monomer or oligomer is contained, radicals are generated by light irradiation. It is preferable to include a photopolymerization initiator to be allowed to be used.

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, polyacrylamide resin, silicone and the like.
As the binder resin contained in the organic solvent dispersion liquid of the highly conductive composite of this embodiment, a compound that forms an acrylic resin after curing, a polyurethane resin, or a polyester resin is preferable because it has good dispersibility in an organic solvent. A compound that forms an acrylic resin after curing, a polyurethane resin, is more preferable.

The content ratio of the binder component in the organic solvent dispersion liquid of the highly conductive composite of this embodiment is preferably 500 parts by mass or more and 50,000 parts by mass or less, and 1000 parts by mass with respect to 100 parts by mass of the highly conductive composite. More preferably, it is 20000 parts by mass or less. When the content ratio of the binder component is at least the above lower limit value, the film-forming property and the film strength when the aqueous dispersion of the highly conductive composite of this embodiment is applied to the film substrate can be improved. When the content ratio of the binder component is not more than the upper limit value, it is possible to suppress the decrease in conductivity due to the decrease in the content ratio of the highly conductive composite.

≪Manufacturing method of organic solvent dispersion liquid of highly conductive composite≫
A fourth aspect of the present invention is to obtain a mixed solution obtained by mixing an organic solvent with a prepared solution containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a transition metal ion, and an aqueous dispersion medium. After precipitating the highly conductive composite in the mixed solution, an amine compound is added to the mixed solution containing the highly conductive composite, and the highly conductive composite to which the amine compound is added is separated. It is a method for producing a highly conductive composite including the above.

In this embodiment, the method of precipitating the highly conductive complex in the mixed solution is the same as the method of the first aspect, and thus the duplicate description will be omitted.
The following description of the addition of the amine compound includes the same description as the addition of the amine compound in the third aspect described above.

[Addition of amine compound]
By adding an amine compound to the mixed solution in which the above-mentioned highly conductive complex is precipitated, the amine compound is added to some anionic groups of the polyanions constituting the highly conductive complex to form a highly conductive complex. It can be made hydrophobic. The highly conductive complex before hydrophobization has high dispersibility in water, and the hydrophobized highly conductive complex has high dispersibility in organic solvents.
The structure of the substituent in which the amine compound is added to the surplus anion group not involved in the doping of the polyanion is considered to be the structure represented by the following chemical formula (X).
−HN ⁺ R ²¹ R ²² R ²³ ... (X)
[In formula (X), R ^{21 to} R ²³ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, except that at least one of ^{R 21 to} R ^{23 is a substituent.} It is a hydrocarbon group which may have. ]

In the formula (X), the leftmost bond represents that the negative charge of the anion group and the positive charge of the amine compound are bonded. As an anion group capable of negatively charged, for example, "-SO ₃ ^-" as include anionic groups active proton is bonded to an oxygen atom.

^{R 21 to} R ²³ in the formula (X) are hydrogen atoms or hydrocarbon groups which may have a substituent. ^{R 21 to} R ²³ in the formula (X) are substituents derived from the amine compound.
The hydrocarbon group in the formula (X) is an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and an aromatic hydrocarbon having 6 to 20 carbon atoms which may have a substituent. The group is mentioned.
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like.
Examples of the substituent of the aliphatic hydrocarbon group include a phenyl group and a hydroxyl group.
Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
Examples of the substituent of the aromatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group and the like.

(Amine compound)
The amine compound is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. One type of amine compound may be used alone, or two or more types may be used in combination.
Since the specific example of the amine compound is the same as the example of the amine compound in the third aspect, redundant description will be omitted.

Since the highly conductive composite to which the amine compound is added has high dispersibility in the low polar organic solvent, the amine compound added to the mixed solution has a substituent having 4 or more carbon atoms on the nitrogen atom. It is more preferable to have a substituent having 6 or more carbon atoms on the nitrogen atom, and it is further preferable to have a substituent having 8 or more carbon atoms on the nitrogen atom.

The method of adding the amine compound to the mixed solution is not particularly limited. Since the mixed solution contains an organic solvent to the extent that a highly conductive complex is precipitated, the hydrophobic amine compound can be sufficiently dissolved.

The amount of the amine compound added to the mixed solution shall be 1 part by mass or more and 10000 parts by mass or less with respect to 100 parts by mass of the total mass of the π-conjugated conductive polymer and the polyanion contained in the mixed solution. It is more preferably 10 parts by mass or more and 5000 parts by mass or less, and further preferably 50 parts by mass or more and 1000 parts by mass or less. When the addition ratio of the amine compound is at least the lower limit value, the dispersibility of the highly conductive composite with respect to the organic solvent becomes higher, and when it is at least the upper limit value, the decrease in conductivity of the highly conductive composite is prevented. be able to.

[Separation of highly conductive composite]
The method for separating (recovering) the highly conductive composite to which the amine compound is added in the mixed solution is not particularly limited, and for example, filtration, decantation, centrifugation, vacuum drying, freeze drying, spray drying. And so on.
Of these, filtration or decantation is preferable because it is easy to separate the components other than the highly conductive complex contained in the mixed solution from the highly conductive complex.

The separated highly conductive composite is preferably washed with an organic solvent in which the highly conductive composite is difficult to dissolve. Specifically, for example, an organic solvent may be poured over a filter that captures the highly conductive composite, or the organic solvent is added to the highly conductive composite remaining at the bottom of the container after decantation and stirred. After that, it may be sorted again by decantation or the like.
A dried body of the highly conductive composite can be obtained by drying and removing the organic solvent or the like adhering to the separated highly conductive composite.

The highly conductive complex obtained by the production method of this embodiment is hydrophobized by the addition of an amine compound. The highly conductive composite thus hydrophobized has high dispersibility in an organic solvent. Therefore, as described in the third aspect, the organic solvent dispersion liquid of the highly conductive composite can be produced by mixing the hydrophobized highly conductive composite with the organic solvent.
A binder component can be added to the organic solvent dispersion of the highly conductive composite as in the case of the third aspect.

≪Other additives≫
The above-mentioned aqueous dispersion and organic solvent dispersion of the highly conductive complex may contain other additives.
The additive is not particularly limited as long as the effect of the present invention can be obtained, and examples thereof include a surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant, and an ultraviolet absorber. However, the additive is other than the π-conjugated conductive polymer, polyanion, organic solvent, and binder component.
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 UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxanilide-based UV absorbers, hindered amine-based UV absorbers, benzoate-based UV absorbers, etc. Can be mentioned.
When the aqueous dispersion and the organic solvent dispersion of the highly conductive composite contain the additive, the content ratio thereof is appropriately determined according to the type of the additive. For example, the conductive polymer composite It can be in the range of 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the solid content of.

<Effect>
Since the aqueous dispersion and the organic solvent dispersion of the highly conductive composite obtained by the production method of the present invention are excellent in the dispersibility of the highly conductive composite, they are formed from the aqueous dispersion and the organic solvent dispersion. The dispersibility of the highly conductive composite in the conductive layer is also excellent. Therefore, the conductivity of the conductive layer can be sufficiently increased. Furthermore, since the highly conductive composite has good dispersibility, the storage stability of the above-mentioned aqueous dispersion and organic solvent dispersion can be improved.

≪Manufacturing method of conductive film≫
A fifth aspect of the present invention is the aqueous dispersion of the highly conductive composite obtained by the production method of the second aspect on at least one surface of the film substrate, or the production method of the third or fourth aspect. This is a method for producing a conductive film, which comprises applying an organic solvent dispersion liquid of the obtained highly conductive composite and drying the formed coating film.

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

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

(Coating process)
Examples of the method of applying the dispersion liquid of the highly conductive composite to the film substrate 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, and a rod coater. Coating methods using coaters such as air protector coaters, knife coaters, blade coaters, cast coaters, screen coaters, spraying methods using sprayers such as air spray, airless spray, rotor dampening, dipping methods such as dips, etc. Can be applied.
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 applied.
The amount of the dispersion liquid applied to the film substrate is not particularly limited, but the solid content should be in the range of ^{0.1 g / m 2} or more and 10.0 g / m ^{2 or less from the viewpoint of obtaining good conductivity.} Is preferable.

(Drying process)
Examples of the method for drying the coating film formed on the film substrate 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. The drying time when drying at the above temperature can be, for example, 30 seconds or more and 3 minutes or less.
When the coating film contains an active energy ray-curable binder component, it may further have an active energy ray irradiation step of irradiating the dried coating film with active energy rays. 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.
Examples of the active energy ray include ultraviolet rays, electron beams, visible rays and the like. 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 from the viewpoint of sufficiently curing the conductive layer. Further, from the viewpoint of sufficiently curing the conductive layer, the integrated light intensity is ^{preferably 50 mJ / cm 2} or more. In addition, the illuminance and the integrated light amount in this specification use 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. This is the measured value.

≪Conductive film≫
The sixth aspect of the present invention is a conductive layer composed of a cured layer of the aqueous dispersion of the highly conductive composite obtained by the production method of the second aspect on at least one surface of the film substrate, or the third aspect or the third aspect. It is a conductive film provided with a conductive layer composed of a cured layer of an organic solvent dispersion liquid of a highly conductive composite obtained by the production method of the fourth aspect. The conductive film of this embodiment can be produced by the production method of the fifth aspect.

The conductive film obtained by this aspect 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 highly conductive composite. The amine compound may be added to a part or all of the excess anion group of the polyanion constituting the highly conductive composite.
When the applied 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 of the conductive film of this embodiment is, for example, preferably 10 nm or more and 50 μm or less, more preferably 20 nm or more and 30 μm or less, and further preferably 30 nm or more and 20 μm or less. .. If the average thickness of the conductive layer is at least the lower limit value, sufficiently high conductivity can be exhibited, and if it is at least the upper limit value, the conductive layer can be easily formed.

The conductive layer of the conductive film of this embodiment preferably has a surface resistance value of ^{1 × 10 2} Ω / □ or more and 1 × 10 ^{8 Ω / □ or less as a measure of good conductivity. It is more preferable to have a surface resistance value of 3} Ω / □ or more and 1 × 10 ⁷ Ω / □ or less, and further preferably to have a surface resistance value of 1 × 10 ⁴ Ω / □ or more and 1 × 10 ⁶ Ω / □ or less. ..

<Effect>
Since the conductive layer of the conductive film of the sixth aspect of the present invention contains a highly conductive composite, it is more conductive than the conventional conductive layer containing the conductive composite.

(Production Example 1) Synthesis of polystyrene sulfonic acid 1.14 g of ammonium persulfate oxidant solution previously dissolved in 10 ml of water was added by dissolving 206 g of sodium styrene sulfonate in 1000 ml of ion-exchanged water and stirring at 80 ° C. The solution was added dropwise for 20 minutes and the solution was stirred for 12 hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium polystyrene sulfonate-containing solution, and about 1000 ml of the solvent of the polystyrene sulfonate-containing solution was removed by an ultrafiltration method. Next, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by an ultrafiltration method, and polystyrene sulfonic acid was washed with water. This washing operation was repeated 6 times.
Water in the obtained solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Production Example 2) Preparation Solution of Conductive Polymer 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid dissolved in 2000 ml of ion-exchanged water were mixed at 20 ° C. ..
The mixed solution thus obtained was kept at 20 ° C., and while stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of a ferric sulfate oxidation catalyst solution were slowly added. The reaction was carried out with stirring for 3 hours.
Thereby, a preparation containing 1.2% polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS), about 0.098% by mass of iron ions, and about 1.3% by mass of ammonium persulfate. Obtained liquid. Here, the content of PSS with respect to the PEDOT-PSS solid content is 75% by mass.

(Production Example 3) Synthesis of conductive polymer aqueous dispersion A solution of 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid dissolved in 2000 ml of ion-exchanged water is mixed at 20 ° C. I let you.
The mixed solution thus obtained was kept at 20 ° C., and while stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion-exchanged water and 8.0 g of a ferric sulfate oxidation catalyst solution were slowly added. The reaction was carried out with stirring for 3 hours.
2000 ml of ion-exchanged water was added to the obtained reaction solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. This operation was repeated 3 times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water were added to the obtained solution, and about 2000 ml of the solvent was removed by an ultrafiltration method. 2000 ml of ion-exchanged water was added to the residual liquid, and about 2000 ml of the solution was removed by an ultrafiltration method. 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 solvent was removed by an ultrafiltration method. This operation was repeated 5 times to obtain an aqueous dispersion of 1.2% polystyrene sulfonate-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS aqueous dispersion). The content of PSS with respect to the PEDOT-PSS solid content is 75% by mass.
The PEDOT-PSS aqueous dispersion obtained here does not substantially contain iron ions or ammonium persulfate.

(Production Example 4) Production of lyophilized product 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 3 was lyophilized to obtain 1.2 g of a lyophilized product of PEDOT-PSS (conductive composite).

(Example 1)
A mixed solution prepared by adding 12.5 g of methanol and 200 g of methyl ethyl ketone to 100 g of the preparation solution of Production Example 2 was stirred at 60 ° C. for 3 hours. Next, the highly conductive complex composed of PEDOT-PSS precipitated in the mixed solution was collected by filtration and washed with 100 g of isopropanol to obtain 1.2 g of the highly conductive complex.
Table 1 shows the results of measuring the iron content of the obtained highly conductive complex with fluorescent X-rays.
Next, 60 g of water was added to 1.2 g of the obtained highly conductive polymer composite and dispersed with a high-pressure homogenizer to obtain an aqueous dispersion of the highly conductive composite having a solid content (nonvolatile component) of 2% by mass. rice field. A highly conductive composite aqueous dispersion (solid content: about 1.0% by mass) obtained by adding 60 g of methanol to this aqueous dispersion was applied to a PET film (manufactured by Toray Co., Ltd., Lumirer T60) using a # 8 bar coater. A conductive film was obtained by applying on top and drying at 150 ° C. for 1 minute.

(Example 2)
A mixed solution prepared by adding 25 g of methanol and 200 g of methyl ethyl ketone to 100 g of the preparation solution of Production Example 2 was stirred at 60 ° C. for 3 hours. Next, the highly conductive complex composed of PEDOT-PSS precipitated in the mixed solution was collected by filtration and washed with 100 g of isopropanol to obtain 1.2 g of the highly conductive complex.
Table 1 shows the results of measuring the iron content of the obtained highly conductive complex with fluorescent X-rays.
Using the highly conductive composite obtained here, a conductive film was produced in the same manner as in Example 1.

(Example 3)
A mixed solution prepared by adding 25 g of isopropanol, 200 g of methyl ethyl ketone, and 17.5 g of ethyl acetate to 100 g of the preparation solution of Production Example 2 was stirred at 60 ° C. for 3 hours. Next, the highly conductive complex composed of PEDOT-PSS precipitated in the mixed solution was collected by filtration and washed with 100 g of isopropanol to obtain 1.2 g of the highly conductive complex.
Table 1 shows the results of measuring the iron content of the obtained highly conductive complex with fluorescent X-rays.
Using the highly conductive composite obtained here, a conductive film was produced in the same manner as in Example 1.

(Comparative Example 1)
212.5 g of water was added to 100 g of the preparation solution of Production Example 2, and the mixture was stirred at 60 ° C. for 3 hours. However, since the conductive complex did not precipitate, the subsequent study was stopped.

(Comparative Example 2)
225 g of water was added to 100 g of the preparation solution of Production Example 2, and the mixture was stirred at 60 ° C. for 3 hours. However, since the conductive complex did not precipitate, the subsequent study was stopped.

(Comparative Example 3)
242.5 g of water was added to 100 g of the preparation solution of Production Example 2, and the mixture was stirred at 60 ° C. for 3 hours. However, since the conductive complex did not precipitate, the subsequent study was stopped.

(Comparative Example 4)
Table 1 shows the results of measuring the iron content of the freeze-dried product of the conductive composite obtained in Production Example 3 by fluorescent X-rays. Next, 60 g of water was added to 1.2 g of this freeze-dried product and dispersed with a high-pressure homogenizer to obtain an aqueous dispersion of a conductive composite having a solid content of 2% by mass. A conductive film was obtained in the same manner as in Example 1 except that this aqueous dispersion was used.

<Evaluation>
Table 1 shows the results of measuring the surface resistance values of the conductive films of each example. At the time of the measurement, a resistivity meter (High Restor manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used, and the applied voltage was set to 10 V. The measurement results are shown in Table 1. In addition, "Ω / □" in the table means ohmper square. Further, "2.0E + 5" represents "2.0 × 10 ⁵ ".
The smaller the surface resistance value (unit: Ω / □), the higher the conductivity. In the results shown in Table 1, the conductivity of the conductive films of Examples 1 to 3 was superior to that of Comparative Example 4.

(Example 4)
A mixed solution prepared by adding 12.5 g of methanol and 200 g of methyl ethyl ketone to 100 g of the preparation solution of Production Example 2 was stirred at 60 ° C. for 3 hours. Next, the highly conductive complex composed of PEDOT-PSS precipitated in the mixed solution was collected by filtration and washed with 100 g of isopropanol to obtain 1.2 g of the highly conductive complex.
472.74 g of isopropanol and 1.06 g of trioctylamine were added to 1.2 g of the obtained highly conductive composite, dispersed with a high-pressure homogenizer, and the isopropanol dispersion of the highly conductive composite to which trioctylamine was added. Got

Next, 100 g of Art Resin UN-904M (manufactured by Negami Kogyo Co., Ltd., urethane acrylate, solid content 80%, methyl ethyl ketone solution), 300 g of pentaerythritol triacrylate, 25 g of hydroxyethyl acrylamide, 100 g of diacetone alcohol, and Irgacure 184 ( An organic solvent dispersion of a highly conductive composite obtained by adding 16.2 g of a photopolymerization initiator manufactured by BASF Co., Ltd. was applied onto a PET film (Lumilar T60 manufactured by Toray Co., Ltd.) using a # 8 bar coater. Was applied to the film, dried at 100 ° C. for 1 minute, and irradiated with ultraviolet rays of 400 mJ to obtain a conductive film. Table 2 shows the results of measuring this surface resistance value by the above method.

(Example 5)
A mixed solution prepared by adding 25 g of methanol and 200 g of methyl ethyl ketone to 100 g of the preparation solution of Production Example 2 was stirred at 60 ° C. for 3 hours. Next, the highly conductive complex composed of PEDOT-PSS precipitated in the mixed solution was collected by filtration and washed with 100 g of isopropanol to obtain 1.2 g of the highly conductive complex.
472.74 g of isopropanol and 1.06 g of trioctylamine were added to 1.2 g of the obtained highly conductive composite, dispersed with a high-pressure homogenizer, and the isopropanol dispersion of the highly conductive composite to which trioctylamine was added. Got A conductive film was prepared in the same manner as in Example 4 except that this dispersion was used, and the surface resistance value thereof was measured.

(Example 6)
A mixed solution prepared by adding 25 g of isopropanol, 200 g of methyl ethyl ketone, and 17.5 g of ethyl acetate to 100 g of the preparation solution of Production Example 2 was stirred at 60 ° C. for 3 hours. Next, the highly conductive complex composed of PEDOT-PSS precipitated in the mixed solution was collected by filtration and washed with 100 g of isopropanol to obtain 1.2 g of the highly conductive complex.
472.74 g of isopropanol and 1.06 g of trioctylamine were added to 1.2 g of the obtained highly conductive composite, dispersed with a high-pressure homogenizer, and the isopropanol dispersion of the highly conductive composite to which trioctylamine was added. Got A conductive film was prepared in the same manner as in Example 4 except that this dispersion was used, and the surface resistance value thereof was measured.

(Example 7)
A mixed solution prepared by adding 12.5 g of methanol and 200 g of methyl ethyl ketone to 100 g of the preparation solution of Production Example 2 was stirred at 60 ° C. for 3 hours. Next, the highly conductive complex composed of PEDOT-PSS precipitated in the mixed solution was collected by filtration and washed with 100 g of isopropanol to obtain 1.2 g of the highly conductive complex.
472.74 g of isopropanol and 1.06 g of trioctylamine were added to 1.2 g of the obtained highly conductive composite, dispersed with a high-pressure homogenizer, and the isopropanol dispersion of the highly conductive composite to which trioctylamine was added. Got A conductive film was prepared in the same manner as in Example 4 except that this dispersion was used, and the surface resistance value thereof was measured.

(Example 8)
A mixed solution prepared by adding 12.5 g of methanol and 200 g of methyl ethyl ketone to 100 g of the preparation solution of Production Example 2 was stirred at 60 ° C. for 3 hours. Next, the highly conductive complex composed of PEDOT-PSS precipitated in the mixed solution was collected by filtration and washed with 100 g of isopropanol to obtain 1.2 g of the highly conductive complex.
473.24 g of isopropanol and 0.56 g of tributylamine were added to 1.2 g of the obtained highly conductive composite and dispersed with a high-pressure homogenizer to obtain an isopropanol dispersion of the highly conductive composite to which tributylamine was added. rice field. A conductive film was prepared in the same manner as in Example 4 except that this dispersion was used, and the surface resistance value thereof was measured.

(Example 9)
A mixed solution prepared by adding 15.0 g of methanol and 200 g of methyl ethyl ketone to 100 g of the preparation solution of Production Example 2 was stirred at 60 ° C. for 3 hours. Next, the mixed solution was allowed to stand, and it waited for 1 hour until the highly conductive complex composed of PEDOT-PSS precipitated in the mixed solution naturally settled on the bottom of the container. Then, 200 g of the supernatant was removed by decantation, 300 g of isopropanol was added and stirred, and then the mixture was allowed to stand to allow the highly conductive complex to settle naturally. Then, 300 g of the supernatant was removed again by decantation, 300 g of isopropanol was added and stirred, and then the mixture was allowed to stand to allow the highly conductive complex to settle naturally. Then, 300 g of the supernatant was further removed by decantation to obtain 115 g of an isopropanol mixed solution containing a highly conductive complex.
To 115 g of the obtained isopropanol mixed solution containing the highly conductive complex, 358.94 g of isopropanol and 1.06 g of trioctylamine were added, dispersed with a high-pressure homogenizer, and the highly conductive composite to which trioctylamine was added. An isopropanol dispersion was obtained.
A conductive film was prepared in the same manner as in Example 4 except that this dispersion was used, and the surface resistance value thereof was measured.

(Example 10)
A mixed solution prepared by adding 12.5 g of methanol and 200 g of methyl ethyl ketone to 100 g of the preparation solution of Production Example 2 was stirred at 60 ° C. for 3 hours. Next, after confirming that the highly conductive composite composed of PEDOT-PSS was precipitated in the mixed solution, 5.0 g of trioctylamine was added to the mixed solution, and the highly conductive complex to which the trioctylamine was added was added. The sex complex was collected by filtration and washed with 100 g of methyl ethyl ketone to obtain 2.3 g of a highly conductive complex to which trioctylamine was added.
472.74 g of isopropanol was added to 2.3 g of the obtained highly conductive composite and dispersed with a high-pressure homogenizer to obtain an isopropanol dispersion of the highly conductive composite to which trioctylamine was added.
A conductive film was prepared in the same manner as in Example 4 except that this dispersion was used, and the surface resistance value thereof was measured.

(Comparative Example 5)
To 1.2 g of the freeze-dried PEDOT-PSS of Production Example 4, 472.74 g of isopropanol and 1.06 g of trioctylamine were added, dispersed with a high-pressure homogenizer, and the conductive composite to which trioctylamine was added. An isopropanol dispersion was obtained.
A conductive film was prepared in the same manner as in Example 4 except that this dispersion was used, and the surface resistance value thereof was measured.

From the above results, according to the method for producing a highly conductive composite according to the present invention, a highly conductive composite having excellent conductivity while being separated from impurities such as iron ions and counter anions of iron ions and an oxidizing agent can be obtained. I was able to sort it out. Since the separated highly conductive complex was hydrophilic, it could be easily dispersed in water. Further, if necessary, an amine compound could be added to the highly conductive complex to make it hydrophobic and easily dispersed in an organic solvent. Further, an amine compound could be added to the highly conductive complex precipitated in the mixed solution and separated.
It is clear that when the highly conductive composite according to the present invention is used, a conductive layer having excellent conductivity can be formed as compared with the case where the conventional conductive composite is used.

Claims (22)

A mixed solution obtained by mixing an organic solvent with a prepared solution containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, a transition metal ion, and an aqueous dispersion medium was obtained.
A method for producing a highly conductive complex, which comprises precipitating a highly conductive complex in the mixed solution and separating the precipitated highly conductive complex. The method for producing a highly conductive composite according to claim 1, wherein the content of the organic solvent contained in the mixed solution is 50% by mass or more with respect to the total mass of the mixed solution. The method for producing a highly conductive composite according to claim 1 or 2, wherein the organic solvent contains at least one of a ketone solvent and an alcohol solvent. The method for producing a highly conductive composite according to claim 3, wherein the organic solvent contains a ketone solvent, and the ketone solvent contains methyl ethyl ketone. The method for producing a highly conductive composite according to claim 3, wherein the organic solvent contains an alcohol solvent and the alcohol solvent contains methanol. The method for producing a highly conductive complex according to claim 1 or 2, wherein the organic solvent contains methyl ethyl ketone and methanol. The method for producing a highly conductive complex according to claim 1 or 2, wherein the organic solvent contains isopropanol and ethyl acetate. The method for producing a highly conductive complex according to claim 7, wherein the organic solvent contains methyl ethyl ketone. Any one of claims 1 to 8, wherein when the highly conductive composite precipitated in the mixed solution is separated, the transition metal ion contained in the mixed solution and the highly conductive composite are separated. The method for producing a highly conductive composite according to. The item according to any one of claims 1 to 9, wherein when the highly conductive composite is precipitated in the mixed solution, the mixed solution contains at least one of a counter anion of the transition metal ion and an oxidizing agent. The method for producing a highly conductive composite according to the above. The method for producing a highly conductive complex according to any one of claims 1 to 10, wherein the method for separating the highly conductive complex precipitated in the mixed solution is filtration or decantation. The method for producing a highly conductive composite according to any one of claims 1 to 11, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). The method for producing a highly conductive complex according to any one of claims 1 to 12, wherein the polyanion is polystyrene sulfonic acid. A mixed solution obtained by mixing an organic solvent with a prepared solution containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, a transition metal ion, and an aqueous dispersion medium was obtained.
After precipitating the highly conductive complex in the mixed solution,
A method for producing a highly conductive complex, which comprises adding an amine compound to the mixed solution containing the highly conductive complex and preparating the highly conductive complex to which the amine compound is added. Production of an aqueous dispersion of a highly conductive composite, which comprises mixing the highly conductive composite obtained by the production method according to any one of claims 1 to 13 with a water-containing aqueous solvent. Method. The method for producing an aqueous dispersion of a highly conductive complex according to claim 15, further comprising mixing a binder component. An organic solvent dispersion of a highly conductive composite, which comprises mixing the highly conductive composite obtained by the production method according to any one of claims 1 to 13, an organic solvent, and an amine compound. Production method. A method for producing an organic solvent dispersion of a highly conductive complex, which comprises mixing the highly conductive complex obtained by the production method according to claim 14 with an organic solvent. The method for producing an organic solvent dispersion of a highly conductive complex according to claim 17 or 18, further comprising mixing a binder component. The method for producing an organic solvent dispersion of a highly conductive composite according to claim 19, wherein the binder component is a compound that forms an acrylic resin after curing. The aqueous dispersion of a highly conductive composite obtained by the production method according to claim 15 or 16 on at least one surface of the film substrate, or the production method according to any one of claims 17 to 20. A method for producing a conductive film, which comprises applying an organic solvent dispersion liquid of the highly conductive composite obtained in the above method and drying the formed coating film. Either a conductive layer made of a cured layer of an aqueous dispersion of a highly conductive composite obtained by the production method according to claim 15 or 16 on at least one surface of the film substrate, or any of claims 17 to 20. A conductive film provided with a conductive layer composed of a cured layer of an organic solvent dispersion of a highly conductive composite obtained by the production method according to item 1.