JP2023088374A - Conductive polymer-containing solution and method for producing the same and conductive laminate and method for producing the same - Google Patents

Abstract

To provide a conductive polymer-containing solution which can be stably stored even in storage environments approximately at 40°C and a method for producing the same and to provide a conductive laminate and a method for producing the same.SOLUTION: There is provided a conductive polymer-containing solution which contains a conductive composite body containing a π-conjugated conductive polymer and a polyanion, the polyanion which does not form the conductive composite body, a molecular weight maintaining agent for suppressing the reduction of the molecular weight of the polyanion which does not form the conductive composite body and a dispersion medium, wherein when the initial weight average molecular weight of the polyanion which does not form the conductive composite body is defined as X and the weight average molecular weight of the polyanion which does not form the conductive composite body after the conductive polymer-containing solution is allowed to stand at 40°C for 720 hours is defined as Y, the molecular weight ratio represented by Y/X is 0.94 or more.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a conductive polymer-containing liquid containing a π-conjugated conductive polymer, a method for producing the same, and a conductive laminate and a method for producing the same.

A π-conjugated conductive polymer whose main chain is composed of a π-conjugated system forms a conductive composite when doped with a polyanion having an anion group, and has dispersibility in water. Manufacture of a conductive film having a conductive layer by applying a conductive polymer-containing liquid (also referred to as a conductive polymer dispersion) containing a conductive composite to a film substrate or the like. can be done. In addition, the conductive composite may be reacted with an epoxy compound for the purpose of increasing the wettability of the conductive polymer-containing liquid to the film substrate or increasing the conductivity of the conductive layer to be formed. For example, Patent Document 1 discloses a method for improving the conductivity of a conductive composite by reacting a cyclic epoxy compound.

Japanese Patent Application Laid-Open No. 2020-111650

By the way, after a storage period of about 30 days (720 hours) after the production of the conductive polymer-containing liquid, the characteristics of the conductive layer formed from the coating film of the conductive polymer-containing liquid may change. This change includes, for example, a decrease in resistance to atmospheric exposure.
When the inventors investigated the cause of this change, it was considered that the temperature during storage affected the change, since the change was likely to occur in lots manufactured in the summer. As a result of confirming this, it was found that there was little change even after 720 hours of storage at room temperature of about 25°C, but that there was a change after 720 hours of storage in a room that reached about 40°C.
Next, when the components contained in the conductive polymer-containing liquid before and after the change were analyzed, a decrease in the weight average molecular weight (lower molecular weight) of the single polyanion that did not form the conductive complex occurred. I found out.
Furthermore, by adding an agent (molecular weight maintaining agent) that suppresses the reduction of the molecular weight to the conductive polymer-containing liquid, even after storage at 40 ° C. for 720 hours, the molecular weight of the single polyanion does not decrease, and the formation It was also found that the characteristics of the conductive layer formed by this method did not change at all.

Through the above studies, the present invention provides a conductive polymer-containing liquid that can be stably stored even in a storage environment of about 40° C., a method for producing the same, and a conductive laminate and a method for producing the same.

[1] A conductive complex containing a π-conjugated conductive polymer and a polyanion, the polyanion that does not form the conductive complex, and the reduction in the molecular weight of the polyanion that does not form the conductive complex and a conductive polymer-containing liquid containing a dispersion medium, wherein the initial weight average molecular weight of the polyanion that does not form the conductive complex is X, and The molecular weight ratio represented by Y/X is 0.94 or more, where Y is the weight-average molecular weight of the polyanion that does not form the conductive complex after the liquid has been allowed to stand at 40° C. for 720 hours. A liquid containing a conductive polymer.
[2] The conductive polymer-containing liquid according to [1], wherein the molecular weight maintaining agent contains a basic compound.
[3] The conductive polymer-containing liquid according to [1] or [2], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene).
[4] The conductive polymer-containing liquid according to any one of [1] to [3], wherein the polyanion is polystyrenesulfonic acid.
[5] Precipitating a reaction product containing the conductive composite by adding an epoxy compound to the conductive polymer-containing liquid according to any one of [1] to [4]; A method for producing a conductive polymer-containing liquid, comprising recovering the precipitated reaction product and adding an organic solvent.
[6] A reaction product containing the conductive composite by adding an amine compound or a quaternary ammonium compound to the conductive polymer-containing liquid according to any one of [1] to [4]. and collecting the precipitated reaction product and adding an organic solvent.
[7] The conductive composite is formed by adding an epoxy compound and an amine compound or a quaternary ammonium compound to the conductive polymer-containing liquid according to any one of [1] to [4]. A method for producing a conductive polymer-containing liquid, comprising precipitating a reaction product containing the liquid, collecting the precipitated reaction product, and adding an organic solvent.
[8] A substrate, and a conductive layer formed of a cured layer of the conductive polymer-containing liquid according to any one of [1] to [4] formed on at least a part of the surface of the substrate; A conductive laminate comprising:
[9] a step of obtaining a conductive polymer-containing liquid by the production method according to any one of [5] to [7]; A method for manufacturing a conductive laminate, comprising the step of machining.
[10] The method for producing a conductive laminate according to [9], wherein the substrate is a film substrate.

The conductive polymer-containing liquid of the present invention can be stably stored even in a storage environment of about 40°C.
According to the method for producing a conductive polymer-containing liquid of the present invention, a paint containing a conductive composite dispersed in an organic solvent can be easily produced.
In the electroconductive laminate of the present invention, the electroconductive layer is sufficiently resistant to atmospheric exposure.
According to the method for producing a conductive laminate of the present invention, it is possible to easily produce a conductive laminate having a conductive layer with sufficient atmospheric exposure resistance.

The present invention is considered to contribute to SDGs Goal 12 “Responsible consumption and production”.

In the present specification and claims, the lower limit and upper limit of the numerical range indicated by "-" shall be included in the numerical range.

≪Liquid containing conductive polymer≫
A first aspect of the present invention is a conductive complex containing a π-conjugated conductive polymer and a polyanion, and the polyanion that does not form the conductive complex (hereinafter, sometimes referred to as a "single polyanion". ), a molecular weight-maintaining agent for suppressing the reduction of the molecular weight of the single polyanion, and a dispersion medium.

In the conductive polymer-containing liquid of this aspect, the conductive composite may be in a dispersed state or in a dissolved state. In this specification, unless otherwise stated, no distinction is made between the dispersed state and the dissolved state.

<π-conjugated conductive polymer>
The π-conjugated conductive polymer is not particularly limited as long as it is an organic polymer whose main chain is composed of a π-conjugated system, as long as it has the effect of the present invention. conductive polymer, polyacetylene-based conductive polymer, polyphenylene-based conductive polymer, polyphenylene vinylene-based conductive polymer, polyaniline-based conductive polymer, polyacene-based conductive polymer, polythiophene vinylene-based conductive polymer, and These copolymers and the like are included. Polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferable from the viewpoint of stability in air, and polythiophene-based conductive polymers are more preferable from the viewpoint of transparency.

Polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), and poly(3-hexylthiophene). , poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly (3-chlorothiophene), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene) , poly(3-hydroxythiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene) , poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3 ,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene) , poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-didodecyloxythiophene), poly( 3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3- methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxy butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), 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).
Polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid).
Among the above π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred from the viewpoint of conductivity, transparency and heat resistance.
The π-conjugated conductive polymer contained in the conductive composite may be of one type or two or more types.

<Polyanion>
A polyanion is a polymer having two or more monomer units having an anionic group in its molecule. The anionic group of this polyanion functions as a dopant for the π-conjugated conductive polymer and can improve the conductivity of the π-conjugated conductive polymer.
The anionic group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyacrylic acid esters having a sulfo group, polymethacrylic acid esters having a sulfo group (e.g., poly(4-sulfobutyl methacrylate) , polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polymers having a sulfo group such as polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, Polymers having a carboxyl group such as polyallylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, etc. These homopolymers can be used. It may be a copolymer of two or more kinds.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be further increased.
The polyanion may be of one type, or two or more types.

A polyanion forms a conductive complex by doping a π-conjugated conductive polymer. However, in the polyanions forming the conductive complex, some anionic groups do not dope the π-conjugated conductive polymer and have surplus anionic groups that do not participate in the doping. Since the surplus anionic groups are hydrophilic groups, the conductive composite has high water dispersibility and low organic solvent dispersibility.
When the number of all anionic groups possessed by the polyanion forming the conductive composite is 100 mol%, the excess anionic group is preferably 30 mol% or more and 90 mol% or less, and 45 mol% or more and 75 mol% or less. more preferred.

The content 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, more preferably 10 parts by mass or more and 700 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer. More preferably 100 parts by mass or more and 500 parts by mass or less. If the polyanion content is at least the above lower limit, the doping effect on the π-conjugated conductive polymer tends to be stronger, resulting in higher conductivity. On the other hand, if the polyanion content is equal to or less than the above upper limit, the π-conjugated conductive polymer can be sufficiently contained, and sufficient conductivity can be ensured.

Filtration treatment of the conductive polymer-containing liquid of this embodiment makes it possible to separate the polyanion forming the conductive complex from the polyanion not forming the conductive complex (single polyanion). That is, while the conductive complexes are trapped in the filter, single polyanions can be permeated and collected in the filtrate. It is preferable to use a membrane filter with an average pore size of 0.2 μm for filtration.

The weight-average molecular weight of a single polyanion is the weight-based average molecular weight (also referred to as weight-average molecular weight) measured by gel permeation chromatography and obtained using pullulan with a known weight-average molecular weight as a standard substance.

In the conductive polymer-containing liquid of this embodiment, regarding the weight average molecular weight of a single polyanion, X is the initial weight average molecular weight before standing at 40°C for 720 hours, and after standing at 40°C for 720 hours. The molecular weight ratio represented by Y/X is 0.94 or more, where Y is the weight average molecular weight of the compound. The closer the molecular weight ratio is to 1.0, the higher the storage stability during the stationary period. Moreover, even after a storage period of 720 hours at 40° C., a conductive layer having excellent resistance to atmospheric exposure can be formed.

In the present specification and claims, the effective digits of the molecular weight ratio (Y/X) shall be two digits. For example, the calculated value 0.94791666 of Y/X=91,000/96,000 is rounded off to the third decimal place to be 0.95. Here, the effective number of each weight average molecular weight may be two digits.

The weight average molecular weight X of the single polyanion is preferably 80,000 or more and 800,000 or less, more preferably 90,000 or more and 700,000 or less, further preferably 95,000 or more and 600,000 or less, and 95,000 or more. 500,000 or less is particularly preferable, and 95,000 or more and 400,000 or less is most preferable.
When it is at least the lower limit of the above range, the conductivity of the conductive layer formed from the conductive polymer-containing liquid can be increased while suppressing gelation of the conductive polymer-containing liquid. Also, a conductive polymer-containing liquid having a desired Y/X ratio can be easily obtained.
When it is at most the upper limit of the above range, the dispersibility of the polyanion in the conductive polymer-containing liquid increases, and the conductivity of the conductive layer can be further increased.

The content of a single polyanion with respect to the total mass of the conductive polymer-containing liquid of this embodiment can be, for example, 0.01% by mass or more and 2.5% by mass or less, and 0.05% by mass or more and 2.0% by mass. % or less, more preferably 0.1 mass % or more and 1.5 mass % or less, and even more preferably 0.5 mass % or more and 1.0 mass % or less.
When it is at least the lower limit of the above range, the resistance to atmospheric exposure of the conductive layer to be formed will be higher.
If it is equal to or less than the upper limit of the above range, the conductivity of the conductive layer to be formed will be higher.

The content of a single polyanion in the conductive polymer-containing liquid of this embodiment can be, for example, 1 part by mass or more and 10000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer. 10 parts by mass or more and 1000 parts by mass or less is more preferable, and 50 parts by mass or more and 500 parts by mass or less is even more preferable.
When it is at least the lower limit of the above range, the resistance to atmospheric exposure of the conductive layer to be formed will be higher.
If it is equal to or less than the upper limit of the above range, the conductivity of the conductive layer to be formed will be higher.

The content of the conductive composite with respect to the total mass of the conductive polymer-containing liquid of this embodiment can be, for example, 0.01% by mass or more and 10.0% by mass or less, and can be 0.05% by mass or more and 7.5% by mass. % by mass or less is preferable, 0.1% by mass or more and 5.0% by mass or less is more preferable, and 0.5% by mass or more and 2.5% by mass or less is even more preferable.
If it is at least the lower limit of the above range, the conductivity of the conductive layer to be formed will be higher.
When it is equal to or less than the upper limit of the above range, the dispersibility of the conductive composite in the conductive polymer-containing liquid can be enhanced, and a uniform conductive layer can be formed.

The content of the π-conjugated conductive polymer relative to the total mass of the conductive polymer-containing liquid of this embodiment can be, for example, 0.1% by mass or more and 2.0% by mass or less.
The total content of polyanions can be, for example, 0.3% by mass or more and 10% by mass or less with respect to the total mass of the conductive polymer-containing liquid of this embodiment. Here, the polyanion does not distinguish between those that form a conductive complex and those that do not.
The content ratio of the π-conjugated conductive polymer and the polyanion contained in the conductive polymer-containing liquid of the present embodiment is preferably (1:2) to (1:5) on a mass basis, and (1:2) to ( 1:4) is more preferred, and (1:2) to (1:3) are even more preferred. Here, the polyanion does not distinguish between those that form a conductive complex and those that do not.

<Molecular weight maintenance agent>
The conductive polymer-containing liquid of this embodiment contains a molecular weight-maintaining agent that suppresses the reduction of the molecular weight of a single polyanion.
The molecular weight-maintaining agent should have a molecular weight ratio Y/X with respect to the weight-average molecular weight of a single polyanion of 0.94 or more before and after the conductive polymer-containing liquid of this embodiment is left to stand at 40° C. for 720 hours. It is a drug that can

The molecular weight maintenance agent preferably contains a basic compound. Here, the basic compound is a compound capable of accepting a proton of an excess anionic group that does not participate in the doping of the polyanion, and is preferably a compound having an electron pair for accepting the proton. Although the detailed mechanism has not been elucidated, the inclusion of the basic compound facilitates making the molecular weight ratio represented by Y/X 0.94 or more.
Examples of the basic compound that can be used include nitrogen-containing organic or inorganic basic compounds, hydroxides of alkali metals or group 2 metals, and various carbonates and hydrogencarbonates. Examples thereof include alkali metal hydroxides, quaternary ammonium hydroxides or salts thereof, ammonia, and amines.
Specific examples of alkali metal hydroxides include potassium hydroxide and sodium hydroxide.
Specific examples of carbonates or hydrogencarbonates include ammonium hydrogencarbonate, ammonium carbonate, potassium hydrogencarbonate, potassium carbonate, sodium hydrogencarbonate, sodium carbonate and the like.
Specific examples of quaternary ammonium hydroxides or salts thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and the like.
Examples of amines include aliphatic tertiary amines and nitrogen-containing heterocyclic aromatic compounds. Aliphatic tertiary amines include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine. Nitrogen-containing heterocyclic aromatic compounds include pyrrole, indole, imidazole, pyridine, pyrimidine, pyrazine and alkyl-substituted products thereof (e.g., alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, substituted), halogen-substituted (for example, substituted with a halogen group such as fluoro, chloro, or bromo), nitrile-substituted, and the like.

The basic compound is preferably a water-soluble compound having a solubility of 1 g or more in 100 g of water at 20° C., more preferably a water-soluble compound containing a nitrogen atom, and containing a nitrogen atom and having 3 to 3 carbon atoms in the molecule. Water-soluble compounds that are 6 are more preferred.
Among the above examples, imidazole, triethylamine, and triethanolamine are particularly preferred.
The number of basic compounds contained in the conductive polymer-containing liquid of this embodiment may be one, or two or more.

The content of the basic compound with respect to the total mass of the conductive polymer-containing liquid of this embodiment can be, for example, 0.01% by mass or more and 10% by mass or less, and can be 0.05% by mass or more and 4.0% by mass. The following are preferable, 0.1 to 3.0 mass % is more preferable, and 0.3 to 2.0 mass % is even more preferable.
When it is at least the lower limit of the above range, a conductive polymer-containing liquid in which the molecular weight ratio Y/X of the single polyanions is at least a predetermined value can be easily obtained. Moreover, the conductivity of the conductive layer to be formed can be further improved. The upper limit of the above range is one standard.

The content ratio of the basic compound contained in the conductive polymer-containing liquid of this embodiment can be, for example, 0.1 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of a single polyanion. 5 parts by mass to 500 parts by mass is preferable, 1 part by mass to 100 parts by mass is more preferable, and 5 parts by mass to 50 parts by mass is even more preferable.
Within the above range, it is possible to easily obtain a conductive polymer-containing liquid in which the molecular weight ratio Y/X of a single polyanion exhibits a predetermined value or more.

The content ratio of the basic compound contained in the conductive polymer-containing liquid of the present embodiment is, for example, 1.0 parts by mass with respect to a total of 100 parts by mass of the polyanion forming the conductive complex and the single polyanion. 1000 parts by mass or less, preferably 5.0 parts by mass or more and 500 parts by mass or less, more preferably 10 parts by mass or more and 300 parts by mass or less, and even more preferably 20 parts by mass or more and 200 parts by mass or less.
Within the above range, it is possible to easily obtain a conductive polymer-containing liquid in which the molecular weight ratio Y/X of a single polyanion exhibits a predetermined value or more.

[Dispersion medium]
Examples of the dispersion medium contained in the conductive polymer-containing liquid of this embodiment include water, organic solvents, and mixtures of water and organic solvents. The molecular weight maintenance agent does not correspond to the dispersion medium.

Examples of organic solvents include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents. A specific example will be described later.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.

Since the conductive composite has high dispersibility in water, the dispersion medium of the conductive polymer-containing liquid of this embodiment is preferably an aqueous dispersion medium containing water.
The content of water in the total dispersion medium contained in the conductive polymer-containing liquid of the present embodiment can be, for example, 50% by mass or more and 100% by mass or less, preferably 60% by mass or more and 100% by mass or less, and 70% by mass. % or more and 100 mass % or less is more preferable. A monohydric alcohol is preferable as a dispersion medium other than water.

<Optional component>
The conductive polymer-containing liquid of this embodiment may further contain a binder component and other additives.

(Other additives)
Additives are not particularly limited as long as the effects of the present invention can be obtained, and for example, surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, ultraviolet absorbers and the like can be used.
Examples of surfactants include nonionic, anionic, and cationic surfactants, with nonionic surfactants being preferred from the standpoint of storage stability. A polymeric surfactant such as polyvinylpyrrolidone may also be added.
Examples of inorganic conductive agents include metal ions and conductive carbon. Metal ions can be generated by dissolving a metal salt in water.
Antifoaming agents include silicone resins, polydimethylsiloxane, silicone oils and the like.
Examples of coupling agents include silane coupling agents having a vinyl group or an amino group.
Antioxidants include phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, sugars and the like.
UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. are mentioned.
When the conductive polymer-containing liquid of this embodiment contains the above additives, the content ratio thereof can be appropriately determined according to the type of additive. It can be in the range of 0.001 parts by mass or more and 5 parts by mass or less.

<<Method for producing liquid containing conductive polymer (1)>>
The conductive polymer-containing liquid of the first aspect can be produced, for example, by a production method including the polymerization step described below.
In the polymerization step, a conductive composite containing the π-conjugated conductive polymer and the polyanion is formed by polymerizing a monomer forming the π-conjugated conductive polymer in a reaction liquid containing a polyanion and an aqueous dispersion medium. It is a step of obtaining a conductive polymer-containing liquid containing a solid, the aqueous dispersion medium, and the polyanion that does not form the conductive complex (single polyanion).
By adding a molecular weight maintaining agent to the conductive polymer-containing liquid obtained in the polymerization step, the conductive polymer-containing liquid of the first embodiment can be obtained.

The weight average molecular weight (Mw) of the polyanion to be subjected to the polymerization step is preferably 80,000 to 1,000,000, more preferably 100,000 to 800,000, and even more preferably 150,000 to 600,000. Here, the weight-average molecular weight is a weight-based average molecular weight measured by gel permeation chromatography (GPC) and obtained using pullulan having a known weight-average molecular weight as a standard substance.
When the weight average molecular weight is within the above preferred range, the conductivity of the conductive layer is further increased.
Before subjecting the polyanion aqueous solution to GPC, it is preferable to filter the aqueous solution with a membrane filter having an average pore size of 0.2 μm and subject the filtrate to GPC measurement for the purpose of removing impurities contained in the aqueous solution.

A method for synthesizing a polyanion having a specific weight-average molecular weight includes, for example, a method of adjusting the amount of an oxidizing agent added to polymerize the monomers constituting the polyanion. Specifically, increasing the concentration of the oxidizing agent can decrease the weight-average molecular weight of the polyanion formed by polymerization of the monomers. By this method, for example, polystyrene sulfonic acid having a weight average molecular weight Mw of 100,000 or more and 1,000,000 or less can be obtained.

[Polymerization step]
A π-conjugated conductive polymer is formed by preparing a reaction solution containing a monomer forming the π-conjugated conductive polymer and the polyanion in an arbitrary content ratio, and polymerizing the monomer. In the reaction solution, the π-conjugated conductive polymer is naturally doped with the polyanion to form a conductive complex composed of the π-conjugated conductive polymer and the polyanion. Also, some of the polyanions do not form conductive complexes and remain as single polyanions.

A catalyst may be added to the reaction solution. The catalyst is not particularly limited as long as it promotes polymerization of the monomer, and examples thereof include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride. . Among them, it is preferable to use a catalyst containing iron because the polymerization of the monomer proceeds stably at room temperature.

It is preferable that the reaction liquid contains an oxidizing agent together with the catalyst. The oxidizing agent can polymerize the monomer. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate.
Preferably, the oxidizing agent is dissolved in ion-exchanged water in advance as an oxidizing agent solution and slowly added to the mixed solution S1 containing the monomer, the polyanion, and the catalyst to initiate polymerization.
The concentration of the oxidant solution is preferably 1.0% by mass or more and 3.0% by mass or less.
When the volume of the mixed solution S1 before the addition of the oxidizing agent solution is V1 and the volume of the oxidizing agent solution is V2, the volume ratio represented by V1/V2 is preferably 1.0 to 2.0. , 1.2 to 1.5 are more preferred.
When all of the oxidant solution is added to the mixed solution S1, the time required from the start of addition to the end of addition is preferably 1 to 8 hours, more preferably 2 to 7 hours, and even more preferably 3 to 6 hours.
The temperature of each of the mixed solution S1 before adding the oxidant solution and the temperature of the oxidant solution is preferably 5 to 30° C. independently.

It is preferable to carry out the polymerization reaction while maintaining the temperature of the reaction solution obtained after the addition of all of the oxidant solution at 5 to 30°C.
The standard reaction time required for completion of the reaction in the reaction solution is 4 to 12 hours, preferably 6 to 10 hours. The completion of the polymerization reaction can be known by confirming disappearance of the monomer forming the π-conjugated conductive polymer by gas chromatography.

The content ratio of the monomer to the polyanion contained in the mixed solution S1 is preferably (1:2) to (1:5), more preferably (1:2) to (1:4) on a mass basis, and ( 1:2) to (1:3) are more preferred.
When it is at least the lower limit of the above range, the doping effect of the polyanion is sufficiently exhibited, and the dispersion stability of the conductive composite is further improved.
When it is at most the upper limit of the above range, a conductive polymer-containing liquid capable of forming a conductive layer with excellent conductivity can be easily obtained. Also, a conductive polymer-containing liquid having a desired Y/X ratio can be easily obtained.

The content of the monomer with respect to the total mass of the mixture S1 is, for example, preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 5.0% by mass or less, and 0.3% by mass. % or more and 1.0 mass % or less is more preferable.
Within the above range, the polymerization reaction can be stably proceeded, so that complexing with the polyanion present in the reaction system proceeds easily. Also, a conductive polymer-containing liquid having a desired Y/X ratio can be easily obtained.

The content of the polyanion with respect to the total mass of the mixture S1 is preferably set based on the content ratio with respect to the monomer. For example, it is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 8.0% by mass or less, and even more preferably 0.6% by mass or more and 4.0% by mass or less.
Within the above range, a conductive polymer-containing liquid having a desired Y/X ratio can be easily obtained.

The weight-average molecular weight of the polyanion contained in the mixture S1 is preferably within the range described above.
Within the above range, a conductive polymer-containing liquid having a desired Y/X ratio can be easily obtained.

The content of the catalyst with respect to the total mass of the reaction solution to which all the oxidizing agents have been added is, for example, preferably 0.001% by mass or more and 2.0% by mass or less with respect to the total mass of the reaction solution, 0.01% by mass or more and 1.0% by mass or less is more preferable, and 0.1% by mass or more and 0.5% by mass or less is even more preferable.
Within the above range, the polymerization reaction can proceed stably, so that complexing with the polyanion proceeds easily. Also, a conductive polymer-containing liquid having a desired Y/X ratio can be easily obtained.

The amount of the oxidizing agent added to the total mass of the reaction solution to which the oxidizing agent has been completely added is, for example, preferably 0.01% by mass or more and 2.0% by mass or less, and 0.1% by mass or more and 1.5% by mass. % by mass or less is more preferable, 0.5% by mass or more and 1.2% by mass or less is even more preferable, and 0.7% by mass or more and 1.0% by mass or less is particularly preferable.
Within the above range, the polymerization reaction can proceed stably, so that complexing with the polyanion proceeds easily. Also, a conductive polymer-containing liquid having a desired Y/X ratio can be easily obtained.

The amount of the monomer charged before the reaction is preferably 0.05% by mass or more and 5.0% by mass or less, and 0.1% by mass or more and 3 0% by mass or less is more preferable, and 0.2% by mass or more and 2.0% by mass or less is even more preferable.
Within the above range, the polymerization reaction can be stably proceeded, so that complexing with the polyanion present in the reaction system proceeds easily. Also, a conductive polymer-containing liquid having a desired Y/X ratio can be easily obtained.

The amount of the polyanion charged before the reaction with respect to the total mass of the reaction solution to which all the oxidizing agents have been added is, for example, preferably 0.1% by mass or more and 10% by mass or less, and 0.3% by mass or more and 6.0% by mass. % by mass or less is more preferable, and 0.5% by mass or more and 4.0% by mass or less is even more preferable.
Within the above range, a conductive polymer-containing liquid having a desired Y/X ratio can be easily obtained.

The aqueous dispersion medium constituting the reaction liquid contains at least water and may further contain a water-soluble organic solvent. Specific examples of the water-soluble organic solvent will be described later.
The water content relative to the total mass of the aqueous dispersion medium is, for example, preferably 60% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and even more preferably 80% by mass or more and 100% by mass or less. , 90% by mass or more and 100% by mass or less is particularly preferable.

(Removal of catalyst and oxidant)
When a reaction solution containing a catalyst and an oxidant is used, it is preferable to remove the catalyst and the oxidant from the conductive polymer-containing solution obtained after the reaction.
As a method for removing, for example, a method of contacting a conductive polymer-containing liquid with an ion-exchange resin to adsorb the catalyst and the oxidizing agent to the ion-exchange resin, and an aqueous dispersion by ultrafiltration of the conductive polymer-containing liquid For example, a method of removing with replacement of the medium can be mentioned. Among these, the method of using an ion exchange resin is preferable because it is simple. The ion exchange resin is preferably a combination of a cation exchange resin and an anion exchange resin.

(Distributed processing)
It is preferable to stir the conductive polymer-containing liquid obtained in the polymerization step and perform a dispersion treatment of the conductive composite. The method of stirring is not particularly limited, and may be stirring with a weak shear force such as a stirrer, or may be stirred using a disperser with a high shear force such as a high-pressure homogenizer, from the viewpoint of improving dispersibility. It is preferable to use a high-pressure homogenizer or the like.

By the above polymerization step, a conductive composite containing a π-conjugated conductive polymer and a polyanion, the aqueous dispersion medium, and the polyanion (single polyanion) that does not form the conductive composite, A conductive polymer-containing liquid is obtained.

It is preferable to separate a single polyanion from the obtained conductive polymer-containing liquid and then measure the weight average molecular weight X thereof, because it can be accurately measured without being affected by the conductive complex.
As the separation method, for example, the conductive polymer-containing liquid is filtered using a membrane filter having an average pore size of 0.2 μm, the conductive complex is trapped in the filter, and a single polyanion is allowed to permeate, and the filtrate is filtered. There is a method of collecting inside.

The weight-average molecular weight X of a single polyanion is a weight-based average molecular weight measured by gel permeation chromatography and determined using pullulan having a known weight-average molecular weight as a standard substance.

The weight average molecular weight X of the single polyanion is preferably smaller than the weight average molecular weight Z of the polyanion subjected to the polymerization step. A ratio represented by X/Z between the weight average molecular weight X and the weight average molecular weight Z can be, for example, 0.1 or more and less than 0.67.

The method of adding the molecular weight-maintaining agent to the conductive polymer-containing liquid obtained in the polymerization step is not particularly limited.
The conductive polymer-containing liquid to which the molecular weight maintaining agent has been added may be subjected to the deposition/recovery step described below.

<<Method for producing conductive polymer-containing liquid (2)>>
In a second aspect of the present invention, the conductive composite is obtained by adding one or more selected from an epoxy compound, an amine compound, and a quaternary ammonium compound to the conductive polymer-containing liquid of the first aspect. (precipitation step), and recovering the precipitated reaction product and adding an organic solvent (recovery step). .

[Precipitation process]
The conductive polymer-containing liquid of the first aspect (hereinafter sometimes referred to as a conductive polymer dispersion) can be obtained, for example, by the above-described production method including the polymerization step. By adding one or more selected from an epoxy compound, an amine compound and a quaternary ammonium compound to the conductive polymer dispersion, a reaction product containing the conductive composite can be precipitated. A single polyanion that does not form a conductive complex reacts similarly and precipitates.
The anionic group such as sulfonic acid group of the reaction product precipitated in this step reacts with the added compound to form any one of the following substituents (A) to (C) to be hydrophobized. there is

Excess anionic groups of the polyanion that do not participate in doping are sometimes referred to as "partial anionic groups" below.
The following substituent (A) is formed by the reaction of some anionic groups with the epoxy compound.
Substituent (B) below is formed by the reaction of some of the anionic groups with the amine compound.
Substituent (C) below is formed by reaction of some anionic groups with quaternary ammonium compounds.

(Substituent A)
The substituent (A) is presumed to be a group represented by the following formula (A1) or a group represented by the following formula (A2).

[In Formula (A1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an arbitrary substituent. ]

[In the formula (A2), m is an integer of 2 or more, and the plurality of R ⁵ , the plurality of R ⁶ , the plurality of R ⁷ , and the plurality of R ⁸ are each independently a hydrogen atom or an arbitrary substituent, a plurality of R ⁵ may be the same or different; a plurality of R ⁶ may be the same or different; a plurality of R ⁷ may be the same or different; a plurality of R ⁸ may be the same or different; may ]

In formulas (A1) and (A2), the leftmost bond represents that the substituent (A) is substituted with a proton of an anionic group such as a sulfonic acid group.

In formula (A1), the optional substituents for R ¹ , R ² , R ³ and R ⁴ include an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent. Examples include an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be present. R ¹ and R ³ may combine to form a ring which may have a substituent. For example, R ¹ and R ³ are the above-mentioned hydrocarbon groups, a divalent hydrocarbon group excluding any one hydrogen atom of the monovalent hydrocarbon group of R ¹ , and a monovalent hydrocarbon group of R ³ A case where a divalent hydrocarbon group from which any one hydrogen atom is removed from the hydrogen group is combined with the carbon atoms from which the hydrogen atom is removed to form a ring is exemplified.
In formula (A2), the optional substituents for R ⁵ , R ⁶ , R ⁷ and R ⁸ include an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent. Examples include an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be present. R ⁵ and R ⁷ may combine to form a ring which may have a substituent. Examples of ring formation are the same as above.
Here, "optionally having a substituent" means a case where a hydrogen atom (--H) is substituted with a monovalent group, and a case where a methylene group ( _--CH.sub.2-- ) is substituted with a divalent group. Including both cases and
Monovalent groups as substituents include alkyl groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), and trialkoxysilyl groups. (trimethoxysilyl group, etc.), and the like.
The divalent group as a substituent includes an oxygen atom (-O-), -C(=O)-, -C(=O)-O- and the like.
m is an integer of 2 or more, preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 25. Hydrophobicity of the conductive composite becomes sufficiently high that m is at least the above lower limit. When m is equal to or less than the upper limit, it is possible to prevent the hydrophobicity from becoming too high and the conductivity from decreasing.

An epoxy compound is a compound having one or more epoxy groups in one molecule (epoxy group-containing compound). From the viewpoint of preventing aggregation or gelation, the epoxy compound is preferably a compound having one epoxy group in one molecule.
One type or two or more types of epoxy compounds that react with the partial anionic groups may be used.

Monofunctional epoxy compounds having one epoxy group in one molecule include, for example, ethylene oxide, propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, 1 ,2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monoxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2- epoxy octadecane, 1,2-epoxyhexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2-(chloromethyl)-1,2-epoxypropane, glycidol, epichlorohydrin, Epibromohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2-(chloromethyl)-1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2- epoxy-1H,1H,2H,2H,3H,3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-methyl-1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H,1H,2H,2H,3H, 3H-heptadecafluorobutane, 3,4-epoxytetrahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzyl glycidyl ether, diethoxy(3-glycidyloxypropyl)methylsilane, 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl- 3-(3-glycidyloxypropyl)trisiloxane, 9,10-epoxy-1,5-cyclododecadiene, glycidyl 4-tert-butylbenzoate, 2,2-bis(4-glycidyloxyphenyl)propane, 2 -tert-butyl-2-[2-(4-chlorophenyl)]ethyloxirane, styrene oxide, glycidyltrityl ether, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α , 6α-epoxide, stilbene oxide, glycidyl p-toluenesulfonate, ethyl 3-methyl-3-phenylglycidate, N-propyl-N-(2,3-epoxypropyl) perfluoro-n-octylsulfonamide, ( 2S,3S)-1,2-epoxy-3-(tert-butoxycarbonylamino)-4-phenylbutane, (R)-glycidyl 3-nitrobenzenesulfonate, glycidyl 3-nitrobenzenesulfonate, parthenolide, N-glycidyl phthalimide, endrin, dieldrin, 4-glycidyloxycarbazole, 7,7-dimethyloctanoic acid [oxiranylmethyl], 1,2-epoxy-4-vinylcyclohexane, higher alcohol glycidyl ether having 10 to 16 carbon atoms, and the like. be done.

As the higher alcohol glycidyl ether, one or more higher alcohol glycidyl ethers having 10 to 16 carbon atoms are preferable, and one or more higher alcohol glycidyl ethers having 12 to 14 carbon atoms are more preferable. At least one of alcohol glycidyl ether and C13 (13 carbon atoms) higher alcohol glycidyl ether is more preferable.

Examples of polyfunctional epoxy compounds having two or more epoxy groups in one molecule include 1,6-hexanediol diglycidyl ether, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, and 4-butanediol. diglycidyl ether, 1,2:3,4-diepoxybutane, diglycidyl 1,2-cyclohexanedicarboxylate, triglycidyl isocyanurate, neopentyl glycol diglycidyl ether, 1,2:3,4-diepoxybutane, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, Trimethylolpropane triglycidyl ether, trimethylolpropane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol poly glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, and the like.

The epoxy compound preferably has a molecular weight of 50 or more and 2,000 or less because it is highly dispersible in an organic solvent. In addition, the epoxy compound preferably has 4 to 120 carbon atoms, more preferably 7 to 100 carbon atoms, and more preferably has 10 carbon atoms, because of its high dispersibility in low-polar hydrocarbon solvents and ester solvents. 80 or less is more preferable, and 15 or more and 50 or less is particularly preferable.

(Substituent B)
The substituent (B) is presumed to be a group represented by the following formula (B).

-HN ⁺ R ¹¹ R ¹² R ¹³ (B)
[In formula (B), R ¹¹ to R ¹³ are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, provided that at least one of R ¹¹ to R ¹³ is a substituent is a hydrocarbon group which may have ]

In the substituent (B), the bond at the left end represents that the negative charge of the anion group, for example, the negative charge “—SO ₃ ⁻ ” of the sulfonic acid group, and the positive charge of the amine compound are bonded.

R ¹¹ to R ¹³ in the chemical formula (B) are hydrogen atoms or optionally substituted hydrocarbon groups. R ¹¹ to R ¹³ in chemical formula (B) are substituents derived from an amine compound to be described later.
The hydrocarbon group in the chemical formula (B) is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. groups.
Examples of aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups.
A phenyl group, a hydroxyl group, etc. are mentioned as a substituent of an aliphatic hydrocarbon group.
A phenyl group, a naphthyl group, etc. are mentioned as an aromatic-hydrocarbon group.
Substituents for the aromatic hydrocarbon group include alkyl groups having 1 to 5 carbon atoms, hydroxyl groups and the like.

The amine compound is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. The amine compound that reacts with the partial anionic group may be of one type, or may be of two or more types.
Examples of primary amines include aniline, toluidine, benzylamine, ethanolamine and the like.
Secondary amines include, for example, diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine and the like.
Tertiary amines include, for example, triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine.
Among the amine compounds, tertiary amines are preferable, and at least one of trioctylamine and tributylamine is more preferable, since they can enhance the electrical conductivity of the electrically conductive composite of the present embodiment.

Dispersibility in organic solvents, especially in low-polar hydrocarbon solvents and ester solvents increases, so the amine compound may have a substituent with 4 or more carbon atoms on the nitrogen atom. It preferably has 6 or more substituents, and more preferably has a substituent with 8 or more carbon atoms on the nitrogen atom. The upper limit of the carbon number of the substituent on the nitrogen atom is not particularly limited, and in consideration of solubility and reactivity in solvents, for example, 50 or less is preferable, 40 or less is more preferable, and 30 or less is even more preferable. .
The total number of carbon atoms of R ¹¹ to R ¹³ in the amine compound is preferably 6-33, more preferably 9-30, even more preferably 12-27.
The number of carbon atoms of each substituent on the nitrogen atom may be the same or different.

When some of the anionic groups have a substituent (A) and a substituent (B), the mass ratio represented by [substituent (A)]:[substituent (B)] (hereinafter referred to as A / B ratio) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, even more preferably 25:75 to 75:25. When the A/B ratio is within the above range, it becomes easier to balance dispersibility and conductivity. The mass of the [substituent (A)] is [(the mass of the reaction product A obtained by reacting the epoxy compound) - (the conductive composite before reacting with the epoxy compound and the conductive composite The mass of polyanions that do not have a mass)]. Further, the mass of the [substituent (B)] is calculated from [(the mass of the reaction product B obtained by reacting the reaction product A with the amine compound) - (the mass of the reaction product A)]. can do.

(Substituent C)
Substituent (C) is presumed to be a group represented by the following formula (C).

-N ⁺ R ¹¹ R ¹² R ¹³ R ¹⁴ (C)
[In Formula (C), R ¹¹ to R ¹⁴ are each independently a hydrocarbon group which may have a substituent. ]

In the substituent (C), the bond on the left end is the bond between the negative charge of the anion group, for example, the negative charge of the sulfonic acid group "—SO ₃ ^- " and the positive charge of the quaternary ammonium cation. show.

R ¹¹ to R ¹⁴ in chemical formula (C) are hydrocarbon groups which may have a substituent. R ¹¹ to R ¹⁴ in chemical formula (C) are substituents derived from a quaternary ammonium compound.
The hydrocarbon group in the chemical formula (C) is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. groups.
Examples of aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups.
A phenyl group, a hydroxyl group, etc. are mentioned as a substituent of an aliphatic hydrocarbon group.
A phenyl group, a naphthyl group, etc. are mentioned as an aromatic-hydrocarbon group.
Substituents for the aromatic hydrocarbon group include alkyl groups having 1 to 5 carbon atoms, hydroxyl groups and the like.

The quaternary ammonium compound preferably has a substituent having 3 or more carbon atoms on the nitrogen atom, and has a substituent of 5 or more, because the dispersibility in the organic solvent increases and the conductivity improves. It is more preferable to have a substituent having 7 or more carbon atoms on the nitrogen atom. The upper limit of the carbon number of each substituent on the nitrogen atom is not particularly limited, and in consideration of solubility and reactivity in solvents, for example, 40 or less is preferable, 30 or less is more preferable, and 20 or less is further. preferable.
The total number of carbon atoms of R ¹¹ to R ¹⁴ in the quaternary ammonium compound is preferably 8-44, more preferably 12-40, even more preferably 16-36.
The number of carbon atoms of each substituent on the nitrogen atom may be the same or different.

Specific examples of quaternary ammonium compounds include tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, tetra-n-octylammonium salts, tetraphenylammonium salts, tetrabenzylammonium salts, tetranaphthyl Quaternary ammonium salts such as ammonium salts are included.
Counter anions of ammonium cations include, for example, halogen ions such as bromide ions and chloride ions, and hydroxy ions.

When the conductive composite has a substituent (A) and a substituent (C), the mass ratio represented by [substituent (A)]:[substituent (C)] (hereinafter, A / C ratio is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 25:75 to 75:25. When the A/C ratio is within the above range, it becomes easier to balance dispersibility and conductivity. The mass of the [substituent (A)] is [(the mass of the reaction product A obtained by reacting with the epoxy compound) - (the conductive composite before reacting with the epoxy compound and the conductive composite is formed. The mass of polyanions that do not have a mass)]. Further, the mass of the [substituent (C)] is [(the mass of the reaction product C obtained by reacting the reaction product A with the quaternary ammonium compound) - (the mass of the reaction product A). ] can be calculated from

When one or more epoxy compounds are added to the conductive polymer dispersion, the amount of the epoxy compound to be added is determined by the amount of the π-conjugated conductive polymer and total polyanion (conductive composite (including the polyanion forming .
If it is at least the lower limit of the above range, the hydrophobicity of the conductive composite will be sufficiently high, and the dispersibility in organic solvents will be improved.
If it is equal to or less than the upper limit of the above range, it is possible to prevent a decrease in conductivity due to an unreacted epoxy compound.
When adding the epoxy compound, it may be heated to promote the reaction. The heating temperature is preferably 40° C. or higher and 100° C. or lower.

When one or more amine compounds are added to the conductive polymer dispersion, the amount of the amine compound added varies depending on the amount of the π-conjugated conductive polymer and all polyanions (conductive composites) contained in the conductive polymer dispersion. (including the polyanions forming the .
If it is at least the lower limit of the above range, the hydrophobicity of the conductive composite will be sufficiently high, and the dispersibility in organic solvents will be improved.
If it is at most the upper limit value of the above range, it is possible to prevent a decrease in conductivity due to an unreacted amine compound.

When one or more quaternary ammonium compounds are added to the conductive polymer dispersion, the amount of the quaternary ammonium compound added is 1 part by mass or more and 10000 parts by mass or less is preferable, 10 parts by mass or more and 5000 parts by mass or less is more preferable, and 50 parts by mass or more and 2000 parts by mass with respect to 100 parts by mass of the polyanion (including the polyanions forming the conductive complex). Part by mass or less is more preferable.
If it is at least the lower limit of the above range, the hydrophobicity of the conductive composite will be sufficiently high, and the dispersibility in organic solvents will be improved.
If it is at most the upper limit value of the above range, it is possible to prevent a decrease in conductivity due to unreacted quaternary ammonium compounds.
A quaternary ammonium compound has a reaction mechanism similar to that of an amine compound and exhibits good reactivity with a smaller addition amount than an amine compound. The conductivity of conductive layers comprising conductive composites modified with quaternary ammonium compounds tend to be superior to those modified with amine compounds.

An organic solvent may be added before, simultaneously with, or after adding one or more selected from epoxy compounds, amine compounds, and quaternary ammonium compounds to the conductive polymer dispersion. As the organic solvent, a water-soluble organic solvent is preferred. Examples of water-soluble organic solvents include alcohol-based solvents, ketone-based solvents, and ester-based solvents. The organic solvent to be added may be one kind, or two or more kinds.

When adding both the epoxy compound and the amine compound or the quaternary ammonium compound to the conductive polymer dispersion, the order of addition is not particularly limited. Since the synthetic intermediates (reaction intermediates) are easy to handle, it is preferable to first add and react the epoxy compound and then add and react the amine compound or the quaternary ammonium compound.

[Recovery process]
The method for collecting the precipitated reaction product is not particularly limited, and it can be collected by filtration, decantation, or the like, for example.

It is preferable that the recovered reaction product (precipitate) contains as little water as possible, and most preferably does not contain water at all.
Methods for reducing the water content include, for example, a method of washing away the reaction product with an organic solvent, a method of drying the reaction product, and the like.

[Washing process]
A washing step may be provided for washing the reaction product collected in the collecting step. This washing step removes residual water, unreacted epoxy compounds, unreacted amine compounds or quaternary ammonium compounds, hydrolysates of epoxy compounds, and the like.
The organic solvent for washing is preferably one that can be washed while minimizing the dissolution of reaction products. For this reason, an alcohol-based solvent is preferable as the organic solvent for cleaning. The number of organic solvents contained in the cleaning organic solvent may be one, or two or more.
The washing method is not particularly limited. For example, the reaction product may be washed by pouring a washing organic solvent over the reaction product, or the reaction product may be washed by stirring in the washing organic solvent. You may

[Addition process]
This step is a step of adding a dispersion medium to the reaction product to obtain a conductive polymer-containing liquid. The dispersion medium to be added may be any medium capable of dispersing the reaction product, and preferably contains an organic solvent.
When the conductive polymer-containing liquid contains a hydrophobized conductive composite, the content of the organic solvent with respect to the total mass of the dispersion medium is preferably 70% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass. % by mass or less is more preferable, and 90% by mass or more and 100% by mass or less is even more preferable.

The content of the reaction product with respect to the total mass of the conductive polymer-containing liquid obtained in this step is, for example, preferably 0.01% by mass or more and 10% by mass or less, and 0.1% by mass or more and 3% by mass or less. is more preferable, and 0.2% by mass or more and 1% by mass or less is even more preferable.
When it is at least the lower limit of the above range, the conductivity of the conductive layer formed by applying the conductive polymer-containing liquid can be further improved.
When it is equal to or less than the upper limit of the above range, the dispersibility of the reaction product in the conductive polymer-containing liquid can be enhanced, and a uniform conductive layer can be formed.

<Organic solvent>
Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, hydrocarbon-based solvents, and nitrogen atom-containing compound-based solvents. One type of the organic solvent may be used, or two or more types may be used.

The organic solvent may be a water-soluble organic solvent or a non-water-soluble organic solvent.
The water-soluble organic solvent is an organic solvent that dissolves 1 g or more in 100 g of water at 20°C, and the non-water-soluble organic solvent is an organic solvent that dissolves less than 1 g in 100 g of water at 20°C. As the water-soluble organic solvent, one or more selected from alcohol solvents are preferable.

Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, propylene glycol monomethyl monohydric alcohols such as ether and ethylene glycol monomethyl ether; dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol and 1,4-butanediol are mentioned.
Examples of ether-based solvents include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, and the like.
Ketone solvents include, for example, 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 ester-based solvents and hydrocarbon-based solvents are described later.
Examples of the nitrogen atom-containing compound solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.
Solvents not classified above include, for example, dimethylsulfoxide.

(Ester-based solvent)
An ester solvent is an ester group-containing compound having an ester group (--C(=O)--O--).
When the conductive composite is modified by reaction with an epoxy compound and an amine compound or a quaternary ammonium compound, it is preferable that the organic solvent contains an ester-based solvent because the dispersibility of the conductive composite is further increased. .
From the viewpoint of enhancing the dispersibility of the conductive composite, it is preferable to contain one or more ester-based solvents represented by the following formula 1z.
Formula 1z: R ²¹ -C(=O)-OR ²²
[In the formula, R ²¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ²² represents a linear or branched alkyl group having 1 to 6 carbon atoms. ]

From the viewpoint of enhancing the dispersibility of the conductive composite, R ²¹ is preferably a methyl group or an ethyl group, more preferably a methyl group. The number of carbon atoms in R ²² is preferably 2-5, more preferably 2-4.

Examples of ester solvents include ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate and the like.

The content of the ester solvent contained in the organic solvent is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and 70% by mass or more, relative to the total mass of the organic solvent. is more preferable, 80% by mass or more is particularly preferable, 90% by mass or more is most preferable, and 100% by mass may be sufficient. When the content of the ester solvent is within the above range, the dispersibility of the conductive composite can be enhanced.

When the conductive polymer-containing liquid of this embodiment contains an ester solvent, it may further contain one or more organic solvents other than the ester solvent.
Examples of organic solvents other than ester-based solvents include hydrocarbon-based solvents described later, ketone-based solvents described above, alcohol-based solvents, and nitrogen atom-containing compound-based solvents.

(hydrocarbon solvent)
When the conductive composite contained in the conductive polymer-containing liquid of this embodiment is modified by reaction with an epoxy compound and an amine compound or a quaternary ammonium compound, if a hydrocarbon solvent is included as a dispersion medium, It is preferable because the wettability with respect to the plastic film substrate is increased and a low-polarity binder component can be easily added.

Examples of the hydrocarbon-based solvent include aliphatic hydrocarbon-based solvents and aromatic hydrocarbon-based solvents. Examples of aliphatic hydrocarbon solvents include pentane, hexane, heptane, octane, decane, cyclohexane, and methylcyclohexane. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like. Among them, toluene is preferable because the dispersibility of the conductive composite is high. Moreover, when a silicone compound is added as a binder component, at least one of heptane and toluene is preferable because the solubility of the silicone compound is excellent.

Further containing methyl ethyl ketone in addition to the hydrocarbon-based solvent is preferable because the dispersibility of the conductive composite becomes higher. For example, with respect to 100 parts by mass of the hydrocarbon solvent, methyl ethyl ketone is preferably 20 parts by mass or more and 120 parts by mass or less, more preferably 30 parts by mass or more and 100 parts by mass or less, and even more preferably 40 parts by mass or more and 80 parts by mass or less. .

The content of the hydrocarbon solvent is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and even more preferably 70% by mass or more, relative to the total mass of the organic solvent. 80% by mass or more is particularly preferable, 90% by mass or more is most preferable, and 100% by mass may be sufficient. When the content of the hydrocarbon-based solvent is within the above range, the dispersibility of the conductive composite can be enhanced.

When the conductive polymer-containing liquid of this embodiment contains a hydrocarbon-based solvent, it may further contain one or more organic solvents other than the hydrocarbon-based solvent.
Examples of organic solvents other than hydrocarbon-based solvents include the aforementioned ketone-based solvents, alcohol-based solvents, ester-based solvents, nitrogen atom-containing compound-based solvents, and the like.

Among the above, the organic solvent is preferably one or more selected from alcohol solvents, ketone solvents, and ester solvents, and more preferably one or more selected from isopropanol, methyl ethylton, and ethyl acetate. By using these suitable organic solvents, the dispersibility of the conductive composite contained in the conductive polymer-containing liquid can be further enhanced.

(Distributed processing)
After adding the dispersion medium to the reaction product, the conductive polymer-containing liquid may be stirred for dispersion treatment. The method of stirring is not particularly limited, and may be stirring with a weak shear force such as a stirrer, or may be stirred using a disperser with a high shear force such as a high-pressure homogenizer, from the viewpoint of improving dispersibility. It is preferable to use a high-pressure homogenizer or the like.

(Addition of optional ingredients)
A binder component and other additives may be added to the conductive polymer-containing liquid obtained above.

<Addition of binder component>
The conductive polymer-containing liquid of this embodiment may further contain a binder component. By using a conductive polymer-containing liquid containing a binder component, it is possible to improve the strength of the conductive layer to be formed, and to impart adhesiveness and releasability.
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 the conductive layer is formed. The thermoplastic resin becomes the binder resin as it is, and the resin formed by curing the curable monomer or oligomer becomes the binder resin.
The binder component may be an adhesive, which will be described later.
One type of binder component may be added in this embodiment, or two or more types may be used.

Specific examples of binder resins derived from binder components include epoxy resins, acrylic resins (acrylic compounds), polyester resins, polyurethane resins, polyimide resins, polyether resins, melamine resins, and silicones.

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

When curable monomers or oligomers are included, it is preferable to further include a curing catalyst. For example, if it contains a thermosetting monomer or oligomer, it preferably contains a thermal polymerization initiator that generates radicals by heating, and if it contains a photocurable monomer or oligomer, it generates radicals by light irradiation. It preferably contains a photopolymerization initiator that causes the

The content ratio of the binder component (excluding the silicone compound described later) contained in the conductive polymer-containing liquid of the present embodiment is, for example, , 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, and even more preferably 100 parts by mass or more and 1000 parts by mass or less.
When it is at least the lower limit of the above range, the properties of the binder component contained in the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be sufficiently exhibited.
When it is equal to or less than the upper limit of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be ensured.

(silicone compound)
When the dispersion medium of the conductive polymer-containing liquid of this embodiment contains a hydrocarbon-based solvent or an ester-based solvent, the dispersibility of the silicone compound is further enhanced, which is preferable.
Examples of silicone compounds include curable silicones. When the binder component is curable silicone, the conductive layer can be imparted with releasability by curing the curable silicone.

The curable silicone may be either an addition curable silicone or a condensation curable silicone. This aspect is preferable because curing inhibition is less likely to occur even when an addition-curable silicone is used.

Examples of addition-curable silicones include linear polymers having siloxane bonds and having polydimethylsiloxane having vinyl groups at both ends of the linear chain and hydrogensilane. Such addition-curable silicone forms a three-dimensional crosslinked structure through an addition reaction and cures. A platinum-based curing catalyst may be used to accelerate curing.
Specific examples of addition-curable silicones include KS-3703T, KS-847T, KM-3951, X-52-151, X-52-6068, and X-52-6069 (manufactured by Shin-Etsu Chemical Co., Ltd.). .
Addition-curable silicone dissolved or dispersed in an organic solvent is preferably used.

The content ratio of the silicone compound contained in the conductive polymer-containing liquid of this embodiment is preferably 10 parts by mass or more and 10000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer and all polyanions. It is more preferably from 500 parts by mass to 5000 parts by mass, and even more preferably from 500 parts by mass to 3000 parts by mass.
When it is at least the lower limit value of the above range, sufficient releasability can be imparted to the conductive layer formed by the conductive polymer-containing liquid of this embodiment.
When it is equal to or less than the upper limit of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be ensured.

[Adhesive]
The conductive polymer-containing liquid of this embodiment may contain an adhesive as a binder component. By using a conductive polymer-containing liquid containing an adhesive, a conductive layer having adhesiveness can be formed.
When the dispersion medium of the conductive polymer-containing liquid of this embodiment contains a hydrocarbon-based solvent or an ester-based solvent, it can be easily mixed with the pressure-sensitive adhesive pre-dispersed in the hydrocarbon-based solvent or ester-based solvent. It is preferable because the conductive composite can be stably dispersed in the mixed liquid.

The degree of tackiness of the adhesive is not particularly limited, and may be tackiness to the extent that it can be easily peeled off by hand after application, or tackiness to the extent that it is difficult to peel off after application. may be gender. Tackiness that is difficult to peel off can be rephrased as adhesiveness. In other words, the tackiness may be such that it allows semi-permanent adhesion.

A known adhesive can be applied as the adhesive. An acrylic pressure-sensitive adhesive is preferable from the viewpoint of exhibiting good adhesiveness while maintaining conductivity.

(Acrylic adhesive)
Acrylic pressure-sensitive adhesives can be integrated by laminating surfaces of solids of the same type or different types. The acrylic pressure-sensitive adhesive contains acrylic resin (acrylic polymer).

Specific examples of acrylic monomers forming acrylic resins include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, ditri methylolpropane tetraacrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A/ethylene oxide-modified diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, dipropylene glycol diacrylate, Trimethylolpropane triacrylate, glycerin propoxy triacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, pentaerythritol Acrylates such as triacrylate, tetrahydrofurfuryl acrylate, and tripropylene glycol diacrylate; tetraethylene glycol dimethacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate , benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate , methacrylates such as trimethylolpropane trimethacrylate; -(Meth)acrylamides such as isopropylacrylamide, Nt-butylacrylamide, N-phenylacrylamide, acryloylpiperidine, and 2-hydroxyethylacrylamide.
One type of acrylic monomer forming the acrylic resin may be used, or two or more types may be used. Adhesiveness can be adjusted by combining two or more acrylic monomers.

The acrylic resin may be a copolymer of an acrylic monomer and a vinyl monomer other than the acrylic monomer.
Examples of vinyl monomers include styrene, α-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, maleic anhydride and the like.
The content of acrylic monomer units in the copolymer is preferably 50 mol % or more and less than 100 mol %, and more preferably 70 mol % or more and 98 mol % or less.
If the content of acrylic monomer units is at least the above lower limit, adhesiveness can be easily expressed.
The content of vinyl-based monomer units in the copolymer can be, for example, 2 mol % or more and 20 mol % or less.

The glass transition temperature of the acrylic resin is preferably 80° C. or lower, more preferably 50° C. or lower, and even more preferably 0° C. or lower. An acrylic resin having a glass transition temperature exceeding 80°C has low adhesiveness. The glass transition temperature of acrylic resin is -80°C or higher, and it is difficult to obtain a resin with a glass transition temperature lower than that. The glass transition temperature of the acrylic resin can be determined by differential scanning calorimetry or dynamic viscoelasticity measurement.
Examples of acrylic monomers that tend to lower the glass transition temperature of acrylic resins include ethyl acrylate, butyl acrylate (particularly n-butyl acrylate), 2-ethylhexyl acrylate, and the like. In the acrylic resin, the higher the proportion of these monomer units, the lower the glass transition temperature.

The mass average molecular weight of the acrylic resin is preferably 10,000 or more and 2,000,000 or less, and more preferably 30,000 or more and 1,000,000 or less. If the mass average molecular weight of the acrylic resin is at least the lower limit, sufficient cohesion can be ensured. If it is below the said upper limit, adhesiveness can be improved more.

When the acrylic resin has an acrylic monomer unit having a reactive functional group, it may be cured by reacting with a curing agent. When the acrylic resin is cured, the cohesive force of the conductive layer containing the pressure-sensitive adhesive is improved, and the strength can be improved. Further, by improving the cohesive force of the conductive layer, a re-peelable conductive layer that can be repeatedly adhered and peeled can be obtained.
Examples of the reactive functional group include a hydroxy group, a carboxyl group, an amino group, an amide group, an epoxy group and the like. When reacting with a polyfunctional isocyanate described later, the reactive functional group is preferably a hydroxy group, a carboxy group, or an amino group, more preferably a hydroxy group.
Acrylic monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl acrylate. , 4-hydroxybutyl methacrylate and the like.
Examples of acrylic monomers having a carboxy group include acrylic acid, methacrylic acid and itaconic acid.
Acrylic monomers having an amino group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate and the like.
Acrylic monomers having an amide group include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.
Examples of acrylic monomers having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
When a polyfunctional isocyanate is used as a curing agent, among the acrylic monomers having a reactive functional group, acrylic monomers having a hydroxy group are preferable in consideration of curability and cost, and 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate is more preferred.
One type or two or more types of acrylic monomers having the reactive functional group may be used to form the acrylic resin.

The content ratio of the adhesive contained in the conductive polymer-containing liquid of this embodiment is preferably 10 parts by mass or more and 10000 parts by mass or less, and 100 parts by mass with respect to 1 part by mass of the π-conjugated conductive polymer and all polyanions. Part or more and 5000 mass parts or less are more preferable, and 300 mass parts or more and 1000 mass parts or less are more preferable.
When it is at least the lower limit of the above range, sufficient adhesiveness can be imparted to the conductive layer formed by the conductive polymer-containing liquid of this embodiment.
When it is equal to or less than the upper limit of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be ensured.

(curing agent)
When the adhesive contained in the conductive polymer-containing liquid of this aspect has a reactive functional group, the conductive polymer-containing liquid of this aspect preferably contains a curing agent.
Examples of the curing agent include isocyanate curing agents such as polyfunctional isocyanates having two or more isocyanate groups in one molecule, and epoxy curing agents such as epoxy compounds having two or more epoxy groups in one molecule. Among these curing agents, polyfunctional isocyanates are preferred from the viewpoint of reactivity. In particular, when the pressure-sensitive adhesive has an acrylic monomer unit having a hydroxy group, the curing agent is preferably polyfunctional isocyanate.

Polyfunctional isocyanates include aliphatic polyfunctional isocyanates, alicyclic polyfunctional isocyanates and aromatic polyfunctional isocyanates.
Specific examples of polyfunctional isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, polyphenylene Polymethylene polyisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, 4,4'-dicyclomethane diisocyanate, 3,3 '-dimethyl-4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, tetramethyl xylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, bicyclohepta triisocyanate, trimethylhexamethylene diisocyanate and the like.
The polyfunctional isocyanate may be a modified diisocyanate formed from a modified polyfunctional isocyanate obtained by modifying the above diisocyanate so that the NCO/OH molar ratio is 2/1 or more.
A polyfunctional isocyanate may be a modified polyisocyanate. Modified polyisocyanates include, for example, polyurethane polyisocyanates obtained by reacting polyfunctional isocyanates with polyhydric alcohols, polyisocyanates containing isocyanurate rings obtained by polymerizing polyfunctional isocyanates, and polyfunctional isocyanates. and polyisocyanate containing burette bonds obtained by reacting with water.
The type of curing agent contained in the conductive polymer-containing liquid of this embodiment may be one type, or two or more types.

The content of the curing agent contained in the conductive polymer-containing liquid of this aspect is preferably, for example, 1 part by mass or more and 100 parts by mass or less, and 2 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the adhesive. is more preferable, and 3 parts by mass or more and 10 parts by mass or less is even more preferable.
Within the above range, sufficient adhesiveness can be imparted to the conductive layer formed by the conductive polymer-containing liquid of the present embodiment.

(high conductivity agent)
The conductive polymer-containing liquid of this embodiment may contain a conductivity enhancer.
Here, the above-described π-conjugated conductive polymer, polyanion, organic solvent, adhesive, curing agent, and binder component are not classified as high-conductivity agents. The epoxy compound, the amine compound, and the quaternary ammonium compound may correspond to the high-conductivity agent described here.
Conductive agents include sugars, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxyl groups, compounds having one or more hydroxyl groups and one or more carboxyl groups, compounds having an amide group, and imide groups. is preferably at least one compound selected from the group consisting of compounds having
The conductive polymer-containing liquid of the present embodiment may contain one type of conductivity enhancer, or two or more types thereof.
The content of the conductive agent is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, with respect to 100 parts by mass of the π-conjugated conductive polymer and all polyanions. More preferably 100 parts by mass or more and 2500 parts by mass or less.
If the content ratio of the high-conductivity agent is at least the above lower limit, the effect of improving conductivity by adding the high-conductivity agent is sufficiently exhibited, and if it is at or below the above upper limit, the concentration of the π-conjugated conductive polymer decreases. It is possible to prevent a decrease in conductivity caused by

(Other additives)
The conductive polymer-containing liquid of this embodiment may contain other known additives.
Descriptions of other additives are the same as those described above, so redundant descriptions are omitted here.

<<Conductive laminate>>
A third aspect of the present invention is a conductive polymer comprising a substrate and a conductive layer formed on at least a part of the surface of the substrate and comprising a cured layer of the conductive polymer-containing liquid of the first aspect. It is a laminate.
The conductive polymer-containing liquid may be a conductive polymer-containing liquid containing a hydrophobized conductive composite produced by the production method of the second aspect.

[Conductive layer]
The formation range of the conductive layer may be the entire arbitrary surface of the substrate, or may be a part thereof. In the conductive film, it is preferable that a conductive layer having a substantially uniform thickness is formed over substantially the entire surface of one or the other surface of the film substrate. When the conductive layer is formed only on part of the surface of the substrate, for example, the conductive layer may be a fine conductive pattern such as a circuit or an electrode, or the area provided with the conductive layer may be provided. It is also possible that the non-stripped area exists on the same plane and is only roughly divided.

The average thickness of the conductive layer is, for example, preferably 10 nm or more and 100 μm or less, more preferably 20 nm or more and 50 μm or less, and even more preferably 30 nm or more and 30 μm or less.
If the average thickness of the conductive layer is at least the lower limit, high conductivity can be exhibited, and if the average thickness is at most the upper limit, the adhesion of the conductive layer to the substrate is further improved.
The average thickness of the conductive layer is a value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

[Base material]
The substrate may be a substrate made of an insulating material, or may be a substrate made of a conductive material. The shape of the substrate is not particularly limited, and examples thereof include shapes mainly composed of planes such as films and substrates.
Examples of insulating materials include glass, synthetic resins, and ceramics.
Examples of conductive materials include metals, conductive metal oxides, and carbon.

(Film substrate)
When a film substrate is used as the substrate, the conductive laminate becomes a conductive film.
Examples of the film substrate include a plastic film made of a synthetic resin. Examples of the synthetic resin include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyacrylate. , polycarbonate, polyvinylidene fluoride, polyarylate, styrene elastomer, polyester elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate, and the like.
From the viewpoint of enhancing the adhesion between the film substrate and the conductive layer, the synthetic resin for the film substrate is preferably a polyester resin, and polyethylene terephthalate is particularly preferable.

The synthetic resin for the film substrate may be amorphous or crystalline.
The film substrate may be unstretched or stretched.
The film substrate may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc., in order to further improve the adhesion of the conductive layer.

The average thickness of the film substrate is preferably 5 μm or more and 500 μm or less, more preferably 20 μm or more and 200 μm or less. When the average thickness of the film substrate is at least the lower limit, the film is less likely to break, and when it is at most the upper limit, sufficient flexibility as a film can be ensured.
The average thickness of the film substrate is the value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

(Glass substrate)
Examples of glass substrates include alkali-free glass substrates, soda-lime glass substrates, borosilicate glass substrates, quartz glass substrates, and the like. If the substrate contains an alkali component, the conductivity of the conductive layer tends to decrease, so among the above glass substrates, non-alkali glass is preferable. Here, the alkali-free glass is a glass composition in which the content of alkali components is 0.1% by mass or less with respect to the total mass of the glass composition.

The average thickness of the glass substrate is preferably 100 μm or more and 3000 μm or less, more preferably 100 μm or more and 1000 μm or less. If the average thickness of the glass substrate is at least the lower limit, it will be difficult to break, and if it is at most the upper limit, it can contribute to thinning of the conductive laminate.
The average thickness of the glass substrate is the value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

<<Method for manufacturing conductive laminate>>
A fourth aspect of the present invention is a step of obtaining a conductive polymer-containing liquid containing a hydrophobized conductive composite by the production method of the second aspect; and a step of coating a part of the surface of the conductive laminate.
The conductive polymer-containing liquid applied in the above step may be a conductive polymer-containing liquid containing the conductive composite that is not hydrophobized according to the first embodiment.

Since the description of the base material is the same as that described above, redundant description is omitted here.

Methods for coating (applying) the conductive polymer-containing liquid to any surface of the substrate include, for example, gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, fountain coaters, Methods using coaters such as rod coaters, air doctor coaters, knife coaters, blade coaters, cast coaters, and screen coaters; methods using atomizers such as air spray, airless spray, and rotor dampening; and immersion methods such as dipping. can be applied.

The amount of the conductive polymer-containing liquid to be applied to the substrate is not particularly limited, but the solid content is 0.01 g/m ² or more in consideration of uniform coating, conductivity and film strength. It is preferably in the range of 10.0 g/m ² or less.

The conductive layer can be formed by drying the coating film of the conductive polymer-containing liquid applied on the base material to remove at least part of the dispersion medium and curing the coating film.
Heat drying, vacuum drying, etc. are mentioned as a method of drying a coating film. As heat drying, for example, a method such as hot air heating or infrared heating can be employed.
When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium to be used, but is usually in the range of 50°C or higher and 200°C or lower. Here, the heating temperature is the set temperature of the drying device. A suitable drying time within the above heating temperature range is preferably 0.5 minutes or more and 30 minutes or less, more preferably 1 minute or more and 15 minutes or less.
UV irradiation may be performed after drying to cure the binder component contained in the coating film.

The formation range of the conductive layer may be the entire arbitrary surface of the substrate, or may be a part thereof. In the conductive film, it is preferable that a conductive layer having a substantially uniform thickness is formed on substantially the entire surface of one side or the other side of the film substrate. When the conductive layer is formed only on part of the surface of the substrate, for example, the conductive layer may be a fine conductive pattern such as a circuit or an electrode, or may be a region provided with a conductive layer. It is also possible that the non-stripped area exists on the same plane and is only roughly divided.

Since the explanation of the average thickness of the conductive layer is the same as the above, duplicate explanation is omitted here.

≪Using liquid containing conductive polymer≫
In a fifth aspect of the present invention, after the conductive polymer-containing liquid of the first aspect is gently stored at 40° C. or higher for 720 hours or more, the stored conductive polymer-containing liquid is treated with the conductive polymer-containing liquid of the second aspect. A method of using it as a material for the method for producing a conductive polymer-containing liquid, using it as a material for the conductive layer of the conductive laminate of the third aspect, or using it as a material for the method for producing the electrically conductive laminate of the fourth aspect. is.
Since the conductive polymer-containing liquid of the first aspect contains the molecular weight maintaining agent, it is stable even under the storage conditions described above, and can form a conductive layer with sufficient atmospheric exposure resistance.
The upper limit of the temperature in the above storage conditions is 50° C. or less or 60° C. or less, and the upper limit of the storage period (time) is not particularly limited. mentioned.

(Production Example 1) Production 1 of polystyrene sulfonic acid
Dissolve 206 g of sodium styrenesulfonate in 1000 ml of ion-exchanged water, add 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water dropwise for 20 minutes while stirring at 80° C., and keep this solution for 12 hours. Stirred.
1000 ml of sulfuric acid diluted to 10% by mass was added to the resulting sodium polystyrenesulfonate solution, and about 1000 ml of the solvent in the resulting polystyrenesulfonic acid solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by ultrafiltration, and the polystyrene sulfonic acid was washed with water. This washing operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.
Next, 10 g of the obtained polystyrene sulfonic acid was dissolved in 90 g of ion-exchanged water to obtain a 10 mass % polystyrene sulfonic acid aqueous solution.

The weight average molecular weight (Mw) of the polystyrene sulfonic acid (PSS) obtained above was measured by gel permeation chromatography (GPC) using pullulan having a known weight average molecular weight as a standard substance, and the weight average molecular weight was 180,000. rice field.
The weight average molecular weight was measured using a high-performance liquid chromatograph Prominence manufactured by Shimadzu Corporation, using 0.1% _NaNO3 aqueous solution as a solvent, using Shodex OHpack SB-806M HQ as a column, and using a detector. Using RID-20A as a sample, setting the solvent temperature to 40 ° C., setting the flow rate to 0.6 ml / min, setting the PSS concentration in the sample to 0.1% by mass, and filtering through a membrane filter with a pore size of 0.2 μm An injection of 100 μl was performed using analysis software Lab Solutions (manufactured by Shimadzu Corporation).

(Production Example 2) Production of polystyrene sulfonic acid 2
206 g of sodium styrenesulfonate is dissolved in 1000 ml of ion-exchanged water, and while stirring at 80° C., 0.38 g of ammonium persulfate oxidant solution previously dissolved in 10 ml of water is added dropwise for 20 minutes, and this solution is allowed to stand for 12 hours. Stirred.
1000 ml of sulfuric acid diluted to 10% by mass was added to the resulting sodium polystyrenesulfonate solution, and about 1000 ml of the solvent in the resulting polystyrenesulfonic acid solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by ultrafiltration, and the polystyrene sulfonic acid was washed with water. This washing operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.
Next, 10 g of the obtained polystyrene sulfonic acid was dissolved in 90 g of ion-exchanged water to obtain a 10 mass % polystyrene sulfonic acid aqueous solution.
The weight average molecular weight of the polystyrene sulfonic acid (PSS) obtained above, which was measured using GPC in the same manner as in Production Example 1, was 540,000.

(Example 1)
3.0 g of 3,4-ethylenedioxythiophene (EDOT), 90 g of the 10 mass % PSS aqueous solution of Production Example 1, and 325 g of ion-exchanged water were mixed at 20.degree.
The resulting mixed solution was kept at 20° C. and 1.2 g of ferric sulfate was added while stirring.
Next, an oxidizing agent solution (25° C.) in which 6.6 g of sodium persulfate was dissolved in 293.4 g of deionized water was slowly added over 4 hours, and the addition of all the oxidizing agent solution was completed. The reaction solution (25° C.) was stirred for 8 hours to react.
By the above reaction, a conductive composite (PEDOT-PSS) containing poly(3,4-ethylenedioxythiophene), which is a π-conjugated conductive polymer, and polystyrene sulfonic acid, and water as a dispersion medium. A liquid containing a flexible polymer was obtained.
39 g of Duolite C255LFH (manufactured by Sumika Chemtex Co., Ltd., cation exchange resin) and 39 g of Duolite A368S (manufactured by Sumika Chemtex Co., Ltd., anion exchange resin) are added to this conductive polymer-containing liquid, and filtered to obtain an ion exchange resin. 710 g of a conductive polymer-containing liquid (concentration of non-volatile components: 1.4% by mass) from which the oxidizing agent and the catalyst were removed was obtained.
Next, ion-exchanged water was added to the resulting conductive polymer-containing liquid to adjust the non-volatile component concentration to 1.0% by mass, followed by dispersion using a high-pressure homogenizer.

A portion of the conductive polymer-containing liquid was sampled and analyzed with a gas chromatography-mass spectrometer to find that the amount of unreacted EDOT was below the measurement limit. From this result, it was found that almost all EDOT formed PEDOT.
The above gas chromatography measurement uses GCMS-QP2010Plus manufactured by Shimadzu Corporation, uses helium as a carrier gas, uses DB-5MS as a column, and uses a secondary electron multiplier with a conversion diode as a detector. Use, set the vaporization temperature to 250 ° C., set the flow rate to 1.2 mL / min, inject 1 μL of the sample, set the PEDOT-PSS concentration in the sample to 1.0% by mass, and use the analysis software GCMSsolution, gone.

A portion of the above conductive polymer-containing liquid is separated and filtered through a membrane filter with a pore size of 0.2 μm (manufactured by Membrane Solution Japan, model number: NY-030022) to trap PEDOT-PSS on the membrane. , a single PSS (not forming PEDOT-PSS) contained in the conductive polymer-containing liquid was permeated and recovered in the filtrate. When the weight average molecular weight of PSS contained in this filtrate was measured by GPC as described in Production Example 1, it was 96,000.

Next, 0.1 g of imidazole was added to 100 g of the conductive polymer-containing liquid, and the mixture was allowed to stand at 40 ° C. for 720 hours, simulating a storage environment such as a room without air conditioning in the summer, and then PEDOT-PSS. The weight-average molecular weight of the PSS that did not form was measured by GPC in the same manner as described above, and found to be 91,000.
Therefore, the weight average molecular weight X of the single PSS before standing is 96,000, the weight average molecular weight Y of the single PSS after standing is 91,000, and Y/X = 0.95. there were.

Subsequently, the conductive polymer-containing liquid after standing was applied onto a PET film using a #4 bar coater and dried at 120° C. for 1 minute to obtain a conductive film. Table 1 shows the results of measuring the surface resistance value _R0 of this conductive film.
Furthermore, the conductive film whose surface resistance value R ₀ was measured was left exposed to the atmosphere for 30 days under the conditions of a temperature of 25 ° C. and a humidity of 50% RH. ₁ was measured. Table 1 shows the result and the increase ratio (R ₁ /R ₀ ) of the surface resistance value.

The surface resistance value of the conductive layer of the conductive film was measured using a resistivity meter (Hiresta manufactured by Nitto Seiko Analyticc Co., Ltd.) under the condition of an applied voltage of 10V. In the table, "1.0E+05" means "1.0×10 ⁵ ", and so on.

(Example 2)
A conductive polymer-containing liquid was obtained in the same manner as in Example 1 except that the amount of imidazole added was changed to 0.5 g, the weight average molecular weight was measured, and a conductive film was produced. A surface resistance value was measured.

(Example 3)
A conductive polymer-containing liquid was obtained in the same manner as in Example 1 except that 0.1 g of triethylamine was added instead of 0.1 g of imidazole in Example 1, and the weight average molecular weight was measured to obtain a conductive film. It was produced and its surface resistance value was measured.

(Example 4)
A conductive polymer-containing liquid was obtained in the same manner as in Example 1 except that 0.5 g of triethylamine was added instead of 0.1 g of imidazole in Example 1, and the weight average molecular weight was measured to obtain a conductive film. It was produced and its surface resistance value was measured.

(Example 5)
A conductive polymer-containing liquid was obtained in the same manner as in Example 1 except that 0.1 g of triethanolamine was added instead of 0.1 g of imidazole in Example 1, and the weight average molecular weight was measured. A film was produced and its surface resistance value was measured.

(Example 6)
A conductive polymer-containing liquid was obtained in the same manner as in Example 1 except that 0.5 g of triethanolamine was added instead of 0.1 g of imidazole in Example 1, and the weight average molecular weight was measured. A film was produced and its surface resistance value was measured.

(Comparative example 1)
A conductive polymer-containing liquid was obtained in the same manner as in Example 1 except that imidazole was not added in Example 1, the weight average molecular weight was measured, a conductive film was produced, and the surface resistance value was measured. bottom.

(Example 7)
Example 1 "90 g of the 10% by mass PSS aqueous solution of Production Example 1 and 325 g of ion-exchanged water were mixed at 20 ° C." The conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that 710 g of the conductive polymer-containing liquid (nonvolatile component concentration: 1.8% by mass) was obtained in the same manner as in Example 1, except that it was changed to A conductive polymer-containing liquid was obtained, the weight average molecular weight was measured, a conductive film was produced, and the surface resistance value was measured. Table 1 shows the results.

(Comparative example 2)
A conductive polymer-containing liquid was obtained in the same manner as in Example 7 except that imidazole was not added in Example 7, the weight average molecular weight was measured, a conductive film was produced, and the surface resistance value was measured. bottom.

(Example 8)
710 g of a conductive polymer-containing liquid ( A conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that a nonvolatile component concentration of 1.4% by mass) was obtained, the weight average molecular weight was measured, a conductive film was produced, and its surface resistance was values were measured. Table 1 shows the results.

(Comparative Example 3)
A conductive polymer-containing liquid was obtained in the same manner as in Example 8 except that imidazole was not added in Example 8, the weight average molecular weight was measured, a conductive film was produced, and the surface resistance value was measured. bottom.

(Example 9)
50 g of isopropanol and 10 g of trioctylamine were added to 100 g of the conductive polymer-containing liquid of Example 1 after standing at 40° C. for 720 hours, and the mixture was stirred for 1 hour to partially dissolve the sulfonic acid groups of the conductive composite. Trioctylamine was reacted. As a result, all the reaction products were deposited on the upper layer of the reaction solution. This precipitate was filtered to obtain a powder of the reaction product of the conductive composite and trioctylamine. Isopropanol was added to this powder to obtain 500 g of a mixed liquid, which was dispersed using a high-pressure homogenizer to obtain 500 g of a conductive polymer-containing liquid. Table 2 shows the results of measuring the concentration of non-volatile components in this containing liquid.
Next, the obtained conductive polymer-containing liquid was applied on a PET film with a #8 bar coater and dried at 100° C. for 1 minute to obtain a conductive film. values were measured. Table 2 shows the results.

(Comparative Example 4)
Isopropanol was added in the same manner as in Example 9, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Comparative Example 1 (nonvolatile component concentration: 1.0% by mass). A conductive polymer-containing liquid was obtained as a dispersion medium, and a conductive film was produced. Table 2 shows the results.

(Example 10)
25 g of an epoxy compound (manufactured by Kyoeisha Chemical Co., Ltd., Epolite M-1230, C12,13 mixed higher alcohol glycidyl ether) was added to 100 g of the conductive polymer-containing liquid of Example 1 after standing at 40 ° C. for 720 hours. C. for 4 hours, and the epoxy compound was reacted with a part of the sulfonic acid groups of the conductive composite. As a result, a reaction product precipitated. This precipitate was filtered to obtain a reaction product of the conductive composite and the epoxy compound. Methyl ethyl ketone was added to this reaction product to obtain 300 g of a mixed liquid, which was dispersed using a high-pressure homogenizer to obtain 300 g of a conductive polymer-containing liquid. Table 2 shows the results of measuring the concentration of non-volatile components in this containing liquid.
Next, the obtained conductive polymer-containing liquid was applied onto a PET film using a #8 bar coater, dried at 100° C. for 1 minute to obtain a conductive film, and the surface resistance value thereof was measured. bottom. Table 2 shows the results.

(Comparative Example 5)
Methyl ethyl ketone was added in the same manner as in Example 10, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid (nonvolatile component concentration: 1.0% by mass) of Comparative Example 1. A conductive polymer-containing liquid was obtained as a dispersion medium, and a conductive film was produced. Table 2 shows the results.

(Example 11)
25 g of an epoxy compound (manufactured by Kyoeisha Chemical Co., Ltd., Epolite M-1230, C12,13 mixed higher alcohol glycidyl ether) was added to 100 g of the conductive polymer-containing liquid of Example 1 after standing at 40 ° C. for 720 hours. The mixture was heated and stirred at ℃ for 4 hours. Next, 50 g of isopropanol and 10 g of trioctylamine were added and stirred for 1 hour, whereby the epoxy compound and trioctylamine reacted with some sulfonic acid groups of the conductive composite. As a result, a reaction product precipitated. This precipitate was filtered to obtain a reaction product of the conductive composite with the epoxy compound and trioctylamine. Ethyl acetate was added to this reaction product to obtain 800 g of a mixed liquid, which was dispersed using a high-pressure homogenizer to obtain 800 g of a conductive polymer-containing liquid. Table 2 shows the results of measuring the concentration of non-volatile components in this containing liquid.
Next, the obtained conductive polymer-containing liquid was applied onto a PET film using a #8 bar coater, dried at 100° C. for 1 minute to obtain a conductive film, and the surface resistance value thereof was measured. bottom. Table 2 shows the results.

(Comparative Example 6)
Ethyl acetate was obtained as a dispersion medium, a conductive film was obtained, and its surface resistance was measured. Table 2 shows the results.

<Results>
From the results of Comparative Examples 1 to 3, PEDOT-PSS contained in the conductive polymer-containing liquid was formed after standing at 40 ° C. for 720 hours (storage conditions assuming a room without air conditioning in summer). It was found that the molecular weight of the PSS without PSS (individual PSS) was low, and the weight average molecular weight ratio (Y/X) was less than 0.94. The resistance to atmospheric exposure of the conductive layer formed by applying the conductive polymer-containing liquid containing a single PSS having a low molecular weight was inferior to that of the examples.
On the other hand, in the conductive polymer-containing liquids of Examples 1 to 8, since the molecular weight maintaining agent is contained, the single PSS contained in the conductive polymer-containing liquid has a low molecular weight even after the standing. It was found that the weight-average molecular weight ratio (Y/X) was 0.94 or more. The atmospheric exposure resistance of the conductive layer formed by coating the conductive polymer-containing liquid in which the reduction in the molecular weight of the single PSS was suppressed was superior to that of Comparative Examples 1-3.

In the conductive polymer-containing liquids produced in Examples 9 to 11, the molecular weight maintaining agent was contained in the conductive polymer-containing liquid of Example 1 used as a raw material, so that the single PSS had a low molecular weight. had not changed. Therefore, the resistance to atmospheric exposure of the conductive layers formed by applying the conductive polymer-containing liquids produced in Examples 9-11 was superior to that of Comparative Examples 4-6.
The single PSS contained in the conductive polymer-containing liquid of Comparative Example 1, which was used to produce the conductive polymer-containing liquids of Comparative Examples 4 to 6, had a low molecular weight after the standing. Therefore, the resistance to atmospheric exposure of the conductive layers formed by applying the conductive polymer-containing liquids produced in Comparative Examples 4-6 was inferior to that of Examples 9-11.

<Mechanism of action>
In the conductive polymer-containing liquid of the comparative example, the single polyanion has a low molecular weight during the stationary period (storage), and the ratio of the single polyanion present on the surface of the coating film is reduced. As a result, the conductive composite on the surface of the conductive layer is likely to come into contact with the air, and the resistance to air exposure of the conductive layer is low.
On the other hand, in the conductive polymer-containing liquids of Examples, since the single polyanion can be maintained at a high molecular weight after storage, the single polyanion tends to gather on the surface of the coating film (excluded from the deep part). easily accumulate on the surface), the single polyanion on the surface of the coating film reduces the contact between the atmosphere and the conductive composite, and functions as a protective agent for the conductive composite, thereby increasing the resistance to atmospheric exposure of the conductive layer. presumed to be excellent.

Claims (10)

Suppressing reduction in molecular weight of a conductive complex containing a π-conjugated conductive polymer and a polyanion, the polyanion not forming the conductive complex, and the polyanion not forming the conductive complex A conductive polymer-containing liquid containing a molecular weight maintaining agent and a dispersion medium,
Let X be the initial weight-average molecular weight of the polyanion that does not form the conductive complex, and the conductive polymer-containing liquid that does not form the conductive complex after standing at 40 ° C. for 720 hours. A conductive polymer-containing liquid having a molecular weight ratio represented by Y/X, where Y is the weight average molecular weight of the polyanion, of 0.94 or more. 2. The conductive polymer-containing liquid according to claim 1, wherein said molecular weight maintaining agent contains a basic compound. 3. The conductive polymer-containing liquid according to claim 1, wherein said π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). The conductive polymer-containing liquid according to any one of claims 1 to 3, wherein the polyanion is polystyrenesulfonic acid. Precipitating a reaction product containing the conductive composite by adding an epoxy compound to the conductive polymer-containing liquid according to any one of claims 1 to 4;
A method for producing a conductive polymer-containing liquid, comprising recovering the precipitated reaction product and adding an organic solvent. Precipitating a reaction product containing the conductive composite by adding an amine compound or a quaternary ammonium compound to the conductive polymer-containing liquid according to any one of claims 1 to 4. ,
A method for producing a conductive polymer-containing liquid, comprising recovering the precipitated reaction product and adding an organic solvent. By adding an epoxy compound and an amine compound or a quaternary ammonium compound to the conductive polymer-containing liquid according to any one of claims 1 to 4, a reaction product containing the conductive composite is produced. precipitating;
A method for producing a conductive polymer-containing liquid, comprising recovering the precipitated reaction product and adding an organic solvent. A conductive conductive layer comprising a substrate and a cured layer of the conductive polymer-containing liquid according to any one of claims 1 to 4 formed on at least a part of the surface of the substrate. laminate. obtaining a conductive polymer-containing liquid by the production method according to any one of claims 5 to 7; and coating the conductive polymer-containing liquid on at least a part of a substrate. A method for manufacturing a conductive laminate. The method for producing a conductive laminate according to claim 9, wherein the substrate is a film substrate.