Method for producing a conductive polymer-containing liquid, and method for producing a conductive laminate.

Abstract

To provide a method for storing a conductive polymer-containing liquid which can be stored stably even in a storage environment at about 40°C, a method for producing a conductive polymer-containing liquid, a method for producing a conductive laminate, and a conductive complex storage container.SOLUTION: A method for storing a conductive polymer-containing liquid is to store the conductive polymer-containing liquid in a sealed container, wherein the conductive polymer-containing liquid contains a conductive complex containing π-conjugated conductive polymers and polyanions, the polyanions not forming the conductive complex, and a dispersion medium. The level of oxygen included in a space left after subtracting the volume of the conductive polymer-containing liquid from the volume of the container is 9.9 vol.% or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for storing a conductive polymer-containing liquid containing a π-conjugated conductive polymer, a method for producing a conductive polymer-containing liquid, a method for producing a conductive laminate, and a storage device for a conductive composite.

Background Art

[0002] A π-conjugated conductive polymer whose main chain is composed of a π-conjugated system forms a conductive composite by doping with a polyanion having an anion group, and exhibits dispersibility in water. By coating a film substrate or the like with a conductive polymer-containing liquid (sometimes referred to as a conductive polymer dispersion) containing the conductive composite, a conductive film provided with a conductive layer can be produced. Further, an epoxy compound may be reacted with the conductive composite for the purpose of enhancing the wettability of the conductive polymer-containing liquid with respect to the film substrate or enhancing 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.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, when a storage period of about 30 days (720 hours) elapses 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. Examples of this change include a decrease in the atmospheric exposure resistance. When the present inventor examined the cause of this change, it was considered that the temperature during storage was affecting it because the change was likely to occur in the lots manufactured in summer. When this was confirmed, it was found that there was little change even when stored at room temperature of about 25°C for 720 hours, but there was a change when stored at room temperature reaching about 40°C for 720 hours. Next, when analyzing the components contained in the conductive polymer-containing liquid before and after the change occurred, it was found that the weight average molecular weight of the single polyanion that did not form a conductive complex decreased (became lower molecular weight). Furthermore, as a method for suppressing the decrease in the molecular weight, by reducing the oxygen concentration in the container for storing the conductive polymer-containing liquid in a sealed manner, even after storing at 40°C for 720 hours, the molecular weight of the single polyanion did not decrease, and the characteristics of the formed conductive layer hardly changed.

[0005] Through the above examinations, the present invention provides a method for storing a conductive polymer-containing liquid that can be stably stored even in a storage environment of about 40°C, a method for manufacturing a conductive polymer-containing liquid, a method for manufacturing a conductive laminate, and a container for storing a conductive complex.

Means for Solving the Problems

[0006] [1] A method for storing a conductive polymer-containing liquid containing a conductive complex containing a π-conjugated conductive polymer and a polyanion, the polyanion that does not form the conductive complex, and a dispersion medium in a sealed container, wherein the oxygen concentration contained in the space remaining after subtracting the volume of the conductive polymer-containing liquid from the volume of the container is 9.9% by volume or less. [2] When the initial weight average molecular weight of the polyanion that does not form the conductive complex at the start of storage of the conductive polymer-containing liquid is X, and the weight average molecular weight of the polyanion that does not form the conductive complex at the time when the conductive polymer-containing liquid is stored at 40°C or higher and 50°C or lower for 720 hours is Y, the method for storing a conductive polymer-containing liquid according to [1], wherein the molecular weight ratio represented by Y / X is 0.89 or more. [3] A method for storing a conductive polymer-containing liquid according to [1] or [2], wherein the oxygen concentration is reduced by blowing nitrogen gas or argon gas into the container. [4] A method for storing a conductive polymer-containing liquid according to any one of [1] to [3], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). [5] A method for storing a conductive polymer-containing liquid according to any one of [1] to [4], wherein the polyanion is polystyrene sulfonic acid. A method for producing a conductive polymer-containing liquid, comprising: adding an epoxy compound to a conductive polymer-containing liquid stored by any one of the methods described in [1] to [5] to precipitate a reaction product containing the conductive composite; and recovering the precipitated reaction product and adding an organic solvent. A method for producing a conductive polymer-containing liquid, comprising: adding an amine compound or a quaternary ammonium compound to a conductive polymer-containing liquid stored by the method described in any one of items [1] to [5] to precipitate a reaction product containing the conductive composite; and recovering the precipitated reaction product and adding an organic solvent. A method for producing a conductive polymer-containing liquid, comprising: adding an epoxy compound and an amine compound or a quaternary ammonium compound to a conductive polymer-containing liquid stored by any one of the methods described in [1] to [5], thereby precipitating a reaction product containing the conductive composite; and recovering the precipitated reaction product and adding an organic solvent. A method for manufacturing a conductive laminate, comprising the step of coating at least a portion of a substrate surface with a conductive polymer-containing liquid stored by the method described in any one of items [1] to [5], or a conductive polymer-containing liquid manufactured by the method described in any one of items [6] to [8].

[10] A conductive composite storage container in which a conductive polymer-containing liquid is sealed inside the container, wherein the conductive polymer-containing liquid contains a conductive composite comprising a π-conjugated conductive polymer and a polyanion, the polyanion not forming the conductive composite, and a dispersion medium, and a residual space not filled by the conductive polymer-containing liquid exists inside the container, and the oxygen concentration in the residual space is 9.9% by volume or less. [Effects of the Invention]

[0007] According to the method for storing conductive polymer-containing liquids and the conductive composite storage container of the present invention, stable storage is possible even in storage environments of 40°C or higher. According to the method for producing a conductive polymer-containing liquid of the present invention, a conductive layer with sufficient resistance to atmospheric exposure can be formed, and a paint containing a conductive composite dispersed in an organic solvent can be easily manufactured. According to the present invention's method for manufacturing conductive laminates, a conductive laminate equipped with a conductive layer that has sufficient resistance to atmospheric exposure can be easily manufactured.

[0008] This invention is believed to contribute to SDG Goal 12, "Responsible Consumption and Production."

[0009] In this specification and the claims, the lower and upper limits of the numerical ranges indicated by "~" are to be included within those numerical ranges. [Modes for carrying out the invention]

[0010] ≪Storage method for conductive polymer-containing liquids≫ A first aspect of the present invention is a method for storing a conductive polymer-containing liquid in a sealed container, which contains a conductive composite comprising a π-conjugated conductive polymer and a polyanion, the polyanion that does not form the conductive composite (hereinafter sometimes referred to as "a single polyanion"), and a dispersion medium.

[0011] In the storage method of this embodiment, when the volume of the space remaining after subtracting the volume of the conductive polymer-containing liquid from the volume of the container (residual space) is set to 100% by volume, the oxygen concentration in that residual space is set to 9.9% by volume or less. By reducing the oxygen concentration in this way to a level lower than the oxygen concentration of the air that makes up the general atmosphere, the demilitarization of individual polyanions contained in the conductive polymer-containing liquid is suppressed, and stable storage is possible. As a result, even after long-term storage at temperatures of 40°C or higher, the atmospheric exposure resistance of the conductive layer formed from the conductive polymer-containing liquid can be sufficiently maintained.

[0012] The remaining space may contain gas or be under vacuum. When the conductive polymer-containing liquid and gas are contained within the container, the gas is in contact with at least a portion of the conductive polymer-containing liquid within the container. If the residual space contains gas, the oxygen content (oxygen concentration) relative to the total volume of the gas (volume of the residual space) shall be 9.9% by volume or less.

[0013] The oxygen concentration in the residual space is preferably 8.0% by volume or less, more preferably 6.0% by volume or less, even more preferably 4.0% by volume or less, particularly preferably 2.0% by volume or less, and most preferably 1.0% by volume or less. Reducing the oxygen concentration to the above-mentioned suitable range further suppresses the reduction of molecular weight of individual polyanions, thereby further maintaining the atmospheric exposure resistance of the conductive layer.

[0014] Methods for reducing the oxygen concentration in the residual space include, for example, injecting a conductive polymer-containing liquid into the container, and then blowing an inert gas such as nitrogen gas or argon gas into the container to expel the air contained in the residual space. Alternatively, the conductive polymer-containing liquid may be injected into the container after the inert gas has been injected. Another method involves injecting the conductive polymer-containing liquid into the container and then using a vacuum pump to remove the air contained in the residual space.

[0015] A conductive composite storage container (hereinafter sometimes referred to as a storage container) is obtained by injecting a conductive polymer-containing liquid into the aforementioned container, reducing the oxygen concentration in the remaining space to 9.9% by volume or less, and then sealing the container. The conductive polymer-containing liquid can be stably stored in the sealed storage container. The constituent material of the container is not particularly limited as long as it can seal the conductive polymer-containing liquid inside the container, and examples include glass, synthetic resin, metal, ceramics, etc. The shape of the container is not particularly limited as long as it can seal the conductive polymer-containing liquid inside the container, and examples include bottles with lids, resealable bags, test tubes with lids, cans with lids, etc.

[0016] When the initial weight-average molecular weight of a single polyanion at the start of storage of the conductive polymer-containing liquid using the aforementioned storage container is X, and the weight-average molecular weight of a single polyanion after 720 hours of storage of the conductive polymer-containing liquid at 40°C to 50°C is Y, the molecular weight ratio expressed as Y / X is preferably 0.89 or higher, more preferably 0.91 or higher, and even more preferably 0.93 or higher. The closer the molecular weight ratio is to 1.0, the less the individual polyanions degrade in molecular weight during storage, indicating higher storage stability. Furthermore, even after storage, a conductive layer with excellent resistance to atmospheric exposure can be formed.

[0017] In this specification and the claims, the molecular weight ratio (Y / X) shall have two significant figures. For example, the calculated value of Y / X = 90,000 / 96,000, which is 0.9375, is rounded to 0.94 by rounding to the third decimal place. Here, each weight-average molecular weight may have two significant figures.

[0018] The ratio (V1 / V2) of the volume of the residual space V1 in the container to the volume V2 of the conductive polymer-containing liquid contained in the container is preferably 1.5 or less, more preferably 0.5 or less, and even more preferably 0.1 or less. The lower limit is not particularly limited and can be, for example, around 0.01. Within the above preferred range, the reduction of molecular weight of individual polyanions can be further suppressed, and the atmospheric exposure resistance of the conductive layer can be further maintained.

[0019] <Conductive polymer containing liquid> The conductive polymer-containing liquid contains a conductive composite comprising a π-conjugated conductive polymer and a polyanion, the polyanion not forming the conductive composite (a single polyanion), and a dispersion medium. In the conductive polymer-containing liquid of this embodiment, the conductive composite may be in a dispersed state or in a dissolved state. Unless otherwise specified herein, there is no distinction between the dispersed state and the dissolved state.

[0020] <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 and has the effects of the present invention. Examples include polypyrrole-based conductive polymers, polythiophene-based conductive polymers, polyacetylene-based conductive polymers, polyphenylene-based conductive polymers, polyphenylene-vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene-vinylene-based conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferred, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferred.

[0021] Examples of polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3-chlorothiophene), and poly(3-iodine). 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-Dodecyl 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-di Examples include dodecyloxythiophene, 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), and poly(3-methyl-4-carboxybutylthiophene). Examples of polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butylpyrrole), 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), and poly(3-methyl-4-hexyloxypyrrole). Examples of polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid). Among the π-conjugated conductive polymers mentioned above, poly(3,4-ethylenedioxythiophene) is particularly preferred in terms of conductivity, transparency, and heat resistance. The conductive composite may contain one type of π-conjugated conductive polymer, or two or more types.

[0022] <Polyanion> A polyanion is a polymer that has two or more monomer units containing anionic groups within its molecule. The anionic groups of this polyanion function as dopants for π-conjugated conductive polymers, which can improve the conductivity of the π-conjugated conductive polymer. The anionic group of the polyanion is preferably a sulfo group or a carboxyl group. Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid esters having sulfo groups, polymethacrylic acid esters having sulfo groups (for example, poly(4-sulfobutyl methacrylate, polysulfoethyl methacrylate, polymethacryloyloxybenzene sulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, and other polymers having sulfo groups, as well as polymers having carboxyl groups such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), and polyisoprene carboxylic acid. These may be homopolymers or copolymers of two or more types. Among these polyanions, polymers having sulfo groups are preferred because they can achieve higher conductivity, and polystyrene sulfonic acid is even more preferred. The aforementioned polyanion may be one type or two or more types.

[0023] Polyanions form conductive composites by doping π-conjugated conductive polymers. However, in polyanions that form conductive composites, some anionic groups do not dope the π-conjugated conductive polymer, resulting in excess anionic groups that do not participate in doping. Since these excess anionic groups are hydrophilic, the conductive composites have high water dispersibility and low organic solvent dispersibility. When the total number of anionic groups in the polyanion forming the conductive composite is taken as 100 mol%, the excess anionic groups are preferably 30 mol% to 90 mol%, and more preferably 45 mol% to 75 mol%.

[0024] The polyanion content in the conductive composite is preferably in the range of 1 to 1000 parts by mass, more preferably 10 to 700 parts by mass, and even more preferably 100 to 500 parts by mass, per 100 parts by mass of the π-conjugated conductive polymer. If the polyanion content is above the 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 below the upper limit, the π-conjugated conductive polymer can be sufficiently contained, thus ensuring sufficient conductivity.

[0025] When the conductive polymer-containing liquid of this embodiment is filtered, polyanions forming conductive composites can be separated from polyanions that do not form conductive composites (single polyanions). That is, the conductive composites can be trapped in the filter, while the single polyanions can be allowed to pass through and recovered in the filtrate. It is preferable to use a membrane filter with an average pore size of 0.2 μm for the filtering process.

[0026] The weight-average molecular weight of a single polyanion is determined by gel permeation chromatography, using pullulan of known weight-average molecular weight as a standard substance. This is the average molecular weight (which may also be called the mass-average molecular weight).

[0027] The weight-average molecular weight X of a single polyanion is preferably between 80,000 and 800,000, more preferably between 90,000 and 700,000, even more preferably between 95,000 and 600,000, particularly preferably between 95,000 and 500,000, and most preferably between 95,000 and 400,000. If the value is above the lower limit of the above range, it is possible to suppress the gelation of the conductive polymer-containing liquid while increasing the conductivity of the conductive layer formed from the conductive polymer-containing liquid. Furthermore, a conductive polymer-containing liquid with a suitable Y / X ratio can be easily obtained. If the value is below the upper limit of the above range, the dispersibility of polyanions in the conductive polymer-containing liquid increases, and the conductivity of the conductive layer can be further enhanced.

[0028] The content of individual polyanions relative to the total mass of the conductive polymer-containing liquid in this embodiment can be, for example, 0.01% by mass or more and 2.5% by mass or less, preferably 0.05% by mass or more and 2.0% by mass or less, more preferably 0.1% by mass or more and 1.5% by mass or less, and even more preferably 0.5% by mass or more and 1.0% by mass or less. If the value is above the lower limit of the above range, the resistance of the formed conductive layer to atmospheric exposure will be higher. If the value is below the upper limit of the above range, the conductivity of the formed conductive layer will be higher.

[0029] The content of individual polyanions in the conductive polymer-containing liquid of this embodiment can be, for example, 1 part by mass or more and 10,000 parts by mass or less per 100 parts by mass of π-conjugated conductive polymer, preferably 5 parts by mass or more and 5,000 parts by mass or less, more preferably 10 parts by mass or more and 1,000 parts by mass or less, and even more preferably 50 parts by mass or more and 500 parts by mass or less. If the value is above the lower limit of the above range, the resistance of the formed conductive layer to atmospheric exposure will be higher. If the value is below the upper limit of the above range, the conductivity of the formed conductive layer will be higher.

[0030] The content of the conductive composite relative to the total mass of the conductive polymer-containing liquid in this embodiment can be, for example, 0.01% by mass or more and 10.0% by mass or less, preferably 0.05% by mass or more and 7.5% by mass or less, more preferably 0.1% by mass or more and 5.0% by mass or less, and even more preferably 0.5% by mass or more and 2.5% by mass or less. If the value is above the lower limit of the above range, the conductivity of the formed conductive layer will be higher. If the value is below the upper limit of the above range, the dispersibility of the conductive composite in the conductive polymer-containing liquid can be improved, and a uniform conductive layer can be formed.

[0031] The content of the π-conjugated conductive polymer relative to the total mass of the conductive polymer-containing liquid in this embodiment can be, for example, 0.1% by mass or more and 2.0% by mass or less. The total content of polyanions relative to the total mass of the conductive polymer-containing liquid in this embodiment can be, for example, 0.3% by mass or more and 10% by mass or less. Here, there is no distinction made between polyanions that form a conductive composite and those that do not. The content ratio of the π-conjugated conductive polymer and polyanions in the conductive polymer-containing liquid of this embodiment is preferably (1:2) to (1:5) by mass, more preferably (1:2) to (1:4), and even more preferably (1:2) to (1:3). Here, there is no distinction made between polyanions that form conductive composites and those that do not.

[0032] [Dispersion medium] Examples of dispersion media included in the conductive polymer-containing liquid of this embodiment include water, an organic solvent, and a mixture of water and an organic solvent.

[0033] Examples of organic solvents include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents. Specific examples will be given later. Organic solvents may be used individually or in combination of two or more types.

[0034] Since conductive composites have high dispersibility in water, the dispersion medium for the conductive polymer-containing liquid in this embodiment is preferably an aqueous dispersion medium containing water. The water content relative to the total mass of the dispersion medium in the conductive polymer-containing liquid of this 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 more preferably 70% by mass or more and 100% by mass or less. A monohydric alcohol is preferred as the dispersion medium other than water.

[0035] <Optional ingredients> The conductive polymer-containing liquid of this embodiment may further contain a binder component, a high-conductivity agent, other additives, etc.

[0036] (Other additives) The additives are not particularly limited as long as the effects of the present invention are obtained, and for example, surfactants, inorganic conductive agents, defoaming agents, coupling agents, antioxidants, ultraviolet absorbers, etc. can be used. Examples of surfactants include nonionic, anionic, and cationic surfactants, but nonionic surfactants are preferred in terms of storage stability. Polymer-based surfactants 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 metal salts in water. Examples of defoaming agents include silicone resins, polydimethylsiloxanes, and silicone oils. Examples of coupling agents include silane coupling agents having a vinyl group or an amino group. Examples of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and sugars. Examples of UV absorbers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxanilide-based UV absorbers, hindered amine-based UV absorbers, and benzoate-based UV absorbers. When the conductive polymer-containing liquid of this embodiment contains the above-mentioned additive, the content ratio can be appropriately determined according to the type of additive, but for example, it can be in the range of 0.001 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the π-conjugated conductive polymer and total polyanions.

[0037] ≪Method for producing a conductive polymer-containing liquid (1)≫ The conductive polymer-containing liquid of the first embodiment can be produced, for example, by a manufacturing method including a polymerization step described below. The polymerization step involves polymerizing monomers that form a π-conjugated conductive polymer in a reaction solution containing a polyanion and an aqueous dispersion medium to obtain a conductive polymer-containing liquid that includes a conductive composite containing the π-conjugated conductive polymer and the polyanion, the aqueous dispersion medium, and the polyanion that does not form the conductive composite (a single polyanion).

[0038] The weight-average molecular weight (Mw) of the polyanion used in the polymerization process is preferably between 80,000 and 1,000,000, more preferably between 100,000 and 800,000, and even more preferably between 150,000 and 600,000. Here, the weight-average molecular weight is the average molecular weight on a mass basis, determined by measuring it by gel permeation chromatography (GPC) and using pullulan of 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 enhanced. Furthermore, before subjecting the aqueous solution of polyanions to GPC, it is preferable to filter it using a membrane filter with an average pore size of 0.2 μm to remove impurities and other contaminants contained in the aqueous solution, and then use the resulting filtrate for GPC measurement.

[0039] One method for synthesizing polyanions with a specific weight-average molecular weight is to adjust the amount of oxidizing agent added to polymerize the monomers that make up the polyanion. Specifically, increasing the concentration of the oxidizing agent can reduce the weight-average molecular weight of the polyanion formed by the polymerization of the monomers. By this method, for example, polystyrene sulfonic acid with a weight-average molecular weight Mw of 100,000 to 1,000,000 can be obtained.

[0040] [Polymerization process] A reaction solution is prepared containing monomers that form the π-conjugated conductive polymer and polyanions in any ratio, and the monomers are polymerized to form the π-conjugated conductive polymer. In the reaction solution, the polyanions spontaneously dope the π-conjugated conductive polymer, forming a conductive composite consisting of the π-conjugated conductive polymer and polyanions. In addition, some of the polyanions do not form a conductive composite and remain as individual polyanions.

[0041] A catalyst may be added to the reaction solution. The catalyst is not particularly limited as long as it promotes the polymerization of the monomer, and examples include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride. In particular, it is preferable to use a catalyst containing iron because the polymerization of the monomer proceeds stably at room temperature.

[0042] It is preferable that the reaction solution contains an oxidizing agent along with the catalyst. The oxidizing agent can polymerize the monomer. Examples of oxidizing agents include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. It is preferable to slowly add the oxidizing agent, which has been pre-dissolved in deionized water, as an oxidizing agent solution to the mixed solution S1 containing the monomer, the polyanion, and the catalyst, in order to start polymerization. The concentration of the oxidizing agent solution is preferably 1.0% by mass or more and 3.0% by mass or less. When the volume of the mixed liquid S1 before adding the oxidizing agent solution is V1 and the volume of the oxidizing agent solution is V2, the volume ratio expressed as V1 / V2 is preferably 1.0 to 2.0, and more preferably 1.2 to 1.5. When adding all of the oxidizing agent solution to the mixed liquid S1, the time required from the start to the end of the addition is preferably 1 to 8 hours, more preferably 2 to 7 hours, and even more preferably 3 to 6 hours. The temperatures of the mixed liquid S1 before adding the oxidizing agent solution and the oxidizing agent solution are preferably 5 to 30°C, independently of each other.

[0043] It is preferable to maintain the temperature of the reaction solution obtained after adding all of the oxidizing agent solution at 5 to 30°C while carrying out the polymerization reaction. The approximate reaction time required for the reaction to be completed in the aforementioned reaction solution is 4 to 12 hours, with a preferred reaction time of 6 to 10 hours. The completion of the polymerization reaction can be determined by gas chromatography, which confirms that the monomers forming the π-conjugated conductive polymer have disappeared.

[0044] The monomer to polyanion content ratio in the mixed liquid S1 is preferably (1:2) to (1:5) by mass, more preferably (1:2) to (1:4), and even more preferably (1:2) to (1:3). When the value is above the lower limit of the above range, the doping effect by polyanions is fully realized, and the dispersion stability of the conductive composite is further improved. If the value is below 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. Furthermore, a conductive polymer-containing liquid in which the Y / X ratio is within a suitable range can be easily obtained.

[0045] The monomer content relative to the total mass of the mixed liquid S1 is preferably, for example, 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 even more preferably 0.3% by mass or more and 1.0% by mass or less. Within the above range, the polymerization reaction can proceed stably, and the compounding with polyanions present in the reaction system proceeds easily. Furthermore, a conductive polymer-containing liquid with a suitable Y / X ratio can be easily obtained.

[0046] The content of the polyanion relative to the total mass of the mixed liquid S1 is preferably set based on the content ratio relative to the monomer. For example, 0.1% by mass or more and 10% by mass or less is preferred, 0.3% by mass or more and 8.0% by mass or less is more preferred, and 0.6% by mass or more and 4.0% by mass or less is even more preferred. Within the above range, a conductive polymer-containing liquid in which the Y / X ratio is within a suitable range can be easily obtained.

[0047] The weight-average molecular weight of the polyanion contained in the aforementioned mixture S1 is preferably within the range described above. Within the above range, a conductive polymer-containing liquid in which the Y / X ratio is within a suitable range can be easily obtained.

[0048] The content of the catalyst relative to the total mass of the reaction solution after all the oxidizing agents have been added is preferably, for example, 0.001% by mass or more and 2.0% by mass or less, more preferably 0.01% by mass or more and 1.0% by mass or less, and even more preferably 0.1% by mass or more and 0.5% by mass or less, relative to the total mass of the reaction solution. Within the above range, the polymerization reaction can proceed stably, making it easy to compound with polyanions. Furthermore, a conductive polymer-containing liquid with a suitable Y / X ratio can be easily obtained.

[0049] The amount of oxidizing agent added relative to the total mass of the reaction solution after all the oxidizing agent has been added is preferably, for example, 0.01% by mass or more and 2.0% by mass or less, more preferably 0.1% by mass or more and 1.5% by mass or less, even more preferably 0.5% by mass or more and 1.2% by mass or less, and particularly preferably 0.7% by mass or more and 1.0% by mass or less. Within the above range, the polymerization reaction can proceed stably, making it easy to compound with polyanions. Furthermore, a conductive polymer-containing liquid with a suitable Y / X ratio can be easily obtained.

[0050] The amount of monomer added before the reaction, relative to the total mass of the reaction solution after all the oxidizing agents have been added, is preferably 0.05% by mass or more and 5.0% by mass or less, more preferably 0.1% by mass or more and 3.0% by mass or less, and even more preferably 0.2% by mass or more and 2.0% by mass or less. Within the above range, the polymerization reaction can proceed stably, and the compounding with polyanions present in the reaction system proceeds easily. Furthermore, a conductive polymer-containing liquid with a suitable Y / X ratio can be easily obtained.

[0051] The amount of the polyanion added before the reaction, relative to the total mass of the reaction solution after all the oxidizing agents have been added, is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 6.0% by mass or less, and even more preferably 0.5% by mass or more and 4.0% by mass or less. Within the above range, a conductive polymer-containing liquid in which the Y / X ratio is within a suitable range can be easily obtained.

[0052] The aqueous dispersion medium constituting the reaction solution may contain at least water and may further contain a water-soluble organic solvent. Specific examples of water-soluble organic solvents will be described later. The water content relative to the total mass of the aqueous dispersion medium is preferably, for example, 60% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, even more preferably 80% by mass or more and 100% by mass or less, and particularly preferably 90% by mass or more and 100% by mass or less.

[0053] (Removal of catalyst and oxidizing agent) When a reaction solution containing a catalyst and an oxidizing agent is used, it is preferable to remove the catalyst and oxidizing agent from the conductive polymer-containing solution obtained after the reaction. Methods for removal include, for example, contacting an ion exchange resin with a conductive polymer-containing liquid to adsorb the catalyst and oxidizing agent onto the ion exchange resin, and removing the conductive polymer-containing liquid along with the replacement of the aqueous dispersion medium by ultrafiltration. Of these, the method using an ion exchange resin is preferred because it is simple. It is preferable to use a combination of a cation exchange resin and an anion exchange resin.

[0054] (Distributed processing) It is preferable to stir the conductive polymer-containing liquid obtained in the polymerization process to disperse the conductive composite. The stirring method is not particularly limited; it may be stirred using a stirrer or other device with low shear force, or it may be stirred using a high-shear force disperser such as a high-pressure homogenizer. However, from the viewpoint of improving dispersibility, it is preferable to use a high-pressure homogenizer or the like.

[0055] Through the polymerization process described above, a conductive polymer-containing liquid is obtained, which includes a conductive composite comprising a π-conjugated conductive polymer and a polyanion, the aqueous dispersion medium, and the polyanion (a single polyanion) that does not form the conductive composite.

[0056] It is preferable to separate individual polyanions from the obtained conductive polymer-containing liquid and then measure their weight-average molecular weight X, as this allows for accurate measurement without being affected by the conductive composite. One example of the separation method is to filter the conductive polymer-containing liquid using a membrane filter with an average pore size of 0.2 μm, trapping the conductive composite in the filter while allowing the individual polyanions to pass through and recover them in the filtrate.

[0057] The weight-average molecular weight X of a single polyanion is measured by gel permeation chromatography and is the mass-based average molecular weight determined using pullulan of known weight-average molecular weight as a standard substance. The weight-average molecular weight Y of a single polyanion contained in a conductive polymer-containing solution after storage is measured in the same manner.

[0058] The weight-average molecular weight X of a single polyanion is preferably smaller than the weight-average molecular weight Z of the polyanions subjected to the polymerization process. The ratio of the weight-average molecular weight X to the weight-average molecular weight Z, expressed as X / Z, can be, for example, 0.1 or more and less than 0.67.

[0059] The conductive polymer-containing liquid obtained in the polymerization step may be subjected to the precipitation and recovery step described below.

[0060] ≪Method for producing a conductive polymer-containing liquid (2)≫ A second aspect of the present invention is a method for producing a conductive polymer-containing liquid, comprising: adding one or more compounds selected from epoxy compounds, amine compounds, and quaternary ammonium compounds to a conductive polymer-containing liquid stored by the method of the first aspect to precipitate a reaction product containing the conductive composite (precipitation step); and recovering the precipitated reaction product and adding an organic solvent (recovery step).

[0061] [Precipitation process] By adding one or more compounds selected from epoxy compounds, amine compounds, and quaternary ammonium compounds to a conductive polymer-containing liquid (hereinafter sometimes referred to as a conductive polymer dispersion) stored by the method of the first embodiment, a reaction product containing the conductive composite can be precipitated. Similarly, individual polyanions that do not form a conductive composite also react and precipitate. The anionic groups, such as sulfonic acid groups, of the reaction product precipitated in this process are hydrophobized by the reaction of the added compound described above, forming one of the following substituents (A) to (C).

[0062] In the following, the excess anionic groups in a polyanion that do not participate in doping may be referred to as "some anionic groups." The following substituent (A) is formed by the reaction of some anionic groups with epoxy compounds. The following substituent (B) is formed by the reaction of some anionic groups with amine compounds. The following substituent (C) is formed by the reaction of some anionic groups with quaternary ammonium compounds.

[0063] (Substituent A) The substituent (A) is presumed to be a group represented by the following formula (A1) or the following formula (A2).

[0064] [ka]

[0065] [In formula (A1), R 1 , R 2 , R 3 , and R 4 Each of these is independently a hydrogen atom or any substituent.

[0066] [ka]

[0067] [In 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, and the plurality of R 5 may be the same or different, the plurality of R 6 may be the same or different, the plurality of R 7 may be the same or different, and the plurality of R 8 may be the same or different.]

[0068] In formulas (A1) and (A2), the left - hand bond represents that the substituent (A) is substituted with the proton of an anionic group such as a sulfonic acid group.

[0069] In formula (A1), as any substituent of R 1 , R 2 , R 3 , and R 4 , there may be mentioned an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the like. R 1 and R 3 may combine to form a ring which may have a substituent. For example, when R 1 and R 3 are the above - mentioned hydrocarbon groups, a divalent hydrocarbon group obtained by removing any one hydrogen atom from the monovalent hydrocarbon group of R 1 and a divalent hydrocarbon group obtained by removing any one hydrogen atom from the monovalent hydrocarbon group of R 3 may be bonded to each other at the carbon atoms from which the hydrogen atoms have been removed to form a ring. In formula (A2), as any substituent of R 5 , R 6 , R 7 , and R 8 , there may be mentioned an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the like. R 5 and R 7It may bond to form a ring which may have substituents. Examples of ring formation are the same as described above. Here, "may have substituents" includes both cases where a hydrogen atom (-H) is substituted with a monovalent group and cases where a methylene group (-CH2-) is substituted with a divalent group. Examples of monovalent groups as substituents include C1-C4 alkyl groups, C2-C4 alkenyl groups, halogen atoms (fluorine, chlorine, bromine, iodine, etc.), trialkoxysilyl groups (trimethoxysilyl, etc.), and the like. Examples of divalent groups as substituents include oxygen atoms (-O-), -C(=O)-, and -C(=O)-O-. m is an integer greater than or equal to 2, preferably between 2 and 100, more preferably between 2 and 50, and even more preferably between 2 and 25. When m is above the lower limit, the hydrophobicity of the conductive composite becomes sufficiently high. When m is below the upper limit, it is possible to suppress excessive hydrophobicity or a decrease in conductivity.

[0070] Epoxy compounds are compounds that have one or more epoxy groups in one molecule (epoxy group-containing compounds). In terms of preventing aggregation or gelation, epoxy compounds that have one epoxy group in one molecule are preferred. The epoxy compound that reacts with the aforementioned anionic groups may be one type or two or more types.

[0071] Examples of monofunctional epoxy compounds having one epoxy group in one molecule include 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 monooxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2-epoxyoctadecane, 1,2-epoxyhexadecane, and ethylene oxide. 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 Luether, 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-glycidyloxypropyl trim Toxysilane, epoxy succinic 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, 4-tert-butylbenzoate glycidyl, 2,2-Bis(4-glycidyloxyphenyl)propane, 2-tert-butyl-2-[2-(4-chlorophenyl)]ethyloxirane, styrene oxide, glycidyl trityl ether, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α,6α-epoxide, stilbene oxide, p-glycidyl p-toluenesulfonate, ethyl 3-methyl-3-phenylglycidate, N-propyl-N-(2,3-epoxypropyl)perfluoro-n- Examples include octyl sulfonamide, (2S,3S)-1,2-epoxy-3-(tert-butoxycarbonylamino)-4-phenylbutane, 3-nitrobenzenesulfonic acid (R)-glycidyl, 3-nitrobenzenesulfonic acid-glycidyl, parthenolide, N-glycidylphthalimide, endrin, dieldrin, 4-glycidyloxycarbazole, 7,7-dimethyloctanoic acid [oxyranylmethyl], 1,2-epoxy-4-vinylcyclohexane, and higher alcohol glycidyl ethers having 10 to 16 carbon atoms.

[0072] The aforementioned higher alcohol glycidyl ether is preferably one or more higher alcohol glycidyl ethers having 10 to 16 carbon atoms, more preferably one or more higher alcohol glycidyl ethers having 12 to 14 carbon atoms, and even more preferably at least one of C12 (12 carbon atoms) higher alcohol glycidyl ethers and C13 (13 carbon atoms) higher alcohol glycidyl ethers.

[0073] 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, 4-butanediol diglycidyl ether, 1,2:3,4-diepoxybutane, 1,2-cyclohexanedicarboxylic acid diglycidyl, isocyanurate triglycidyl, neopentyl glycol diglycidyl ether, 1,2:3,4-diepoxybutane, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. Examples include ricidyl 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, hexahydrophthalate diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol-based polyglycidyl ether, ethylene oxide delauryl alcohol glycidyl ether, and the like.

[0074] Epoxy compounds are preferably 50 to 2000 in molecular weight, as this improves their dispersibility in organic solvents. Furthermore, epoxy compounds are preferably 4 to 120 carbon atoms, more preferably 7 to 100 carbon atoms, even more preferably 10 to 80 carbon atoms, and particularly preferably 15 to 50 carbon atoms, as these improve their dispersibility in low-polarity hydrocarbon solvents and ester solvents.

[0075] (Substituent B) The substituent (B) is presumed to be a group represented by the following formula (B).

[0076] -HN + R 11 R 12 R 13 ...(B) [In formula (B), R 11 ~R 13 Each of these is independently a hydrogen atom or a hydrocarbon group which may have substituents, however R 11 ~R 13 At least one of these is a hydrocarbon group which may have substituents.

[0077] In substituent (B), the leftmost bond is the negative charge of the anionic group, for example, the negative charge of the sulfonic acid group "-SO3". - This indicates that the positive charge of the amine compound is bonded to it.

[0078] R in chemical formula (B) 11 ~R 13 R is a hydrogen atom or a hydrocarbon group which may have substituents. 11 ~R 13 This substituent is derived from the amine compound described later. The hydrocarbon group in chemical formula (B) may be an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents. Examples of aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of substituents on aliphatic hydrocarbon groups include phenyl groups and hydroxyl groups. Examples of aromatic hydrocarbon groups include phenyl groups and naphthyl groups. Examples of substituents on aromatic hydrocarbon groups include alkyl groups having 1 to 5 carbon atoms and hydroxyl groups.

[0079] 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 some of the anionic groups may be one type or two or more types. Examples of primary amines include aniline, toluidine, benzylamine, and ethanolamine. Examples of secondary amines include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, and dinaphthylamine. Examples of tertiary amines include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, trynzylamine, and trinaphthylamine. Among the amine compounds, tertiary amines are preferred, and at least one of trioctylamine and tributylamine is more preferred, as they can enhance the conductivity of the conductive composite in this embodiment.

[0080] To improve dispersibility in organic solvents, particularly in low-polarity hydrocarbon solvents and ester solvents, amine compounds preferably have substituents with 4 or more carbon atoms on the nitrogen atom, more preferably 6 or more carbon atoms, and even more preferably 8 or more carbon atoms. The upper limit of the carbon number of substituents on the nitrogen atom is not particularly limited, and considering solubility and reactivity in solvents, for example, 50 or less is preferred, 40 or less is more preferred, and 30 or less is even more preferred. Furthermore, the R possessed by the amine compound 11 ~R 13 The total number of carbon atoms is preferably 6 to 33, more preferably 9 to 30, and even more preferably 12 to 27. The number of carbon atoms in each substituent on the nitrogen atom may be the same or different.

[0081] When some of the aforementioned anionic groups have substituents (A) and (B), the mass ratio of [substituent (A)]:[substituent (B)] (hereinafter also referred to as the A / B 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 / B ratio is within the above range, it is easier to balance dispersibility and conductivity. The mass of [substituent (A)] can be calculated as [(mass of reaction product A obtained by reacting with the epoxy compound) - (mass of the conductive composite and the polyanion that does not form a conductive composite before reacting with the epoxy compound)]. The mass of [substituent (B)] can be calculated as [(mass of reaction product B obtained by reacting reaction product A with the amine compound) - (mass of reaction product A)].

[0082] (Substituent C) The substituent (C) is presumed to be a group represented by the following formula (C).

[0083] -N + R 11 R 12 R 13 R 14 ...(C) [In formula (C), R 11 ~R 14 Each of these is independently a hydrocarbon group that may have substituents.

[0084] In substituent (C), the leftmost bond is the negative charge of the anionic group, for example, the negative charge of the sulfonic acid group "-SO3". - This indicates that the positive charge of the quaternary ammonium cation is bonded to it.

[0085] R in chemical formula (C) 11 ~R 14 R is a hydrocarbon group which may have substituents. 11 ~R 14 This substituent is derived from a quaternary ammonium compound. The hydrocarbon group in chemical formula (C) may be an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have substituents. Examples of aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of substituents on aliphatic hydrocarbon groups include phenyl groups and hydroxyl groups. Examples of aromatic hydrocarbon groups include phenyl groups and naphthyl groups. Examples of substituents on aromatic hydrocarbon groups include alkyl groups having 1 to 5 carbon atoms and hydroxyl groups.

[0086] Because dispersibility in organic solvents is improved and conductivity is enhanced, quaternary ammonium compounds preferably have substituents with 3 or more carbon atoms on the nitrogen atom, more preferably have substituents with 5 or more carbon atoms, and even more preferably have substituents with 7 or more carbon atoms on the nitrogen atom. The upper limit of the number of carbon atoms of each substituent on the nitrogen atom is not particularly limited, and considering solubility and reactivity in solvents, for example, 40 or less is preferred, 30 or less is more preferred, and 20 or less is even preferred. Furthermore, the R possessed by the quaternary ammonium compound 11 ~R 14 The total number of carbon atoms is preferably 8 to 44, more preferably 12 to 40, and even more preferably 16 to 36. The number of carbon atoms in each substituent on the nitrogen atom may be the same or different.

[0087] Specific examples of quaternary ammonium compounds include quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tetra-n-octylammonium salt, tetraphenylammonium salt, tetrabenzylammonium salt, and tetranaphthylammonium salt. Examples of counteranions for ammonium cations include halogen ions such as bromide ions and chloride ions, as well as hydroxyl ions.

[0088] When the conductive composite has substituents (A) and (C), the mass ratio of [substituent (A)]:[substituent (C)] (hereinafter also referred to as the 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 is easier to balance dispersibility and conductivity. The mass of [substituent (A)] can be calculated as [(mass of reaction product A obtained by reacting with the epoxy compound) - (mass of the conductive composite and polyanion that does not form a conductive composite before reacting with the epoxy compound)]. The mass of [substituent (C)] can be calculated as [(mass of reaction product C obtained by reacting reaction product A with a quaternary ammonium compound) - (mass of reaction product A)].

[0089] When adding one or more epoxy compounds to a conductive polymer dispersion, the amount of epoxy compound added is preferably 10 to 10,000 parts by mass, more preferably 100 to 5,000 parts by mass, and even more preferably 500 to 3,000 parts by mass, per 100 parts by mass of the π-conjugated conductive polymer and total polyanions (including polyanions forming conductive composites) contained in the conductive polymer dispersion. When the value is above the lower limit of the above range, the hydrophobicity of the conductive composite becomes sufficiently high, and its dispersibility in organic solvents improves. If the value is below the upper limit of the above range, it is possible to prevent a decrease in conductivity due to unreacted epoxy compounds. When adding epoxy compounds, heating may be performed to accelerate the reaction. The heating temperature is preferably between 40°C and 100°C.

[0090] When adding one or more amine compounds to a conductive polymer dispersion, the amount of amine compound added is preferably 1 to 10,000 parts by mass, more preferably 10 to 5,000 parts by mass, and even more preferably 100 to 2,000 parts by mass, per 100 parts by mass of the π-conjugated conductive polymer and total polyanions (including polyanions forming conductive composites) contained in the conductive polymer dispersion. When the value is above the lower limit of the above range, the hydrophobicity of the conductive composite becomes sufficiently high, and its dispersibility in organic solvents improves. If the value is below the upper limit of the above range, the decrease in conductivity due to unreacted amine compounds can be prevented.

[0091] When adding one or more quaternary ammonium compounds to a conductive polymer dispersion, the amount of quaternary ammonium compound added is preferably 1 to 10,000 parts by mass, more preferably 10 to 5,000 parts by mass, and even more preferably 50 to 2,000 parts by mass, per 100 parts by mass of the π-conjugated conductive polymer and total polyanions (including polyanions forming conductive composites) contained in the conductive polymer dispersion. When the value is above the lower limit of the above range, the hydrophobicity of the conductive composite becomes sufficiently high, and its dispersibility in organic solvents improves. If the value is below the upper limit of the above range, it is possible to prevent a decrease in conductivity due to unreacted quaternary ammonium compounds. Quaternary ammonium compounds exhibit good reactivity with a smaller amount added than amine compounds, through a reaction mechanism similar to that of amine compounds. Conductive layers containing conductive composites modified with quaternary ammonium compounds tend to have better conductivity than those modified with amine compounds.

[0092] Before, simultaneously with, or after adding one or more compounds selected from epoxy compounds, amine compounds, and quaternary ammonium compounds to the conductive polymer dispersion, an organic solvent may be added. A water-soluble organic solvent is preferred. Examples of water-soluble organic solvents include alcohol-based solvents, ketone-based solvents, and ester-based solvents. One or more organic solvents may be added.

[0093] When adding both an epoxy compound and an amine compound or a quaternary ammonium compound to the conductive polymer dispersion, the order of addition is not particularly limited. It is preferable to add the epoxy compound first and react it, and then add the amine compound or quaternary ammonium compound and react it, as this makes handling of the synthetic intermediate (reaction intermediate) easier.

[0094] [Recovery Process] The method for recovering the precipitated reaction product is not particularly limited and can be recovered by, for example, filtration or decantation.

[0095] The recovered reaction product (precipitation) should preferably contain as little water as possible, and most preferably no water at all. However, from a practical standpoint, it may contain water up to 10% by mass or less. Methods to reduce the amount of water include, for example, washing away the reaction products with an organic solvent or drying the reaction products.

[0096] [Washing process] The recovery process may include a washing step to wash the reaction products recovered in the recovery step. This washing step removes residual water, unreacted epoxy compounds, unreacted amine compounds or quaternary ammonium compounds, and hydrolysates of epoxy compounds, etc. The cleaning organic solvent should preferably be one that can clean while minimizing the dissolution of reaction products. For this reason, alcohol-based solvents are preferred as cleaning organic solvents. The cleaning organic solvent may contain one type of organic solvent or two or more types. There are no particular restrictions on the washing method; for example, the reaction product may be washed by pouring a washing organic solvent over it, or the reaction product may be washed by stirring it in the washing organic solvent.

[0097] [Addition process] This process involves adding a dispersion medium to the reaction product to obtain a conductive polymer-containing liquid. The dispersion medium to be added can be any medium capable of dispersing the reaction product, and it is preferable that it contains an organic solvent. When the conductive polymer-containing liquid contains a hydrophobized conductive composite, the content of the organic solvent relative to the total mass of the dispersion medium is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and even more preferably 90% by mass or more and 100% by mass or less.

[0098] The content of the reaction product relative to the total mass of the conductive polymer-containing liquid obtained in this process is preferably, for example, 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and even more preferably 0.2% by mass or more and 1% by mass or less. If the value is above 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. If the value is below the upper limit of the above range, the dispersibility of the reaction product in the conductive polymer-containing liquid is improved, and a uniform conductive layer can be formed.

[0099] <Organic solvents> Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, hydrocarbon-based solvents, nitrogen atom-containing compound-based solvents, and the like. The organic solvent may be one type or two or more types.

[0100] The aforementioned organic solvent may be a water-soluble organic solvent or a non-water-soluble organic solvent. Water-soluble organic solvents are organic solvents whose solubility in 100g of water at 20°C is 1g or more, while non-water-soluble organic solvents are organic solvents whose solubility in 100g of water at 20°C is less than 1g. As water-soluble organic solvents, one or more selected from alcohol-based solvents are preferred.

[0101] Examples of alcohol-based solvents include monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether; and dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. Examples of ether-based solvents include diethyl ether, dimethyl ether, and propylene glycol dialkyl ether. Examples of ketone-based solvents include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, and diacetone alcohol. Examples of ester-based solvents and hydrocarbon-based solvents will be described later. Examples of nitrogen atom-containing compound solvents include N-methylpyrrolidone, dimethylacetamide, and dimethylformamide. Examples of solvents not classified as above include dimethyl sulfoxide.

[0102] (Ester-based solvents) Ester solvents are compounds containing ester groups (-C(=O)-O-) that have an ester group. When the conductive composite is modified by a reaction between an epoxy compound and an amine compound or a quaternary ammonium compound, it is preferable that the organic solvent includes an ester-based solvent, as this further enhances the dispersibility of the conductive composite. From the viewpoint of improving the dispersibility of the conductive composite, it is preferable to include 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 R represents a hydrogen atom, a methyl group, or an ethyl group. 22 [This represents a linear or branched alkyl group having 1 to 6 carbon atoms.]

[0103] From the perspective of improving the dispersibility of conductive composites, R 21 A methyl group or an ethyl group is preferred, and a methyl group is more preferred. Also, R 22 The number of carbon atoms is preferably 2 to 5, and more preferably 2 to 4.

[0104] Examples of ester solvents include ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, and isobutyl acetate.

[0105] The content of the ester solvent in the organic solvent is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and may also be 100% by mass, based on the total mass of the organic solvent. When the content of the ester solvent is within the above range, the dispersibility of the conductive composite can be improved.

[0106] If the conductive polymer-containing liquid of this embodiment contains an ester-based solvent, it may also contain one or more other organic solvents besides the ester-based solvent. Examples of organic solvents other than ester-based solvents include hydrocarbon-based solvents (described later), ketone-based solvents (mentioned above), alcohol-based solvents, and nitrogen atom-containing compound-based solvents.

[0107] (Hydroxide-based solvents) In this embodiment, when the conductive composite contained in the conductive polymer-containing liquid is modified by reaction with an epoxy compound and an amine compound or a quaternary ammonium compound, the inclusion of a hydrocarbon solvent as a dispersion medium is preferable because it increases the wettability to the plastic film substrate and allows for easy addition of low-polarity binder components.

[0108] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents and aromatic hydrocarbon 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, and isopropylbenzene. Among these, toluene is preferred because of its high dispersibility of the conductive composite. Furthermore, when a silicone compound is added as a binder component, at least one of heptane and toluene is preferred because of its excellent solubility of the silicone compound.

[0109] It is preferable to include methyl ethyl ketone in addition to the hydrocarbon solvent, as this further improves the dispersibility of the conductive composite. For example, per 100 parts by mass of the hydrocarbon solvent, the amount of methyl ethyl ketone is preferably 20 to 120 parts by mass, more preferably 30 to 100 parts by mass, and even more preferably 40 to 80 parts by mass.

[0110] The hydrocarbon solvent content is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and may also be 100% by mass, relative to the total mass of the organic solvent. When the hydrocarbon solvent content is within the above range, the dispersibility of the conductive composite can be improved.

[0111] If the conductive polymer-containing liquid of this embodiment contains a hydrocarbon solvent, it may also contain one or more other organic solvents besides the hydrocarbon solvent. Examples of organic solvents other than hydrocarbon solvents include the aforementioned ketone solvents, alcohol solvents, ester solvents, and nitrogen atom-containing compound solvents.

[0112] Among the above, the organic solvent is preferably one or more selected from alcohol-based solvents, ketone-based solvents, and ester-based solvents, and more preferably one or more selected from isopropanol, methyl ethyl

[0113] (Distributed processing) After adding a dispersion medium to the reaction product, the conductive polymer-containing liquid may be stirred to perform dispersion treatment. The stirring method is not particularly limited; stirring with a weak shear force, such as with a stirrer, may be used, or stirring may be performed using a high-shear force disperser, such as a high-pressure homogenizer. However, from the viewpoint of improving dispersibility, it is preferable to use a high-pressure homogenizer or the like.

[0114] (Addition of optional ingredients) A binder component, a high-conductivity agent, and other additives may be added to the conductive polymer-containing liquid obtained above.

[0115] <Addition of binder components> By using a conductive polymer-containing liquid that includes a binder component, it is possible to improve the strength of the formed conductive layer and impart tackiness and release properties. The binder component is a resin other than the π-conjugated conductive polymer or the polyanion, or a precursor thereof, and is a thermoplastic resin, or a curable monomer or oligomer that hardens during the formation of the conductive layer. The thermoplastic resin becomes the binder resin as is, and the resin formed by the hardening of the curable monomer or oligomer becomes the binder resin. The aforementioned binder component may be an adhesive as described later. In this embodiment, the binder component added may be one type or two or more types.

[0116] 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.

[0117] The curable monomer or oligomer may be a thermosetting monomer or oligomer, or a photocurable monomer or oligomer. Here, an oligomer is a polymer with a mass-average molecular weight of less than 10,000. Examples of curable monomers include acrylic monomers (acrylic compounds), epoxy monomers, and organosiloxanes. Examples of curable oligomers include acrylic oligomers (acrylic compounds), epoxy oligomers, and silicone oligomers (curable silicones). When acrylic monomers or acrylic oligomers are used as the binder component, the material can be easily cured by heating or light irradiation.

[0118] If the material contains a curable monomer or oligomer, it is preferable to further include a curing catalyst. For example, if the material contains a thermosetting monomer or oligomer, it is preferable to include a thermal polymerization initiator that generates radicals upon heating, and if the material contains a photocurable monomer or oligomer, it is preferable to include a photopolymerization initiator that generates radicals upon light irradiation.

[0119] The content ratio of the binder component (excluding the silicone compound described later) in the conductive polymer-containing liquid of this embodiment is preferably, for example, 1 part by mass or more and 10,000 parts by mass or less, more preferably 10 parts by mass or more and 5,000 parts by mass or less, and even more preferably 100 parts by mass or more and 1,000 parts by mass or less, per 1 part by mass of the π-conjugated conductive polymer and the total polyanions. If the value is above 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 fully exhibited. If the value is below 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.

[0120] (Silicone compounds) In this embodiment, it is preferable that the dispersion medium of the conductive polymer-containing liquid includes a hydrocarbon solvent or an ester solvent, as this further enhances the dispersibility of the silicone compound. Examples of silicone compounds include curable silicones. When the binder component is a curable silicone, the conductive layer can be given release properties by curing the curable silicone.

[0121] The curable silicone may be either an addition-curing silicone or a condensation-curing silicone. In this embodiment, an addition-curing silicone is preferred because curing inhibition is less likely to occur.

[0122] Examples of addition-curing silicones include linear polymers having siloxane bonds, specifically polydimethylsiloxane having vinyl groups at both ends of the linear chain, and hydrogensilane. Such addition-curing silicones harden by forming a three-dimensional crosslinked structure through an addition reaction. Platinum-based curing catalysts may be used to accelerate the curing process. Specific examples of addition-curing 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-curing silicones are preferably used in a form that is dissolved or dispersed in an organic solvent.

[0123] The content ratio of the silicone compound in the conductive polymer-containing liquid of this embodiment is preferably 10 parts by mass or more and 10,000 parts by mass or less, more preferably 100 parts by mass or more and 5,000 parts by mass or less, and even more preferably 500 parts by mass or more and 3,000 parts by mass or less, based on 100 parts by mass of the π-conjugated conductive polymer and the total polyanions. If the value is above the lower limit of the above range, sufficient release properties can be imparted to the conductive layer formed by the conductive polymer-containing liquid of this embodiment. If the value is below 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.

[0124] [Adhesive] The conductive polymer-containing liquid in this embodiment may contain an adhesive as a binder component. By using a conductive polymer-containing liquid containing an adhesive, a conductive layer with adhesive properties can be formed. In this embodiment, when the dispersion medium of the conductive polymer-containing liquid contains a hydrocarbon solvent or an ester solvent, it is preferable that it can be easily mixed with an adhesive pre-dispersed in the hydrocarbon solvent or ester solvent, and that the conductive composite can be stably dispersed in the mixture.

[0125] The degree of tackiness of the adhesive is not particularly limited. It may be tacky enough to be easily peeled off by hand after application, or it may be tacky enough to be difficult to peel off after application. Tackiness that is difficult to peel off can be rephrased as adhesiveness. In other words, the tackiness may be such that it is possible to adhere semi-permanently.

[0126] Any known adhesive can be used as the aforementioned adhesive. From the viewpoint of maintaining conductivity while exhibiting good tackiness, an acrylic adhesive is preferred.

[0127] (Acrylic adhesive) Acrylic adhesives can bond and integrate surfaces of the same or different types of solids. Acrylic adhesives contain acrylic resin (acrylic polymer).

[0128] Specific examples of acrylic monomers that form 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, ditrimethylolpropanetetraacrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A ethylene oxide modified diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, glycerin propoxytriacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate Acrylates such as isobornyl acrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, and tripropylene glycol diacrylate; methacrylates such as 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, and trimethylolpropane trimethacrylate;Examples include (meth)acrylamides such as diacetone acrylamide, N,N-dimethylacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, methacrylamide, N-methylolacrylamide, acryloylformoline, N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-phenylacrylamide, acryloylpiperidine, and 2-hydroxyethylacrylamide. The acrylic monomer forming the aforementioned acrylic resin may be one type or two or more types. The tackiness can be adjusted by combining two or more types of acrylic monomers.

[0129] The acrylic resin may be a copolymer of an acrylic monomer and a vinyl monomer other than an acrylic monomer. Examples of vinyl monomers include styrene, α-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, and maleic anhydride. The content of acrylic monomer units in the above 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 above the aforementioned lower limit, tackiness can be easily achieved. The content of vinyl monomer units in the above copolymer can be, for example, 2 mol% or more and 20 mol% or less.

[0130] 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. Acrylic resins with a glass transition temperature above 80°C have low tackiness. The glass transition temperature of acrylic resins is -80°C or higher, and it is difficult to obtain those with a glass transition temperature lower than that. The glass transition temperature of acrylic resins 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 (especially n-butyl acrylate), and 2-ethylhexyl acrylate. In acrylic resins, the glass transition temperature decreases as the proportion of these monomer units increases.

[0131] The mass-average molecular weight of the acrylic resin is preferably between 10,000 and 2,000,000, and more preferably between 30,000 and 1,000,000. If the mass-average molecular weight of the acrylic resin is above the lower limit, sufficient cohesive force can be ensured. If it is below the upper limit, the tackiness can be further improved.

[0132] If the acrylic resin contains acrylic monomer units with reactive functional groups, it may be cured by reacting it with a curing agent. Curing the acrylic resin improves the cohesive strength of the conductive layer containing the adhesive, thereby increasing its strength. Furthermore, by improving the cohesive strength of the conductive layer, it is possible to create a re-peelable conductive layer that can be repeatedly bonded and peeled off. Examples of the reactive functional groups include hydroxyl groups, carboxyl groups, amino groups, amide groups, and epoxy groups. When reacting with polyfunctional isocyanates, which will be described later, the reactive functional groups are preferably hydroxyl groups, carboxyl groups, and amino groups, with hydroxyl groups being more preferred. Examples of acrylic monomers having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate. Examples of acrylic monomers having a carboxyl group include acrylic acid, methacrylic acid, and itaconic acid. Examples of acrylic monomers having an amino group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, and diethylaminoethyl methacrylate. Examples of acrylic monomers having an amide group include acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide. Examples of acrylic monomers having epoxy groups include glycidyl acrylate and glycidyl methacrylate. When using polyfunctional isocyanates as curing agents, among the acrylic monomers having the reactive functional groups, acrylic monomers having hydroxyl groups are preferred, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are more preferred, considering curability and cost. The acrylic monomer having the reactive functional group that forms the acrylic resin may be one type or two or more types.

[0133] The content ratio of the adhesive in the conductive polymer-containing liquid of this embodiment is preferably 10 parts by mass or more and 10,000 parts by mass or less, more preferably 100 parts by mass or more and 5,000 parts by mass or less, and even more preferably 300 parts by mass or more and 1,000 parts by mass or less, per 1 part by mass of the π-conjugated conductive polymer and total polyanions. If the value is above the lower limit of the above range, sufficient tackiness can be imparted to the conductive layer formed by the conductive polymer-containing liquid of this embodiment. If the value is below 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.

[0134] (Hardening agent) If the adhesive contained in the conductive polymer-containing liquid of this embodiment has a reactive functional group, it is preferable that the conductive polymer-containing liquid of this embodiment contains a curing agent. Examples of curing agents include isocyanate-based curing agents such as polyfunctional isocyanates having two or more isocyanate groups in one molecule, and epoxy-based 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 adhesive has acrylic monomer units having hydroxyl groups, it is preferable that the curing agent be a polyfunctional isocyanate.

[0135] Examples of 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, Examples include 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, tetramethylxylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, bicyclohepta triisocyanate, and trimethylhexamethylene diisocyanate. The polyfunctional isocyanate may be a modified diisocyanate formed from a modified polyfunctional isocyanate obtained by modifying the diisocyanate so that the NCO / OH molar ratio is 2 / 1 or more. The polyfunctional isocyanate may also be a modified polyisocyanate. Examples of modified polyisocyanates include polyurethane polyisocyanates obtained by reacting the polyfunctional isocyanate with a polyhydric alcohol, polyisocyanates containing isocyanurate rings obtained by polymerizing the polyfunctional isocyanate, and polyisocyanates containing biuret bonds obtained by reacting the polyfunctional isocyanate with water. The conductive polymer-containing liquid in this embodiment may contain one type of curing agent or two or more types.

[0136] The proportion of the curing agent contained in the conductive polymer-containing liquid in this embodiment is preferably, for example, 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, and even more preferably 3 to 10 parts by mass, per 100 parts by mass of the adhesive. Within the above range, sufficient tackiness can be imparted to the conductive layer formed by the conductive polymer-containing liquid of this embodiment.

[0137] (High-conductivity agent) The conductive polymer-containing liquid in this embodiment may also contain a high-conductivity agent. Here, the π-conjugated conductive polymer, polyanion, organic solvent, adhesive, curing agent, and binder component mentioned above are not classified as high-conductivity agents. However, the epoxy compound, amine compound, and quaternary ammonium compound may fall under the category of high-conductivity agents described herein. The highly conductive agent is preferably at least one compound selected from the group consisting of 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, compounds having an imide group, lactam compounds, and compounds having a glycidyl group. The conductive polymer-containing liquid of this embodiment may contain one or more types of high-conductivity agents. The content ratio of the highly conductive agent is preferably 1 to 10,000 parts by mass, more preferably 10 to 5,000 parts by mass, and even more preferably 100 to 2,500 parts by mass, per 100 parts by mass of the π-conjugated conductive polymer and total polyanions. If the content of the high-conductivity agent is above the lower limit, the conductivity-improving effect due to the addition of the high-conductivity agent will be fully exhibited, and if it is below the upper limit, the decrease in conductivity caused by a decrease in the concentration of the π-conjugated conductive polymer can be prevented.

[0138] (Other additives) The conductive polymer-containing liquid of this embodiment may also contain other known additives. The explanations for the other additives are the same as described above, so we will omit any redundant explanations here.

[0139] <<Conductive Laminate>> The conductive laminate according to the present invention comprises a substrate and a conductive layer formed on at least a portion of the surface of the substrate, the conductive layer being a cured layer of a conductive polymer-containing liquid. The conductive polymer-containing liquid may be stored using the storage method of the first embodiment, or it may be a conductive polymer-containing liquid containing a hydrophobized conductive composite produced by the manufacturing method of the second embodiment.

[0140] [Conductive layer] The area in which the conductive layer is formed may be the entire surface of any surface of the substrate, or it may be only a part of it. In the case of a conductive film, it is preferable that a conductive layer of substantially uniform thickness is formed on substantially the entire surface of one or the other surface of the film substrate. If the conductive layer is formed on only a 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 with the conductive layer and the area without the conductive layer may exist on the same surface and be roughly separated.

[0141] The average thickness of the conductive layer is preferably, for example, 10 nm to 100 μm, more preferably 20 nm to 50 μm, and even more preferably 30 nm to 30 μm. If the average thickness of the conductive layer is above the lower limit, high conductivity can be achieved, and if it is below the upper limit, the adhesion of the conductive layer to the substrate is further improved. The average thickness of the conductive layer is the average of the measurements taken at 10 randomly selected locations.

[0142] [Base material] The substrate may be made of an insulating material or a conductive material. The shape of the substrate is not particularly limited, and examples include mainly flat shapes 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.

[0143] (Film substrate) When a film substrate is used as the aforementioned substrate, the conductive laminate becomes a conductive film. Examples of the film substrate include plastic films made of synthetic resins. Examples of the synthetic resins include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene elastomer, polyester elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, and cellulose acetate propionate. From the viewpoint of improving adhesion between the film substrate and the conductive layer, the synthetic resin for the film substrate is preferably a polyester resin, and among these, polyethylene terephthalate is preferred.

[0144] The synthetic resin used 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 treatments such as corona discharge treatment, plasma treatment, or flame treatment in order to further improve the adhesion of the conductive layer.

[0145] The average thickness of the film substrate is preferably 5 μm to 500 μm, and more preferably 20 μm to 200 μm. If the average thickness of the film substrate is above the lower limit, it becomes less prone to tearing, and if it is below the upper limit, sufficient flexibility as a film can be ensured. The average thickness of the film substrate is the average of the measurements taken at 10 randomly selected locations.

[0146] (Glass substrate) Examples of glass substrates include alkali-free glass substrates, soda-lime glass substrates, borosilicate glass substrates, and quartz glass substrates. Since the presence of alkaline components in the substrate tends to reduce the conductivity of the conductive layer, alkali-free glass is preferred among the glass substrates. Here, alkali-free glass refers to a glass composition in which the content of alkaline components is 0.1% by mass or less of the total mass of the glass composition.

[0147] The average thickness of the glass substrate is preferably 100 μm to 3000 μm, and more preferably 100 μm to 1000 μm. If the average thickness of the glass substrate is above the lower limit, it becomes less prone to breakage, and if it is below the upper limit, it contributes to thinning the conductive laminate. The average thickness of the glass substrate is the average of the measurements taken at 10 randomly selected locations.

[0148] ≪Method for manufacturing conductive laminates≫ A third aspect of the present invention is a method for manufacturing a conductive laminate, comprising the step of coating a conductive polymer-containing liquid onto at least a portion of the surface of a substrate. The conductive polymer-containing liquid may be stored using the storage method of the first embodiment, or it may be a conductive polymer-containing liquid containing a hydrophobized conductive composite produced by the manufacturing method of the second embodiment.

[0149] The description of the substrate is the same as described above, so any redundant explanation will be omitted here.

[0150] Methods for coating (applying) a conductive polymer-containing liquid to any surface of a substrate include, for example, methods using coaters such as gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, fountain coaters, rod coaters, air doctor coaters, knife coaters, blade coaters, cast coaters, and screen coaters; methods using sprayers such as air sprayers, airless sprayers, and rotor dampening devices; and immersion methods such as dipping.

[0151] There are no particular restrictions on the amount of conductive polymer-containing liquid applied to the substrate, but considering uniform and even coating, conductivity, and film strength, the solid content should be approximately 0.01 g / m². 2 More than 10.0g / m 2 The following range is preferable.

[0152] A conductive layer can be formed by drying a coating film made of a conductive polymer-containing liquid applied to a substrate, removing at least a portion of the dispersion medium, and curing it. Methods for drying the coating include heat drying and vacuum drying. For heat drying, for example, methods such as hot air heating and infrared heating can be used. When applying heat drying, the heating temperature is set appropriately according to the dispersion medium used, but is usually within the range of 50°C to 200°C. Here, the heating temperature is the set temperature of the drying apparatus. Within the above heating temperature range, a suitable drying time is preferably 0.5 minutes to 30 minutes, and more preferably 1 minute to 15 minutes. After drying, UV irradiation may be performed to cure the binder components contained in the coating film.

[0153] The area in which the conductive layer is formed may be the entire surface of any surface of the substrate, or it may be only a part of it. In the case of a conductive film, it is preferable that a conductive layer of substantially uniform thickness is formed on substantially the entire surface of one or the other surface of the film substrate. If the conductive layer is formed on only a 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 with the conductive layer and the area without the conductive layer may exist on the same surface and be roughly separated.

[0154] The explanation for the average thickness of the conductive layer is the same as described above, so we will omit the redundant explanation here.

[0155] ≪Conductive composite storage device≫ A fourth aspect of the present invention is a conductive composite storage container in which a conductive polymer-containing liquid is sealed inside the container. Since the conductive polymer-containing liquid is the same as that described in the first embodiment, a redundant explanation will be omitted here. Within the container, there is a residual space not filled by the conductive polymer-containing liquid, and when the volume of this residual space is taken as 100% by volume, the oxygen concentration in that residual space is 9.9% by volume or less. Here, the volume of the residual space is the volume obtained by subtracting the volume of the conductive polymer-containing liquid from the volume of the container. The range of suitable oxygen concentrations in the residual space is the same as that described in the first embodiment, so a redundant explanation will be omitted here. By using the conductive composite storage container of this embodiment, the storage method of the first embodiment can be implemented. [Examples]

[0156] (Manufacturing Example 1) Production of Polystyrene Sulfonic Acid 1 206 g of sodium styrene sulfonate was dissolved in 1000 ml of deionized water, and while stirring at 80°C, 1.14 g of ammonium persulfate oxidizing agent solution, which had been previously dissolved in 10 ml of water, was added dropwise for 20 minutes, and this solution was stirred for 12 hours. To the obtained sodium polystyrene sulfonate solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, and approximately 1000 ml of the solvent from the resulting polystyrene sulfonate solution was removed by ultrafiltration. Next, 2000 ml of deionized water was added to the remaining solution, and approximately 2000 ml of solvent was removed by ultrafiltration to wash the polystyrene sulfonate with water. This washing procedure was repeated three times. The water in the resulting solution was removed under reduced pressure to obtain colorless, solid polystyrene sulfonic acid. Next, 10 g of the obtained polystyrene sulfonic acid was dissolved in 90 g of deionized water to obtain a 10% by mass aqueous solution of polystyrene sulfonic acid.

[0157] Using gel permeation chromatography (GPC), the weight-average molecular weight (Mw) of the polystyrene sulfonic acid (PSS) obtained above was measured using pullulan of known weight-average molecular weight as a standard substance, and the result showed a weight-average molecular weight of 180,000. Weight-average molecular weight was measured using a Prominence high-performance liquid chromatograph manufactured by Shimadzu Corporation. A 0.1% NaNO3 aqueous solution was used as the solvent, a Shodex OHpack SB-806M HQ column was used, and a RID-20A detector was used. The solvent temperature was set to 40°C, the flow rate to 0.6 ml / min, and the PSS concentration in the sample was adjusted to 0.1% by mass. 100 μl of the sample, filtered through a 0.2 μm pore size membrane filter, was injected, and the analysis was performed using Lab Solutions software (Shimadzu Corporation).

[0158] (Manufacturing Example 2) Production of Polystyrene Sulfonic Acid 2 206 g of sodium styrene sulfonate was dissolved in 1000 ml of deionized water, and while stirring at 80°C, 0.38 g of ammonium persulfate oxidizing agent solution, which had been previously dissolved in 10 ml of water, was added dropwise for 20 minutes, and this solution was stirred for 12 hours. To the obtained sodium polystyrene sulfonate solution, 1000 ml of sulfuric acid diluted to 10% by mass was added, and approximately 1000 ml of the solvent from the resulting polystyrene sulfonate solution was removed by ultrafiltration. Next, 2000 ml of deionized water was added to the remaining solution, and approximately 2000 ml of solvent was removed by ultrafiltration to wash the polystyrene sulfonate with water. This washing procedure was repeated three times. The water in the resulting solution was removed under reduced pressure to obtain colorless, solid polystyrene sulfonic acid. Next, 10 g of the obtained polystyrene sulfonic acid was dissolved in 90 g of deionized water to obtain a 10% by mass aqueous solution of polystyrene sulfonic acid. The weight-average molecular weight of the polystyrene sulfonic acid (PSS) obtained above, measured using GPC as in Production Example 1, was 540,000.

[0159] (Example 1) 3.0 g of 3,4-ethylenedioxythiophene (EDOT), 90 g of a 10% by mass PSS aqueous solution from Production Example 1, and 325 g of deionized water were mixed at 20°C. 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 (at 25°C) prepared by dissolving 6.6 g of sodium persulfate in 293.4 g of deionized water was slowly added over 4 hours. The reaction mixture (at 25°C) obtained after all of the oxidizing agent solution had been added was stirred and allowed to react for 8 hours. The above reaction yielded a conductive polymer-containing liquid containing a conductive composite (PEDOT-PSS) comprising poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid, which are π-conjugated conductive polymers, and water as a dispersion medium. 39 g of Duolite C255LFH (manufactured by Sumika Chemtex, cation exchange resin) and 39 g of Duolite A368S (manufactured by Sumika Chemtex, anion exchange resin) were added to this conductive polymer-containing liquid, and the mixture was filtered to remove the ion exchange resins, yielding 710 g of conductive polymer-containing liquid (non-volatile component concentration 1.4% by mass) from which the oxidizing agent and catalyst had been removed. Next, ion-exchanged water was added to the obtained conductive polymer-containing liquid to adjust the non-volatile component concentration to 1.0% by mass, and the mixture was dispersed using a high-pressure homogenizer.

[0160] When a portion of the conductive polymer-containing liquid described above was sampled and analyzed using a gas chromatography-mass spectrometer, the amount of unreacted EDOT was below the detection limit. From this result, it was found that almost all of the EDOT formed PEDOT. The gas chromatography measurements described above were performed using a Shimadzu GCMS-QP2010Plus, with helium as the carrier gas, a DB-5MS column, and a secondary electron multiplier tube with a conversion diode as the detector. The vaporization temperature was set to 250°C, the flow rate to 1.2 mL / min, and 1 μL of sample was injected to adjust the PEDOT-PSS concentration in the sample to 1.0 mass%. The analysis was then performed using the GCMSsolution software.

[0161] A portion of the conductive polymer-containing liquid described above was separated and filtered through a 0.2 μm pore size membrane filter (manufactured by Membrane Solutions Japan, model number: NY-030022). PEDOT-PSS was trapped on the membrane, while individual PSS (those not forming PEDOT-PSS) contained in the conductive polymer-containing liquid were allowed to pass through and recovered in the filtrate. The weight-average molecular weight of the PSS contained in this filtrate was measured by GPC as described in Production Example 1, and was found to be 96,000.

[0162] Next, 100 g of the conductive polymer-containing liquid described above was transferred to a 250 mL brown polyethylene bottle, nitrogen gas was blown in for 10 seconds to adjust the oxygen concentration of the gas filling the remaining space in the bottle to 5.2 vol%. The bottle was then sealed tightly and stored at 40°C for 720 hours. The ratio of the volume of the remaining space in the bottle (V1) to the volume of the conductive polymer-containing liquid (V2) contained in the bottle (V1 / V2) was 1.5. After storage, the weight-average molecular weight of individual PSS that did not form PEDOT-PSS was measured by GPC in the same manner as described above, and it was found to be 90,000. Therefore, the weight-average molecular weight X of the individual PSS before storage was 96,000, and the weight-average molecular weight Y of the individual PSS after storage was 90,000, resulting in Y / X = 0.94.

[0163] Next, the conductive polymer-containing solution, after storage, was applied onto a PET film using a #4 bar coater and dried at 120°C for 1 minute to obtain a conductive film. The surface resistance R0 of this conductive film was measured, and the results are shown in Table 1. Furthermore, the conductive film whose surface resistance R0 was measured was left exposed to air for 30 days under conditions of 25°C and 50% RH humidity, and then its surface resistance R1 was measured again in the same manner as above. The results and the ratio of increase in surface resistance (R1 / R0) are shown in Table 1.

[0164] The surface resistance (unit: Ω / □) of the conductive layer of the conductive film was measured using a resistivity meter (Highresta, manufactured by Nitto Seiko Analytech Co., Ltd.) under the condition of an applied voltage of 10V. In the table, "1.0E+06" is "1.0×10 6 This means "[...]" and the same applies to the others.

[0165] The oxygen concentration of the gas filling the remaining space inside the bottle was measured using a commercially available oxygen concentration meter (manufactured by Shin-Cosmos Electric Co., Ltd., model: XP-3380II).

[0166] (Example 2) In Example 1, a conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that nitrogen gas was blown into the bottle for 30 seconds to make the oxygen concentration of the gas filling the remaining space in the bottle 2.6% by volume. The weight-average molecular weight was measured, a conductive film was prepared, and its surface resistance was measured.

[0167] (Example 3) In Example 1, a conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that the gas blown into the bottle was changed from nitrogen gas to argon gas, and the oxygen concentration of the gas filling the remaining space in the bottle was set to 5.2% by volume. The weight-average molecular weight was measured, a conductive film was prepared, and its surface resistance was measured.

[0168] (Comparative Example 1) In Example 1, a conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that nitrogen gas was not blown into the bottle and the oxygen concentration was not reduced (the remaining space was filled with air). The weight-average molecular weight was measured, a conductive film was prepared, and its surface resistance was measured.

[0169] (Example 4) Except for changing the instruction in Example 1 from "90 g of the 10% by mass PSS aqueous solution from Production Example 1 and 325 g of deionized water were mixed at 20°C" to "150 g of the 10% by mass PSS aqueous solution from Production Example 1 and 265 g of deionized water were mixed at 20°C," 710 g of conductive polymer-containing solution (non-volatile component concentration 1.8% by mass) was obtained in the same manner as in Example 1. Otherwise, conductive polymer-containing solution was obtained in the same manner as in Example 1, the weight-average molecular weight was measured, a conductive film was prepared, and its surface resistance value was measured. The results are shown in Table 1.

[0170] (Comparative Example 2) In Example 4, a conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that nitrogen gas was not blown into the bottle and the oxygen concentration was not reduced (the remaining space was filled with air). The weight-average molecular weight was measured, a conductive film was prepared, and its surface resistance was measured.

[0171] (Example 5) Except for changing "90 g of 10% by mass PSS aqueous solution from Production Example 1" to "90 g of 10% by mass PSS aqueous solution from Production Example 2" in the same manner as in Example 1, 710 g of conductive polymer-containing solution (non-volatile component concentration 1.4% by mass) was obtained. Otherwise, the conductive polymer-containing solution was obtained in the same manner as in Example 1, the weight-average molecular weight was measured, a conductive film was prepared, and its surface resistance value was measured. The results are shown in Table 1.

[0172] (Comparative Example 3) In Example 5, a conductive polymer-containing liquid was obtained in the same manner as in Example 1, except that nitrogen gas was not blown into the bottle and the oxygen concentration was not reduced (the remaining space was filled with air). The weight-average molecular weight was measured, a conductive film was prepared, and its surface resistance was measured.

[0173] [Table 1]

[0174] (Example 6) To 100 g of the conductive polymer-containing solution from Example 1, which had been stored at 40°C for 720 hours, 50 g of isopropanol and 10 g of trioctylamine were added and the mixture was stirred for 1 hour to allow the trioctylamine to react with some of the sulfonic acid groups of the conductive composite. As a result, all of the reaction product precipitated in the upper layer of the reaction solution. This precipitate was filtered to obtain a powder of the reaction product between the conductive composite and trioctylamine. Isopropanol was added to this powder to make a 500 g mixture, which was dispersed using a high-pressure homogenizer to obtain 500 g of conductive polymer-containing solution. The results of measuring the non-volatile component concentration of this solution are shown in Table 2. Next, the obtained conductive polymer-containing solution was applied to a PET film using a #8 bar coater and dried at 100°C for 1 minute to obtain a conductive film. The surface resistance value was then measured in the same manner as in Example 1. The results are shown in Table 2.

[0175] (Comparative Example 4) A conductive polymer-containing solution was prepared using isopropanol as the dispersion medium, in the same manner as in Example 6, except that 100 g of the conductive polymer-containing solution in Example 1 was replaced with 100 g of the conductive polymer-containing solution (non-volatile component concentration 1.0% by mass) in Comparative Example 1. The results are shown in Table 2.

[0176] (Example 7) To 100 g of the conductive polymer-containing solution from Example 1, which had been stored at 40°C for 720 hours, 25 g of epoxy compound (Epolite M-1230, C12,13 mixed higher alcohol glycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.) was added, and the mixture was heated and stirred at 60°C for 4 hours to allow the epoxy compound to react with some of the sulfonic acid groups of the conductive composite. As a result, a reaction product precipitated. This precipitate was filtered to obtain the reaction product between the conductive composite and the epoxy compound. Methyl ethyl ketone was added to this reaction product to make a 300 g mixture, which was dispersed using a high-pressure homogenizer to obtain 300 g of conductive polymer-containing solution. The results of measuring the non-volatile component concentration of this solution are shown in Table 2. Next, the obtained conductive polymer-containing solution was applied onto a PET film using a #8 bar coater and dried at 100°C for 1 minute to obtain a conductive film, whose surface resistance was then measured. The results are shown in Table 2.

[0177] (Comparative Example 5) A conductive polymer-containing solution was obtained using methyl ethyl ketone as the dispersion medium, in the same manner as in Example 7, except that 100 g of the conductive polymer-containing solution in Example 1 was replaced with 100 g of the conductive polymer-containing solution (non-volatile component concentration 1.0% by mass) in Comparative Example 1. A conductive film was then prepared using this solution. The results are shown in Table 2.

[0178] (Example 8) To 100 g of the conductive polymer-containing solution from Example 1, which had been stored at 40°C for 720 hours, 25 g of epoxy compound (Epolite M-1230, C12,13 mixed higher alcohol glycidyl ether, manufactured by Kyoeisha Chemical Co., Ltd.) was added, and the mixture was heated and stirred at 60°C for 4 hours. Next, 50 g of isopropanol and 10 g of trioctylamine were added and stirred for 1 hour, causing the epoxy compound and trioctylamine to react with some of the sulfonic acid groups of the conductive complex. As a result, a reaction product precipitated. This precipitate was filtered to obtain the reaction product of the conductive complex, epoxy compound, and trioctylamine. Ethyl acetate was added to this reaction product to make an 800 g mixture, which was dispersed using a high-pressure homogenizer to obtain 800 g of conductive polymer-containing solution. The results of measuring the non-volatile component concentration of this solution are shown in Table 2. Next, the obtained conductive polymer-containing liquid was applied onto a PET film using a bar coater #8, and dried at 100°C for 1 minute to obtain a conductive film, and the surface resistance value thereof was measured. The results are shown in Table 2.

[0179] (Comparative Example 6) A conductive polymer-containing liquid having ethyl acetate as a dispersion medium was obtained in the same manner as in Example 8, 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 film was obtained, and the surface resistance value thereof was measured. The results are shown in Table 2.

[0180] [Table 2]

[0181] [Results] From the results of Comparative Examples 1 to 3, after storage at 40°C for 720 hours (storage conditions assuming an indoor environment without air conditioning in summer), it was found that the molecular weight of PSS (single PSS) that did not form PEDOT-PSS contained in the conductive polymer-containing liquid was reduced, and the ratio (Y / X) of the weight average molecular weight became lower. The atmospheric exposure resistance of the conductive layer formed by coating the conductive polymer-containing liquid containing such low molecular weight single PSS was inferior to that of the examples. On the other hand, in the conductive polymer-containing liquids of Examples 1 to 5, since they were stored sealed in a bottle with a reduced oxygen concentration, it was found that the reduction in the molecular weight of the single PSS contained in the conductive polymer-containing liquid was suppressed even after the above storage. 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 to 3.

[0182] In the conductive polymer-containing liquids produced in Examples 6 to 8, since a conductive polymer-containing liquid in which the reduction in the molecular weight of single PSS as a raw material was suppressed was used, the atmospheric exposure resistance of the formed conductive layer was superior to that of Comparative Examples 4 to 6. The 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 4-6, had undergone a reduction in molecular weight after storage. Therefore, the atmospheric exposure resistance of the conductive layers formed by coating with the conductive polymer-containing liquids produced in Comparative Examples 4-6 was inferior to that of Examples 6-8.

[0183] <Mechanism of Action> In the comparative example of the conductive polymer-containing liquid, the individual polyanions undergo molecular weight reduction during storage, reducing the proportion of individual polyanions present on the surface of the coating film. This relatively increases the proportion of conductive composites present on the surface, which is presumed to make the conductive composites on the surface of the conductive layer more susceptible to contact with the atmosphere, thus lowering the atmospheric exposure resistance of the conductive layer. On the other hand, in the conductive polymer-containing liquid of the example, since individual polyanions can be maintained at a high molecular weight during storage, individual polyanions tend to accumulate on the surface of the coating film (they are easily repelled from the depths and accumulate on the surface). It is presumed that these individual polyanions on the surface of the coating film reduce contact between the atmosphere and the conductive composite and function as a protective agent for the conductive composite, resulting in excellent atmospheric exposure resistance of the conductive layer.

Claims

1. A conductive polymer-containing liquid containing a conductive composite comprising a π-conjugated conductive polymer and a polyanion, the polyanion not forming the conductive composite, and a dispersion medium is stored in a sealed container. In the aforementioned storage, the oxygen concentration in the space remaining after subtracting the volume of the conductive polymer-containing liquid from the volume of the container is set to 9.9% by volume or less. Let X be the initial weight-average molecular weight of the polyanion that does not form the conductive composite at the start of storage of the conductive polymer-containing liquid. After storing the conductive polymer-containing liquid at a temperature of 40°C to 50°C for 720 hours, the molecular weight ratio expressed as Y / X is confirmed, where Y is the weight-average molecular weight of the polyanions that do not form the conductive composite. A method for producing a conductive polymer-containing liquid, wherein the molecular weight ratio has been confirmed.

2. A conductive polymer dispersion containing a conductive composite comprising a π-conjugated conductive polymer and a polyanion, the polyanion not forming the conductive composite, and a dispersion medium is stored in a sealed container. In the aforementioned storage, the oxygen concentration in the space remaining after subtracting the volume of the conductive polymer dispersion from the volume of the container is set to 9.9% by volume or less. Let X be the initial weight-average molecular weight of the polyanions that do not form the conductive composite at the start of storage of the conductive polymer dispersion. After storing the conductive polymer dispersion at a temperature of 40°C to 50°C for 720 hours, the molecular weight ratio expressed as Y / X is confirmed, where Y is the weight-average molecular weight of the polyanions that do not form the conductive composite. By adding an epoxy compound to the conductive polymer dispersion confirmed above, a reaction product containing the conductive composite is precipitated. A method for producing a conductive polymer-containing liquid, comprising: recovering the precipitated reaction product and adding an organic solvent to obtain a conductive polymer-containing liquid.

3. A conductive polymer dispersion containing a conductive composite comprising a π-conjugated conductive polymer and a polyanion, the polyanion not forming the conductive composite, and a dispersion medium is stored in a sealed container. In the aforementioned storage, the oxygen concentration in the space remaining after subtracting the volume of the conductive polymer dispersion from the volume of the container is set to 9.9% by volume or less. Let X be the initial weight-average molecular weight of the polyanions that do not form the conductive composite at the start of storage of the conductive polymer dispersion. After storing the conductive polymer dispersion at a temperature of 40°C to 50°C for 720 hours, the molecular weight ratio expressed as Y / X is confirmed, where Y is the weight-average molecular weight of the polyanions that do not form the conductive composite. By adding an amine compound or a quaternary ammonium compound to the conductive polymer dispersion confirmed above, a reaction product containing the conductive composite is precipitated. A method for producing a conductive polymer-containing liquid, comprising: recovering the precipitated reaction product and adding an organic solvent to obtain a conductive polymer-containing liquid.

4. A conductive polymer dispersion containing a conductive composite comprising a π-conjugated conductive polymer and a polyanion, the polyanion not forming the conductive composite, and a dispersion medium is stored in a sealed container. In the aforementioned storage, the oxygen concentration in the space remaining after subtracting the volume of the conductive polymer dispersion from the volume of the container is set to 9.9% by volume or less. Let X be the initial weight-average molecular weight of the polyanions that do not form the conductive composite at the start of storage of the conductive polymer dispersion. After storing the conductive polymer dispersion at a temperature of 40°C to 50°C for 720 hours, the molecular weight ratio expressed as Y / X is confirmed, where Y is the weight-average molecular weight of the polyanions that do not form the conductive composite. By adding an epoxy compound and an amine compound or a quaternary ammonium compound to the conductive polymer dispersion confirmed above, a reaction product containing the conductive composite is precipitated. A method for producing a conductive polymer-containing liquid, comprising: recovering the precipitated reaction product and adding an organic solvent to obtain a conductive polymer-containing liquid.

5. A method for producing a conductive polymer-containing liquid according to any one of claims 1 to 4, wherein the oxygen concentration is reduced by blowing nitrogen gas or argon gas into the container.

6. A method for producing a conductive polymer-containing liquid according to any one of claims 1 to 5, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene).

7. A method for producing a conductive polymer-containing liquid according to any one of claims 1 to 6, wherein the polyanion is polystyrene sulfonic acid.

8. A step of producing a conductive polymer-containing liquid by the method of any one of claims 1 to 7, A method for manufacturing a conductive laminate, comprising the step of coating at least a portion of the surface of a substrate with the conductive polymer-containing liquid.

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