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

Abstract

To provide a method for producing a conductive laminate provided with a conductive layer having improved atmospheric exposure resistance and to provide a method for producing a conductive polymer-containing solution used in its production method.SOLUTION: There is provided a method for producing a conductive polymer-containing solution which comprises a polymerization step of polymerizing a monomer for forming a π-conjugated conductive polymer with a reaction solution containing a polyanion and an aqueous dispersion medium to obtain a conductive polymer-containing solution which contains a conductive complex containing the π-conjugated conductive polymer and the polyanion, the aqueous dispersion medium and the polyanion which does not form the conductive complex, wherein a ratio represented by Y / X of the weight average molecular weight Y of the polyanion which does not form the conductive complex after the polymerization to the weight average molecular weight X of the polyanion before the polymerization is 0.67 or more.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] A π-conjugated conductive polymer whose main chain is composed of a π-conjugated system forms a conductive complex 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 containing the conductive complex (sometimes referred to as a conductive polymer dispersion), a conductive film provided with a conductive layer can be produced. Further, 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, an epoxy compound may be reacted with the conductive complex. Furthermore, as a technique for suppressing a decrease in the conductivity of a conductive layer containing a conductive complex over time in the atmosphere, for example, Patent Document 1 discloses a method of incorporating an aromatic compound represented by a specific chemical formula into the conductive layer.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention provides a method for producing a conductive laminate provided with a conductive layer having improved atmospheric exposure resistance and a method for producing a conductive polymer-containing liquid used in the production method.

Means for Solving the Problems

[0005] [1] A method for producing a conductive polymer-containing liquid, comprising a polymerization step of polymerizing a monomer that forms a π-conjugated conductive polymer in a reaction liquid containing a polyanion and an aqueous dispersion medium, to obtain 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. In the method, the ratio represented by Y / X of the weight average molecular weight Y of the polyanion that does not form the conductive composite after polymerization to the weight average molecular weight X of the polyanion before polymerization is 0.67 or more. [2] The method for producing a conductive polymer-containing liquid according to [1], wherein a basic compound is contained in the reaction liquid. [3] The method for producing a conductive polymer-containing liquid according to [1] or [2], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene), or the polyanion is polystyrene sulfonic acid. [4] After polymerizing the monomer by adding an oxidizing agent, a basic compound, and a catalyst to the reaction liquid, removing the oxidizing agent, the basic compound, and the catalyst from the conductive polymer-containing liquid. The method for producing a conductive polymer-containing liquid according to any one of [1] to [3]. [5] The method for producing a conductive polymer-containing liquid according to [4], wherein the conductive polymer-containing liquid is brought into contact with at least one of a cation exchange resin and an anion exchange resin to remove the oxidizing agent, the catalyst, and the basic compound. [6] Reacting an epoxy compound with the conductive polymer-containing liquid obtained in the polymerization step to obtain a conductive polymer-containing liquid containing the obtained reaction product and an organic solvent. The method for producing a conductive polymer-containing liquid according to any one of [1] to [5]. [7] Reacting an amine compound or a quaternary ammonium compound with the conductive polymer-containing liquid obtained in the polymerization step to obtain a conductive polymer-containing liquid containing the obtained reaction product and an organic solvent. The method for producing a conductive polymer-containing liquid according to any one of [1] to [5]. [8] React an epoxy compound and an amine compound or a quaternary ammonium compound with the conductive polymer-containing liquid obtained in the polymerization step to obtain a conductive polymer-containing liquid containing the obtained reaction product and an organic solvent, according to the method for producing a conductive polymer-containing liquid according to any one of [1] to [5]. [9] A method for producing a conductive laminate, comprising a step of obtaining a conductive polymer-containing liquid by the production method according to any one of [1] to [8], and a step of applying the conductive polymer-containing liquid to at least a part of the surface of a substrate.

[10] The method for producing a conductive laminate according to [9], wherein the substrate is a film substrate. [Advantages of the Invention]

[0006] According to the method for producing a conductive laminate of the present invention, a conductive laminate having a conductive layer with excellent atmospheric exposure resistance can be easily produced. According to the method for producing a conductive polymer-containing liquid of the present invention, the above conductive polymer-containing liquid can be easily produced.

[0007] The present invention is considered to contribute to SDGs Goal 12, "Responsibility for Production and Consumption".

[0008] In this specification and the claims, the lower limit value and the upper limit value of the numerical range indicated by "~" are included in the numerical range. [Embodiments for Carrying Out the Invention]

[0009] [[Manufacturing Method of Conductive Polymer-Containing Liquid]] The first aspect of the present invention is a method for producing a conductive polymer-containing liquid, which includes a polymerization step of polymerizing a monomer that forms a π-conjugated conductive polymer in a reaction liquid containing a polyanion and an aqueous dispersion medium to obtain a conductive polymer-containing liquid containing the π-conjugated conductive polymer, the polyanion, the aqueous dispersion medium, and the polyanion that has not formed the conductive complex.

[0010] The ratio represented by Y / X of the weight-average molecular weight Y of the polyanion before polymerization to the weight-average molecular weight X of the polyanion not forming the conductive composite after polymerization is 0.67 or more, preferably 0.69 or more, more preferably 0.71 or more, still more preferably 0.73 or more, and most preferably 0.75 or more. As a guideline for the upper limit value of the ratio represented by Y / X, 2.00 or less can be mentioned. When it is in the above range, the atmospheric exposure resistance of the conductive layer formed by the conductive polymer-containing liquid of this aspect can be further enhanced.

[0011] In the conductive polymer-containing liquid of this aspect, the conductive composite may be in a dispersed state or a dissolved state. In this specification, unless otherwise specified, the dispersed state and the dissolved state are not distinguished.

[0012] <Polyanion> A polyanion is a polymer having two or more monomer units having anionic groups in the molecule. The anionic groups of this polyanion function as dopants for the π-conjugated conductive polymer and can improve the conductivity of the π-conjugated conductive polymer. The anionic group of the polyanion is preferably a sulfo group or a carboxy group. Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid esters having a sulfo group, polymethacrylic acid esters having a sulfo group (for example, poly(4-sulfobutyl methacrylate, polysulfoethyl methacrylate, polymethacryloyloxybenzene sulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polymers having a sulfo group such as polyisoprene sulfonic acid, and polymers having a carboxy group such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropane carboxylic acid), polyisoprene carboxylic acid. These may be homopolymers or copolymers of two or more kinds. Among these polyanions, polymers having a sulfo group are preferred because they can achieve higher conductivity, and polystyrene sulfonic acid is more preferred. The polyanion may be of one type or two or more types.

[0013] The weight-average molecular weight (Mw) of the polyanion is preferably 90,000 or more and 1,000,000 or less, more preferably 100,000 or more and 800,000 or less, still more preferably 110,000 or more and 700,000 or less, particularly preferably 120,000 or more and 600,000 or less, and most preferably 130,000 or more and 550,000 or less. Here, the weight-average molecular weight is measured by gel permeation chromatography (GPC) and is the average molecular weight on a mass basis (which may also be referred to as the weight-average molecular weight) determined using pullulan of a known weight-average molecular weight as a standard substance. When the weight-average molecular weight is within the above preferred range, the conductivity of the conductive layer is further enhanced. Before subjecting the aqueous solution of the polyanion to GPC, it is filtered through a membrane filter with an average pore size of 0.2 μm for the purpose of removing impurities and the like contained in the aqueous solution, and the filtrate is used for GPC measurement.

[0014] As a method for synthesizing a polyanion with a specific weight-average molecular weight, for example, a method of adjusting the addition amount of an oxidizing agent for polymerizing the monomers constituting the polyanion can be mentioned. 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 90,000 or more and 1,000,000 or less can be obtained.

[0015] The polyanion forms a conductive complex by doping a π-conjugated conductive polymer. However, in the polyanion, some anion groups do not dope into the π-conjugated conductive polymer and have surplus anion groups that do not participate in doping. Since this surplus anion group is a hydrophilic group, the conductive complex has high water dispersibility and low organic solvent dispersibility. When the number of all the anion groups possessed by the polyanion forming the conductive composite is taken as 100 mol%, the excess anion groups are preferably 30 mol% or more and 90 mol% or less, and more preferably 45 mol% or more and 75 mol% or less.

[0016] <π-conjugated conductive polymer> The π-conjugated conductive polymer is not particularly limited as long as it has the effects of the present invention as long as it is an organic polymer whose main chain is composed of a π-conjugated system. For example, 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 can be mentioned. 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.

[0017] 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), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxy-thiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxy-thiophene), poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-didodecyloxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3-methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-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 above π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred in terms of conductivity, transparency, and heat resistance. The π-conjugated conductive polymer contained in the conductive composite may be one type or two or more types.

[0018] [Polymerization step] A reaction solution containing the monomer that forms the π-conjugated conductive polymer and the polyanion in an arbitrary content ratio is prepared, and the monomer is polymerized to form a π-conjugated conductive polymer. In the reaction solution, the polyanion naturally dopes the π-conjugated conductive polymer, and a conductive composite composed of the π-conjugated conductive polymer and the polyanion is formed.

[0019] The reaction solution preferably contains a basic compound. Here, the basic compound is a compound capable of accepting the proton of the surplus anion group not involved in the doping of the polyanion, and is preferably a compound having an electron pair for accepting the proton. Although the detailed mechanism is unclear, including the basic compound facilitates adjusting the ratio represented by Y / X to 0.67 or more. As the basic compound, for example, an organic or inorganic basic compound containing nitrogen, a hydroxide of an alkali metal or a Group 2 metal, various carbonates, hydrogen carbonates, etc. can be used. For example, hydroxides of alkali metals, quaternary ammonium hydroxides or their salts, ammonia, amines, etc. can be mentioned. Specific examples of the hydroxide of an alkali metal include potassium hydroxide, sodium hydroxide, etc. Specific examples of the carbonate or hydrogen carbonate include ammonium hydrogen carbonate, ammonium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate, sodium carbonate, etc. Specific examples of the quaternary ammonium hydroxide or its salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. Examples of the amine include aliphatic tertiary amines, nitrogen-containing heterocyclic aromatic compounds, etc. Examples of the aliphatic tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, trinaphthylamine, etc. Examples of the nitrogen-containing heterocyclic aromatic compound include pyrrole, indole, imidazole, pyridine, pyrimidine, pyrazine and their alkyl-substituted products (for example, products substituted with an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc.), halogen-substituted products (for example, products substituted with a halogen group such as fluoro, chloro, bromo, etc.), derivatives such as nitrile-substituted products, etc. Among them, imidazole and triethylamine are preferred. The basic compound may be used alone or in combination of two or more.

[0020] A catalyst may be added to the reaction solution. The catalyst is not particularly limited as long as it can promote the polymerization of the monomer. Examples thereof include transition metal compounds such as ferric chloride, ferrous sulfate, ferric nitrate, and cupric chloride. Among them, since the polymerization of the monomer proceeds stably at room temperature, it is preferable to use a catalyst containing iron.

[0021] It is preferable to contain an oxidizing agent in the reaction solution together with the catalyst. The oxidizing agent can polymerize the monomer. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. It is preferable to slowly add the oxidizing agent as an oxidizing agent solution previously dissolved in ion-exchanged water to the mixed solution S1 containing the monomer, the polyanion, the basic compound, and the catalyst to initiate the 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 solution S1 before adding the oxidizing agent solution is V1 and the volume of the oxidizing agent solution is V2, the volume ratio represented by V1 / V2 is preferably 1.0 to 2.0, and more preferably 1.2 to 1.5. When adding all of the oxidizing agent solution to the mixed solution S1, the time required from the start of addition to the end of addition is preferably 1 to 8 hours, more preferably 2 to 7 hours, and even more preferably 3 to 6 hours. The temperature of each of the mixed solution S1 before adding the oxidizing agent solution and the oxidizing agent solution is preferably independently 5 to 30°C.

[0022] 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 and carry out the polymerization reaction. The standard of the reaction time required until the reaction is completed in the reaction solution is 4 to 12 hours, and it is preferable that the reaction is completed in 6 to 10 hours. The completion of the polymerization reaction can be known by confirming that the monomer forming the π-conjugated conductive polymer has disappeared by gas chromatography.

[0023] The content ratio of the monomer to the polyanion contained in the mixed solution S1 is preferably (1:2) to (1:5) on a mass basis, more preferably (1:2) to (1:4), and even more preferably (1:2) to (1:3). When it is at least the lower limit value of the above range, the doping effect by the polyanion is sufficiently exerted, and the dispersion stability of the conductive composite is further improved. When it is at most the upper limit value of the above range, a conductive polymer-containing liquid excellent in conductivity can be obtained. In addition, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0024] The content of the monomer with respect to the total mass of the mixed solution 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 3.0% by mass or less. When it is within the above range, the polymerization reaction can proceed stably, so the complexation with the polyanion present in the reaction system easily proceeds. In addition, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0025] The content of the polyanion with respect to the total mass of the mixed solution S1 is preferably set based on the content ratio to the monomer. For example, it is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 8.0% by mass or less, and even more preferably 0.6% by mass or more and 5.0% by mass or less. When it is within the above range, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0026] The weight average molecular weight of the polyanion contained in the mixed solution S1 is preferably within the above range. When it is within the above range, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0027] The content ratio of the basic compound in the mixed solution S1 is preferably 5 parts by mass or more and 1000 parts by mass or less, more preferably 10 parts by mass or more and 500 parts by mass or less, and still more preferably 20 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the monomer in the mixed solution S1. When it is within the above range, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0028] The content ratio of the basic compound in the mixed solution S1 is preferably 1 part by mass or more and 200 parts by mass or less, more preferably 3 parts by mass or more and 100 parts by mass or less, and still more preferably 6 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyanion in the mixed solution S1. When it is within the above range, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0029] The content of the basic compound with respect to the total mass of the mixed solution S1 is preferably 0.01% by mass or more and 1.0% by mass or less, more preferably 0.05% by mass or more and 0.5% by mass or less, and still more preferably 0.1% by mass or more and 0.3% by mass or less. When it is within the above range, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0030] The content of the catalyst with respect to the total mass of the reaction solution after all the oxidizing agent has been added is, for example, preferably 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 still more preferably 0.1% by mass or more and 0.5% by mass or less with respect to the total mass of the reaction solution. When it is within the above range, the polymerization reaction can proceed stably, so the complexation with the polyanion can proceed easily. Also, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0031] The addition amount of the oxidizing agent 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, still 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. When it is within the above range, the polymerization reaction can proceed stably, so the complexation with the polyanion can proceed easily. In addition, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0032] The amount of the monomer charged before the reaction relative to the total mass of the reaction solution after all the oxidizing agent has been added is preferably, for example, 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 still more preferably 0.2% by mass or more and 2.0% by mass or less. When it is within the above range, the polymerization reaction can proceed stably, so the complexation with the polyanion present in the reaction system can proceed easily. In addition, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0033] The amount of the polyanion charged before the reaction relative to the total mass of the reaction solution after all the oxidizing agent has been added is preferably, for example, 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 still more preferably 0.5% by mass or more and 4.0% by mass or less. When it is within the above range, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0034] The content of the basic compound 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 1% by mass or less, more preferably 0.03% by mass or more and 0.60% by mass or less, and still more preferably 0.05% by mass or more and 0.30% by mass or less. When it is within the above range, a conductive polymer-containing liquid having the target Y / X ratio can be easily obtained.

[0035] The aqueous dispersion medium constituting the reaction solution contains at least water, and may further contain a water-soluble organic solvent. Specific examples of the water-soluble organic solvent will be described later. The content ratio of water 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, still 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.

[0036] (Removal of catalyst, basic compound and oxidizing agent) When using a reaction solution to which a catalyst, a basic compound and an oxidizing agent are added, it is preferable to remove the catalyst, the basic compound and the oxidizing agent from the conductive polymer-containing solution obtained after the reaction. Examples of the removal method include a method of bringing the conductive polymer-containing solution into contact with an ion exchange resin to adsorb the catalyst, the basic compound and the oxidizing agent onto the ion exchange resin, and a method of removing the conductive polymer-containing solution by ultrafiltration to remove it together with the replacement of the aqueous dispersion medium. Among these, the method of using an ion exchange resin is preferable because it is simple. It is preferable to use a combination of a cation exchange resin and an anion exchange resin as the ion exchange resin.

[0037] (Dispersion treatment) When using the conductive polymer-containing solution, it is preferable to perform a dispersion treatment of the conductive composite by stirring. The stirring method is not particularly limited, and stirring with a weak shearing force such as a stirrer may be used, or stirring may be performed using a disperser with a high shearing force such as a high-pressure homogenizer. However, from the viewpoint of enhancing dispersibility, it is preferable to use a high-pressure homogenizer or the like.

[0038] By the above method, a conductive polymer-containing solution can be obtained, which contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, the aqueous dispersion medium, and the polyanion not forming the conductive composite, and the ratio of the weight average molecular weight Y of the polyanion not forming the conductive composite after polymerization to the weight average molecular weight X of the polyanion before polymerization, represented by Y / X, is 0.67 or more.

[0039] The weight average molecular weight Y of the polyanion is the average molecular weight on a mass basis determined by gel permeation chromatography using pullulan with a known weight average molecular weight as a standard substance. It is preferable to measure the weight average molecular weight Y after separating the polyanion that does not form the conductive composite from the conductive polymer-containing liquid obtained by the above method, because it can be accurately measured without being affected by the conductive composite. Examples of the separation method include filtering the conductive polymer-containing liquid using a membrane filter with an average pore size of 0.2 μm to trap the conductive composite on the filter while allowing the polyanion that does not form the conductive composite to permeate and collecting it in the filtrate.

[0040] Using the conductive polymer-containing liquid obtained by the above method, the following precipitation recovery step may be performed to modify and hydrophobize the conductive composite.

[0041] [Precipitation Recovery Step] By adding one or more selected from an epoxy compound, an amine compound, and a quaternary ammonium compound to a conductive polymer-containing liquid containing an aqueous dispersion medium obtained in the polymerization step (hereinafter sometimes referred to as a conductive polymer dispersion), a reaction product containing the conductive composite can be precipitated. Also, the polyanion that does not form the conductive composite reacts and precipitates in the same manner. Anionic groups such as sulfonic acid groups of the reaction product precipitated in this step are hydrophobized by the reaction of the added above-mentioned compound to form any of the following substituents (A) to (C).

[0042] Excess anionic groups that do not participate in the doping of the polyanion are sometimes referred to as "some anionic groups" hereinafter. The following substituent (A) is formed by the reaction of some anionic groups with an epoxy compound. The following substituent (B) is formed by the reaction of some anionic groups with an amine compound. The following substituent (C) is formed by the reaction of some anionic groups with a quaternary ammonium compound.

[0043] (Substituent A) The substituent (A) is presumed to be a group represented by the following formula (A1) or a group represented by the following formula (A2).

[0044] [Chemical formula]

[0045] [In formula (A1), R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom or an arbitrary substituent.]

[0046] [Chemical formula]

[0047] [In formula (A2), m is an integer of 2 or more, and a plurality of R 5 , a plurality of R 6 , a plurality of R 7 , and a plurality of R 8 are each independently a hydrogen atom or an arbitrary substituent, a plurality of R 5 may be the same or different, a plurality of R 6 may be the same or different, a plurality of R 7 may be the same or different, and a plurality of R 8 may be the same or different.]

[0048] In formulas (A1) and (A2), the leftmost bond represents that the substituent (A) is substituted with a proton of an anionic group such as a sulfonic acid group.

[0049] In formula (A1), R 1 , R 2 , R 3 , and R 4Examples of any substituent include an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like. R 1 and R 3 may combine to form an optionally substituted ring. For example, R 1 and R 3 are the hydrocarbon groups, and 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 combine with each other at the carbon atoms from which the hydrogen atoms have been removed to form a ring. In formula (A2), examples of any substituent of R 5 , R 6 , R 7 , and R 8 include an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like. R 5 and R 7 may combine to form an optionally substituted ring. Examples of forming a ring are the same as above. Here, "optionally having a substituent" includes both the case of substituting a hydrogen atom (-H) with a monovalent group and the case of substituting a methylene group (-CH2-) with a divalent group. Examples of the monovalent group as a substituent include an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a trialkoxysilyl group (such as a trimethoxysilyl group), and the like. Examples of the divalent group as a substituent include an oxygen atom (-O-), -C(=O)-, -C(=O)-O-, and the like. m is an integer of 2 or more, preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 25. When m is at least the above lower limit value, the hydrophobicity of the conductive composite becomes sufficiently high. When m is at most the above upper limit value, it is possible to suppress the case where the hydrophobicity becomes too high or the conductivity decreases.

[0050] An epoxy compound is a compound having one or more epoxy groups in one molecule (epoxy group-containing compound). In terms of preventing aggregation or gelation, the epoxy compound is preferably a compound having one epoxy group in one molecule. The epoxy compound that reacts with the partial anion groups may be one type or two or more types.

[0051] Examples of monofunctional epoxy compounds having one epoxy group in the 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 monoxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2-epoxyoctadecane, 1,2-epoxyhexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2-(chloromethyl)-1,2-epoxypropane, glycidol, epichlorohydrin, epibromohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2-(chloromethyl)-1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2-epoxy-1H,1H,2H,2H,3H,3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-methyl-1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H,1H,2H,2H,3H,3H-heptadecafluorobutane, 3,4-epoxytetrahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxy succinic acid, glycidyl phenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, benzyl glycidyl ether, diethoxy(3-glycidyloxypropyl)methylsilane, 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl-3-(3-glycidyloxypropyl)trisiloxane, 9,10-epoxy-1,5-cyclododecadiene, glycidyl 4-tert-butylbenzoate, 2,2,2-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, glycidyl p-toluenesulfonate, ethyl 3-methyl-3-phenylglycidate, N-propyl-N-(2,3-epoxypropyl)perfluorooctylsulfonamide, (2S,3S)-1,2-epoxy-3-(tert-butoxycarbonylamino)-4-phenylbutane, (R)-glycidyl 3-nitrobenzenesulfonate, glycidyl 3-nitrobenzenesulfonate, parthenolide, N-glycidylphthalimide, endrin, dieldrin, 4-glycidyloxycarbazole, [oxiranylmethyl] 7,7-dimethyloctanoate, 1,2-epoxy-4-vinylcyclohexane, higher alcohol glycidyl ethers having 10 to 16 carbon atoms, etc. may be mentioned.,

[0052] As the higher alcohol glycidyl ether, one or more of higher alcohol glycidyl ethers having 10 to 16 carbon atoms are preferable, one or more of higher alcohol glycidyl ethers having 12 to 14 carbon atoms are more preferable, and at least one of C12 (12 carbon atoms) higher alcohol glycidyl ether and C13 (13 carbon atoms) higher alcohol glycidyl ether is even more preferable.

[0053] Examples of the polyfunctional epoxy compound 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, isocyanuric acid triglycidyl, neopentyl glycol diglycidyl ether, 1,2:3,4 - diepoxybutane, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6 - hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol - based polyglycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, and the like.

[0054] Since the epoxy compound has high dispersibility in an organic solvent, it preferably has a molecular weight of 50 or more and 2000 or less. Further, since the epoxy compound has high dispersibility in a low - polarity hydrocarbon - based solvent or ester - based solvent, the epoxy compound preferably has 4 or more and 120 or less carbon atoms, more preferably 7 or more and 100 or less carbon atoms, still more preferably 10 or more and 80 or less carbon atoms, and particularly preferably 15 or more and 50 or less carbon atoms.

[0055] (Substituent B) The substituent (B) is presumed to be a group represented by the following formula (B).

[0056] -HN + R 11 R 12 R 13 ···(B) [In formula (B), R 11 ~R 13 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, provided that at least one of R 11 ~R 13 is a hydrocarbon group which may have a substituent.]

[0057] In the substituent (B), the leftmost bond represents that the negative charge of the anion group, for example, the negative charge of the sulfonic acid group "-SO3 - ", is bonded to the positive charge of the amine compound.

[0058] R 11 ~R 13 in chemical formula (B) is a hydrogen atom or a hydrocarbon group which may have a substituent. R 11 ~R 13 in chemical formula (B) is a substituent derived from the amine compound described later. The hydrocarbon group in chemical formula (B) includes an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like. Examples of the substituent of the aliphatic hydrocarbon group include a phenyl group, a hydroxyl group and the like. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group and the like. Examples of the substituent of the aromatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group and the like.

[0059] The amine compound is at least one selected from the group consisting of a primary amine, a secondary amine and a tertiary amine. The amine compound that reacts with a part of the anion groups may be one kind or two or more kinds. Examples of the primary amine include aniline, toluidine, benzylamine, ethanolamine and the like. Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine, and the like. Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, trinaphthylamine, and the like. Among the amine compounds, since the conductivity of the conductive composite of this embodiment can be increased, a tertiary amine is preferable, and at least one of trioctylamine and tributylamine is more preferable.

[0060] Since the dispersibility in an organic solvent, particularly the dispersibility in a low-polarity hydrocarbon solvent or ester solvent, is increased, the amine compound preferably has a substituent having 4 or more carbon atoms on the nitrogen atom, more preferably has a substituent having 6 or more carbon atoms, and even more preferably has a substituent having 8 or more carbon atoms on the nitrogen atom. The upper limit value of the carbon number of the substituent on this nitrogen atom is not particularly limited, and in consideration of the solubility and reactivity in the solvent, for example, 50 or less is preferable, 40 or less is more preferable, and 30 or less is even more preferable. Also, the R 11 ~R 13 The total carbon number of is preferably 6 to 33, more preferably 9 to 30, and even more preferably 12 to 27. The carbon numbers of the substituents on the nitrogen atom may be the same or different.

[0061] When the partial anion group has substituent (A) and substituent (B), the mass ratio represented by [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 becomes easier to balance dispersibility and conductivity. The mass of [substituent (A)] can be calculated by [(the mass of reaction product A obtained by reacting an epoxy compound)-(the mass of the conductive composite before reacting with the epoxy compound and the polyanion not forming the conductive composite)]. The mass of [substituent (B)] can be calculated from [(the mass of reaction product B obtained by reacting the reaction product A with an amine compound)-(the mass of the reaction product A)].

[0062] (Substituent C) Substituent (C) is presumed to be a group represented by the following formula (C).

[0063] -N + R 11 R 12 R 13 R 14 ···(C) [In formula (C), R 11 ~R 14 are each independently a hydrocarbon group which may have a substituent.]

[0064] In substituent (C), the leftmost bond represents that the negative charge of the anion group, for example, the negative charge of the sulfonic acid group "-SO3 - ", is bonded to the positive charge of the quaternary ammonium cation.

[0065] R 11 ~R 14 in chemical formula (C) is a hydrocarbon group which may have a substituent. R 11 ~R 14 in chemical formula (C) is a substituent derived from a quaternary ammonium compound. The hydrocarbon group in chemical formula (C) includes an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc. Examples of the substituent of the aliphatic hydrocarbon group include a phenyl group, a hydroxyl group, etc. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, etc. Examples of the substituent of the aromatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, etc.

[0066] Since the dispersibility in an organic solvent is high and the conductivity is improved, the quaternary ammonium compound preferably has a substituent having 3 or more carbon atoms on the nitrogen atom, more preferably has a substituent having 5 or more carbon atoms, and even more preferably has a substituent having 7 or more carbon atoms on the nitrogen atom. The upper limit value of the carbon number of each substituent on this nitrogen atom is not particularly limited, and in consideration of the solubility and reactivity in the solvent, for example, 40 or less is preferable, 30 or less is more preferable, and 20 or less is even more preferable. Further, the R 11 ~R 14 The total carbon number of is preferably 8 to 44, more preferably 12 to 40, and even more preferably 16 to 36. The number of carbon atoms of each substituent on the nitrogen atom may be the same or different.

[0067] Specific examples of the quaternary ammonium compound include quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tetra-n-octylammonium salt, tetraphenylammonium salt, tetrabenzylammonium salt, tetranaphthylammonium salt. Examples of the counter anion of the ammonium cation include halogen ions such as bromine ion and chlorine ion, and hydroxy ion.

[0068] When the conductive composite has substituent (A) and substituent (C), the mass ratio represented by [substituent (A)]:[substituent (C)] (hereinafter, also referred to as A / C ratio) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 25:75 to 75:25. When the A / C ratio is within the above range, it becomes easier to balance the dispersibility and conductivity. The mass of [substituent (A)] can be calculated by [(the mass of reaction product A obtained by reacting with an epoxy compound)-(the mass of the conductive composite before reacting with the epoxy compound and the polyanion not forming the conductive composite)]. Also, the mass of [substituent (C)] can be calculated from [(the mass of reaction product C obtained by reacting the reaction product A with a quaternary ammonium compound)-(the mass of the reaction product A)].

[0069] The content of the reaction product with respect to the total mass of the conductive polymer-containing liquid of this embodiment 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. When it is at or above the lower limit value of the above range, the conductivity of the conductive layer formed by coating the conductive polymer-containing liquid can be further improved. When it is at or below the upper limit value of the above range, the dispersibility of the reaction product in the conductive polymer-containing liquid can be enhanced, and a uniform conductive layer can be formed.

[0070] When adding one or more epoxy compounds to the conductive polymer dispersion, the addition amount of the epoxy compound is preferably 10 parts by mass or more and 10000 parts by mass or less, more preferably 100 parts by mass or more and 5000 parts by mass or less, and even more preferably 500 parts by mass or more and 3000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer and all polyanions (including the polyanion forming the conductive composite) contained in the conductive polymer dispersion. When it is at or above the lower limit value of the above range, the hydrophobicity of the conductive composite becomes sufficiently high, and the dispersibility in the organic solvent is improved. If it is below the upper limit value of the above range, it is possible to prevent the decrease in conductivity due to the unreacted epoxy compound. When adding the epoxy compound, it may be heated to promote the reaction. The heating temperature is preferably 40°C or higher and 100°C or lower.

[0071] When adding one or more amine compounds to the conductive polymer dispersion, the addition amount of the amine compound is preferably 1 part by mass or more and 10,000 parts by mass or less, more preferably 10 parts by mass or more and 5,000 parts by mass or less, and even more preferably 100 parts by mass or more and 2,000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer and all polyanions (including the polyanion forming the conductive complex) contained in the conductive polymer dispersion. If it is above the lower limit value of the above range, the hydrophobicity of the conductive complex becomes sufficiently high, and the dispersibility in the organic solvent is improved. If it is below the upper limit value of the above range, it is possible to prevent the decrease in conductivity due to the unreacted amine compound.

[0072] When adding one or more quaternary ammonium compounds to the conductive polymer dispersion, the addition amount of the quaternary ammonium compound is preferably 1 part by mass or more and 10,000 parts by mass or less, more preferably 10 parts by mass or more and 5,000 parts by mass or less, and even more preferably 50 parts by mass or more and 2,000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer and all polyanions (including the polyanion forming the conductive complex) contained in the conductive polymer dispersion. If it is above the lower limit value of the above range, the hydrophobicity of the conductive complex becomes sufficiently high, and the dispersibility in the organic solvent is improved. If it is below the upper limit value of the above range, it is possible to prevent the decrease in conductivity due to the unreacted quaternary ammonium compound. The quaternary ammonium compound shows good reactivity with an addition amount less than that of the amine compound through a reaction mechanism similar to that of the amine compound. The conductivity of the conductive layer containing the conductive complex modified with the quaternary ammonium compound tends to be superior to that when modified with the amine compound.

[0073] Before adding one or more selected from an epoxy compound, an amine compound, and a quaternary ammonium compound to the conductive polymer dispersion, an organic solvent may be added before, simultaneously with, or after the addition. As the organic solvent, a water-soluble organic solvent is preferred. Examples of the water-soluble organic solvent include alcohol solvents, ketone solvents, and ester solvents. The organic solvent to be added may be one type or two or more types.

[0074] When both an epoxy compound and an amine compound or a quaternary ammonium compound are added to the conductive polymer dispersion, the order of addition is not particularly limited. Since the handling of the synthetic intermediate (reaction intermediate) is easy, it is preferable to first add the epoxy compound and react it, and then add the amine compound or the quaternary ammonium compound and react it.

[0075] The method for recovering the precipitated reaction product is not particularly limited, and it can be recovered, for example, by filtration treatment, decantation, or the like.

[0076] The water content of the recovered reaction product (precipitate) is preferably as low as possible, and most preferably contains no water at all. However, from a practical point of view, it may contain water in the range of 10% by mass or less. Examples of the method for reducing the water content include a method of washing away the reaction product with an organic solvent and a method of drying the reaction product.

[0077] [Washing step] There may be a washing step of washing the reaction product recovered in the precipitation recovery step. By this washing step, residual water, unreacted epoxy compound, unreacted amine compound or quaternary ammonium compound, and hydrolysis products of the epoxy compound are removed. The organic solvent for washing is preferably one that can wash while minimizing the dissolution of the reaction product. For this reason, an alcohol solvent is preferred as the organic solvent for washing. The organic solvent contained in the organic solvent for washing may be one type or two or more types. The washing method is not particularly limited. For example, the reaction product may be washed by pouring a washing organic solvent from above the reaction product, or the reaction product may be washed by stirring in the washing organic solvent.

[0078] [Addition Step] This step is a step of adding a dispersion medium to the reaction product to obtain a conductive polymer-containing liquid. The dispersion medium to be added may be any medium that can disperse the reaction product, and preferably contains an organic solvent. When the conductive polymer-containing liquid contains a hydrophobized conductive composite, the content of the organic solvent with respect to the total mass of the dispersion medium is preferably 70% by mass or more and 100% by mass or less, 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.

[0079] [Organic Solvent] Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, hydrocarbon solvents, nitrogen atom-containing compound solvents, etc. The organic solvent may be of one type or two or more types.

[0080] The organic solvent may be a water-soluble organic solvent or a water-insoluble organic solvent. A water-soluble organic solvent is an organic solvent with a solubility of 1 g or more in 100 g of water at 20°C, and a water-insoluble organic solvent is an organic solvent with a solubility of less than 1 g in 100 g of water at 20°C. As the water-soluble organic solvent, one or more selected from alcohol solvents are preferred.

[0081] Examples of the alcohol solvent 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 solvents include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, etc. Examples of ketone 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, diacetone alcohol, etc. Examples of ester solvents and hydrocarbon solvents will be described later. Examples of nitrogen atom-containing compound solvents include N-methylpyrrolidone, dimethylacetamide, dimethylformamide, etc. Examples of solvents not classified above include dimethyl sulfoxide.

[0082] (Ester solvents) Ester solvents are ester group-containing compounds having an ester group (-C(=O)-O-). When the conductive composite is modified by reaction with an epoxy compound and an amine compound or a quaternary ammonium compound, it is preferable that the organic solvent contains an ester solvent because the dispersibility of the conductive composite is further enhanced. From the viewpoint of enhancing the dispersibility of the conductive composite, it is preferable to contain one or more ester solvents represented by the following formula 1z. Formula 1z: R 21 -C(=O)-O-R 22 [In the formula, R 21 represents a hydrogen atom, a methyl group or an ethyl group, and R 22 represents a linear or branched alkyl group having 1 to 6 carbon atoms.]

[0083] From the viewpoint of enhancing the dispersibility of the conductive composite, R 21 is preferably a methyl group or an ethyl group, more preferably a methyl group. Also, the carbon number of R 22 is preferably 2 to 5, more preferably 2 to 4.

[0084] Examples of the ester solvents include ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, and the like.

[0085] The content of the ester solvent contained in the organic solvent is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and may 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 enhanced.

[0086] When the conductive polymer-containing liquid of this embodiment contains an ester solvent, one or more organic solvents other than the ester solvent may be further contained. Examples of the organic solvents other than the ester solvent include hydrocarbon solvents described below, the ketone solvents described above, alcohol solvents, nitrogen atom-containing compound solvents, and the like.

[0087] (Hydrocarbon solvents) When the conductive composite contained in the conductive polymer-containing liquid of this embodiment is modified by reaction with an epoxy compound and an amine compound or a quaternary ammonium compound, it is preferable to contain a hydrocarbon solvent as the dispersion medium because the wettability with respect to the plastic film substrate is increased and a low-polarity binder component can be easily added.

[0088] Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, etc. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, etc. Among them, toluene is preferred because of its high dispersibility of the conductive composite. When a silicone compound is added as the binder component, at least one of heptane and toluene is preferred because of its excellent solubility in the silicone compound.

[0089] It is preferable to further contain methyl ethyl ketone in addition to the hydrocarbon solvent because the dispersibility of the conductive composite becomes higher. For example, with respect to 100 parts by mass of the hydrocarbon solvent, the amount of methyl ethyl ketone is preferably 20 parts by mass or more and 120 parts by mass or less, more preferably 30 parts by mass or more and 100 parts by mass or less, and even more preferably 40 parts by mass or more and 80 parts by mass or less.

[0090] The content of the hydrocarbon solvent is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and may be 100% by mass, based on the total mass of the organic solvent. When the content of the hydrocarbon solvent is within the above range, the dispersibility of the conductive composite can be enhanced.

[0091] When the conductive polymer-containing liquid of this embodiment contains a hydrocarbon solvent, one or more organic solvents other than the hydrocarbon solvent may be further contained. Examples of the organic solvent other than the hydrocarbon solvent include the above-described ketone solvents, alcohol solvents, ester solvents, nitrogen atom-containing compound solvents, etc.

[0092] Among these, the organic solvent is preferably at least one selected from alcohol solvents, ketone solvents, and ester solvents, and more preferably at least one selected from isopropanol, methyl ethyl ketone, and ethyl acetate. By using these suitable organic solvents, the dispersibility of the conductive composite contained in the conductive polymer-containing liquid can be further enhanced.

[0093] (Dispersion treatment) After adding a dispersion medium to the reaction product, the conductive polymer-containing liquid may be stirred to perform a dispersion treatment. The stirring method is not particularly limited, and it may be stirring with weak shearing force such as a stirrer, or it may be stirred using a disperser with high shearing force such as a high-pressure homogenizer. However, from the viewpoint of enhancing dispersibility, it is preferable to use a high-pressure homogenizer or the like.

[0094] (Addition of optional components) A binder component or other additives may be further added to the conductive polymer-containing liquid obtained above.

[0095] (Addition of binder component) The conductive polymer-containing liquid of this embodiment may further contain a binder component. By using a conductive polymer-containing liquid containing a binder component, the strength of the conductive layer to be formed can be improved, and adhesiveness or releasability can be imparted. The binder component is a resin or a precursor thereof other than the π-conjugated conductive polymer and the polyanion, and is a thermoplastic resin, or a curable monomer or oligomer that cures during the formation of the conductive layer. The thermoplastic resin directly becomes the binder resin, and the resin formed by curing of the curable monomer or oligomer becomes the binder resin. The binder component may be an adhesive described later. The binder component added in this embodiment may be one type or two or more types.

[0096] Specific examples of the binder resin derived from the binder component include, for example, epoxy resin, acrylic resin (acrylic compound), polyester resin, polyurethane resin, polyimide resin, polyether resin, melamine resin, silicone, and the like.

[0097] The curable monomer or oligomer may be a thermosetting monomer or oligomer, or may be a photocurable monomer or oligomer. Here, an oligomer is a polymer having a mass average molecular weight of less than 10,000. Examples of the curable monomer include, for example, acrylic monomer (acrylic compound), epoxy monomer, organosiloxane, and the like. Examples of the curable oligomer include, for example, acrylic oligomer (acrylic compound), epoxy oligomer, silicone oligomer (curable silicone), and the like. When an acrylic monomer or acrylic oligomer is used as the binder component, it can be easily cured by heating or light irradiation.

[0098] When containing a curable monomer or oligomer, it is preferably further contained a curing catalyst. For example, when containing a thermosetting monomer or oligomer, it is preferably contained a thermal polymerization initiator that generates radicals by heating, and when containing a photocurable monomer or oligomer, it is preferably contained a photopolymerization initiator that generates radicals by light irradiation.

[0099] The content ratio of the binder component (excluding the silicone compound described later) contained in the conductive polymer-containing liquid of this embodiment is, for example, preferably 1 part by mass or more and 10,000 parts by mass or less, more preferably 10 parts by mass or more and 5,000 parts by mass or less, and still more preferably 100 parts by mass or more and 1,000 parts by mass or less with respect to 1 part by mass of the π-conjugated conductive polymer and all polyanions. When it is above the lower limit value of the above range, the characteristics of the binder component contained in the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be sufficiently exhibited. If it is below the upper limit value of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be ensured.

[0100] (Silicone compound) When the dispersion medium of the conductive polymer-containing liquid of this embodiment contains a hydrocarbon solvent or an ester solvent, the dispersibility of the silicone compound is more enhanced, which is preferable. Examples of the silicone compound include curable silicones. When the binder component is a curable silicone, mold release properties can be imparted to the conductive layer by curing the curable silicone.

[0101] The curable silicone may be either an addition-curable silicone or a condensation-curable silicone. In this embodiment, an addition-curable silicone is preferable because curing inhibition is less likely to occur even when it is used.

[0102] Examples of the addition-curable silicone include linear polymers having siloxane bonds and having vinyl groups at both ends of the linear chain, and those having a hydrogen silane. Such addition-curable silicones form a three-dimensional crosslinked structure by an addition reaction and cure. A platinum-based curing catalyst may be used to accelerate the curing. Specific examples of the addition-curable silicone include KS-3703T, KS-847T, KM-3951, X-52-151, X-52-6068, X-52-6069 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Addition-curable silicones that are dissolved or dispersed in an organic solvent are preferably used.

[0103] The content ratio of the silicone compound contained in the conductive polymer-containing liquid of this embodiment is preferably 10 parts by mass or more and 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 with respect to 100 parts by mass of the π-conjugated conductive polymer and all polyanions. If it is equal to or greater than the lower limit value of the above range, sufficient releasability can be imparted to the conductive layer formed by the conductive polymer-containing liquid of this embodiment. If it is equal to or less than the upper limit value of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be ensured.

[0104] [Adhesive] The conductive polymer-containing liquid of this embodiment may contain an adhesive as a binder component. By using a conductive polymer-containing liquid containing an adhesive, a conductive layer having adhesiveness can be formed. When the dispersion medium of the conductive polymer-containing liquid of this embodiment contains a hydrocarbon-based solvent or an ester-based solvent, it can be easily mixed with an adhesive previously dispersed in the hydrocarbon-based solvent or the ester-based solvent, and the conductive composite can be stably dispersed in the mixed liquid, which is preferable.

[0105] The degree of adhesiveness of the adhesive is not particularly limited, and it may have an adhesiveness that can be easily peeled off by hand after being pasted, or an adhesiveness that is difficult to peel off after being pasted. The adhesiveness that is difficult to peel off can be rephrased as adhesiveness. That is, the adhesiveness may be such that it can adhere semi-permanently.

[0106] As the adhesive, known adhesives can be applied. From the viewpoint of exhibiting good adhesiveness while maintaining conductivity, an acrylic-based adhesive is preferable.

[0107] (Acrylic-based adhesive) The acrylic-based adhesive can bond and integrate the surfaces of the same or different solids. The acrylic-based adhesive contains an acrylic resin (acrylic polymer).

[0108] 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, ditrimethylolpropane tetraacrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A·ethylene oxide modified diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy pentaacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, glycerin propoxytriacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, tripropylene glycol diacrylate and other acrylates; 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, trimethylolpropane trimethacrylate and other methacrylates;Examples of (meth)acrylamide include diacetone acrylamide, N,N-dimethylacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, methacrylamide, N-methylolacrylamide, acryloylformolin, N-methylacrylamide, N-isopropylacrylamide, N-t-butylacrylamide, N-phenylacrylamide, acryloylpiperidine, 2-hydroxyethylacrylamide, etc.; The acrylic monomer forming the acrylic resin may be one kind or two or more kinds. By combining two or more kinds of acrylic monomers, the adhesiveness can be adjusted.

[0109] The acrylic resin may be a copolymer of an acrylic monomer and a vinyl monomer other than the acrylic monomer. Examples of the vinyl monomer include styrene, α-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, maleic anhydride, etc. The content of the acrylic monomer unit 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 the acrylic monomer unit is at least the above lower limit value, the adhesiveness can be easily exhibited. The content of the vinyl monomer unit in the above copolymer can be, for example, 2 mol% or more and 20 mol% or less.

[0110] The glass transition temperature of the acrylic resin is preferably 80 °C or lower, more preferably 50 °C or lower, and still more preferably 0 °C or lower. An acrylic resin with a glass transition temperature exceeding 80 °C has low adhesiveness. The glass transition temperature of the acrylic resin is -80 °C or higher, and it is difficult to obtain one with a lower glass transition temperature. The glass transition temperature of the acrylic resin can be determined by differential scanning calorimetry or dynamic viscoelasticity measurement. Examples of acrylic monomers that tend to lower the glass transition temperature of acrylic resins include ethyl acrylate, butyl acrylate (especially n-butyl acrylate), 2-ethylhexyl acrylate, and the like. In acrylic resins, the higher the proportion of these monomer units, the lower the glass transition temperature.

[0111] The mass average molecular weight of the acrylic resin is preferably 10,000 or more and 2,000,000 or less, and more preferably 30,000 or more and 1,000,000 or less. If the mass average molecular weight of the acrylic resin is at least the lower limit value, sufficient cohesive force can be ensured. If it is at most the upper limit value, the adhesiveness can be further improved.

[0112] When the acrylic resin has an acrylic monomer unit having a reactive functional group, it may be reacted with a curing agent to be cured. When the acrylic resin is cured, the cohesive force of the conductive layer containing the adhesive can be improved and the strength can be improved. Further, by improving the cohesive force of the conductive layer, a re-peelable conductive layer capable of repeating adhesion and peeling can also be obtained. Examples of the reactive functional group include a hydroxy group, a carboxy group, an amino group, an amide group, an epoxy group, and the like. When reacting with a polyfunctional isocyanate described later, the reactive functional group is preferably a hydroxy group, a carboxy group, or an amino group, and more preferably a hydroxy group. Examples of the acrylic monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and the like. Examples of the acrylic monomer having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, and the like. Examples of the acrylic monomer having an amino group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the like. Examples of the acrylic monomer having an amide group include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and the like. Examples of the acrylic monomer having an epoxy group include glycidyl acrylate, glycidyl methacrylate, and the like. When a polyfunctional isocyanate is used as the curing agent, among the acrylic monomers having the reactive functional group, an acrylic monomer having a hydroxy group is preferable in view of curability and cost, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are more preferable. The acrylic monomer having the reactive functional group that forms the acrylic resin may be one kind or two or more kinds.

[0113] The content ratio of the pressure-sensitive adhesive contained 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 with respect to 1 part by mass of the π-conjugated conductive polymer and all polyanions. When it is at or above the lower limit value of the above range, sufficient adhesiveness can be imparted to the conductive layer formed by the conductive polymer-containing liquid of this embodiment. When it is at or below the upper limit value of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer-containing liquid of this embodiment can be ensured.

[0114] (Curing agent) When the pressure-sensitive 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 the curing agent 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 an acrylic monomer unit having a hydroxy group, it is preferable that the curing agent is a polyfunctional isocyanate.

[0115] Examples of the polyfunctional isocyanate include aliphatic polyfunctional isocyanates, alicyclic polyfunctional isocyanates, and aromatic polyfunctional isocyanates. Specific examples of the polyfunctional isocyanate 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, trans-cyclohexane 1,4-diisocyanate, 4,4'-dicyclomethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, and the like. The polyfunctional isocyanate may be a modified diisocyanate formed from the above-mentioned diisocyanate and 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 be a modified polyisocyanate. Examples of the modified polyisocyanate include polyurethane polyisocyanate obtained by reacting the polyfunctional isocyanate with a polyhydric alcohol, polyisocyanate containing an isocyanurate ring obtained by polymerizing the polyfunctional isocyanate, polyisocyanate containing a biuret bond obtained by reacting the polyfunctional isocyanate with water, and the like. The type of the curing agent contained in the conductive polymer-containing liquid of this embodiment may be one type or two or more types.

[0116] The content ratio of the curing agent contained in the conductive polymer-containing liquid of this embodiment is preferably, for example, 1 part by mass or more and 100 parts by mass or less, more preferably 2 parts by mass or more and 50 parts by mass or less, and even more preferably 3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the adhesive. When it is within the above range, sufficient adhesiveness can be imparted to the conductive layer formed by the conductive polymer-containing liquid of this embodiment.

[0117] (High conductivity agent) The conductive polymer-containing liquid of this embodiment may contain a high conductivity agent. Here, the π-conjugated conductive polymer, polyanion, organic solvent, adhesive, curing agent, and binder component described above are not classified as high conductivity agents. Note that the epoxy compound, amine compound, quaternary ammonium compound, and basic compound may correspond to the high conductivity agent described here. The high conductivity agent is preferably at least one compound selected from the group consisting of saccharides, 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 high conductivity agent contained in the conductive polymer-containing liquid of this embodiment may be one type or two or more types. The content ratio of the conductivity improver is preferably 1 part by mass or more and 10,000 parts by mass or less, more preferably 10 parts by mass or more and 5,000 parts by mass or less, and even more preferably 100 parts by mass or more and 2,500 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer and the total polyanion. If the content ratio of the conductivity improver is equal to or higher than the lower limit value, the effect of improving conductivity by adding the conductivity improver is sufficiently exhibited. If it is equal to or lower than the upper limit value, the decrease in conductivity caused by the decrease in the concentration of the π-conjugated conductive polymer can be prevented.

[0118] (Other additives) The conductive polymer-containing liquid of this embodiment may contain other known additives. The additives are not particularly limited as long as the effects of the present invention can be obtained. For example, surfactants, inorganic conductive agents, defoaming agents, coupling agents, antioxidants, ultraviolet absorbers, etc. can be used. Examples of the surfactant include nonionic, anionic, and cationic surfactants. From the viewpoint of storage stability, nonionic surfactants are preferred. Also, polymer surfactants such as polyvinylpyrrolidone may be added. Examples of the inorganic conductive agent include metal ions, conductive carbon, etc. The metal ions can be generated by dissolving a metal salt in water. Examples of the defoaming agent include silicone resins, polydimethylsiloxane, silicone oils, etc. Examples of the coupling agent include silane coupling agents having a vinyl group or an amino group. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, saccharides, etc. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, etc. When the conductive polymer-containing liquid of this aspect contains the above additive, the content ratio can be appropriately determined according to the type of the additive. For example, it can be in the range of 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer and the total polyanion.

[0119] ≪Manufacturing Method of Conductive Laminate≫ The second aspect of the present invention is a manufacturing method of a conductive laminate, which includes a step of obtaining a conductive polymer-containing liquid by the manufacturing method of the first aspect and a step of coating the conductive polymer-containing liquid on at least a part of the surface of a substrate.

[0120] [Substrate] The substrate may be a substrate made of an insulating material or a substrate made of a conductive material. The shape of the substrate is not particularly limited, and examples include shapes mainly composed of a plane such as a film and a substrate. Examples of the insulating material include glass, synthetic resin, and ceramics. Examples of the conductive material include metal, conductive metal oxide, and carbon.

[0121] (Film Substrate) When a film substrate is used as the substrate, the conductive laminate becomes a conductive film. Examples of the film substrate include plastic films made of synthetic resin. Examples of the synthetic resin include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene-based elastomer, polyester-based elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate, and the like. From the viewpoint of enhancing the adhesion between the film substrate and the conductive layer, the synthetic resin for the film substrate is preferably a polyester resin, and among them, polyethylene terephthalate is particularly preferred.

[0122] The synthetic resin for the film substrate may be amorphous or crystalline. The film substrate may be unstretched or stretched. The film substrate may be subjected to surface treatments such as corona discharge treatment, plasma treatment, and flame treatment in order to further improve the adhesion to the conductive layer.

[0123] The average thickness of the film substrate is preferably 5 μm or more and 500 μm or less, and more preferably 20 μm or more and 200 μm or less. If the average thickness of the film substrate is equal to or greater than the lower limit value, it becomes difficult to break, and if it is equal to or less than the upper limit value, sufficient flexibility as a film can be ensured. The average thickness of the film substrate is a value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

[0124] (Glass substrate) Examples of the glass substrate include an alkali-free glass substrate, a soda-lime glass substrate, a borosilicate glass substrate, and a quartz glass substrate. When the substrate contains an alkali component, the conductivity of the conductive layer tends to decrease. Therefore, among the above glass substrates, an alkali-free glass is preferred. Here, the alkali-free glass refers to a glass composition in which the content of the alkali component is 0.1% by mass or less based on the total mass of the glass composition.

[0125] The average thickness of the glass substrate is preferably 100 μm or more and 3000 μm or less, and more preferably 100 μm or more and 1000 μm or less. If the average thickness of the glass substrate is equal to or greater than the lower limit value, it becomes difficult to break, and if it is equal to or less than the upper limit value, it can contribute to thinning of the conductive laminate. The average thickness of the glass substrate is a value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

[0126] As a method of applying (coating) the conductive polymer-containing liquid onto an arbitrary surface of a substrate, for example, methods using coaters such as gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fountain coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, screen coater, etc., methods using sprayers such as air spray, airless spray, rotor damping, etc., dipping methods such as dip, etc. can be applied.

[0127] The coating amount of the conductive polymer-containing liquid on the substrate is not particularly limited, but considering uniform coating without unevenness and conductivity and film strength, as a solid content, 0.01 g / m 2 or more and 10.0 g / m 2 or less is preferably in the range.

[0128] A conductive layer can be formed by drying the coating film composed of the conductive polymer-containing liquid applied on the substrate to remove at least a part of the dispersion medium and curing it. Examples of the method of drying the coating film include heat drying, vacuum drying, etc. As heat drying, for example, methods such as hot air heating and infrared heating can be adopted. When applying heat drying, the heating temperature is appropriately set according to the dispersion medium used, but usually it is in the range of 50°C or more and 200°C or less. Here, the heating temperature is the set temperature of the drying device. As a suitable drying time in the above heating temperature range, 0.5 minutes or more and 30 minutes or less is preferable, and 1 minute or more and 15 minutes or less is more preferable. UV irradiation may be performed after drying to cure the binder component contained in the coating film.

[0129] The formation range of the conductive layer may be the entire surface or a part of any surface of the substrate. In the conductive film, it is preferable that a conductive layer with a substantially uniform thickness is formed on substantially the entire surface of one side or the other side of the film substrate. When the conductive layer is formed only on 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 region where the conductive layer is provided and the region where it is not provided may exist on the same surface and be roughly divided.

[0130] As the average thickness of the conductive layer, for example, 10 nm or more and 100 μm or less is preferable, 20 nm or more and 50 μm or less is more preferable, and 30 nm or more and 30 μm or less is even more preferable. If the average thickness of the conductive layer is equal to or greater than the lower limit value, high conductivity can be exhibited, and if it is equal to or less than the upper limit value, the adhesion of the conductive layer to the substrate is further improved. The average thickness of the conductive layer is a value obtained by measuring the thickness at 10 randomly selected locations and averaging the measured values.

Examples

[0131] (Production Example 1) Production of Polystyrene Sulfonic Acid 1 Dissolve 206 g of sodium styrene sulfonate in 1000 ml of ion-exchanged water, and while stirring at 80 °C, dropwise add a 1.14 g ammonium persulfate oxidant solution dissolved in 10 ml of water in advance over 20 minutes, and stir this solution for 12 hours. Add 1000 ml of sulfuric acid diluted to 10% by mass to the obtained sodium polystyrene sulfonate solution, and remove about 1000 ml of the solvent of the obtained polystyrene sulfonic acid solution by ultrafiltration. Next, add 2000 ml of ion-exchanged water to the residue, and remove about 2000 ml of the solvent by ultrafiltration to wash the polystyrene sulfonic acid. This washing operation was repeated 3 times. Next, dissolve 10 g of the obtained polystyrene sulfonic acid in 90 g of ion-exchanged water to obtain a 10% by mass aqueous polystyrene sulfonic acid solution.

[0132] By gel permeation chromatography (GPC), using pullulan with a known weight average molecular weight as a standard substance, the weight average molecular weight (Mw) of the polystyrene sulfonic acid (PSS) obtained above was measured. As a result, the weight average molecular weight was 180,000. The measurement of the weight average molecular weight was carried out using a high-performance liquid chromatograph Prominence manufactured by Shimadzu Corporation. An aqueous solution of 0.1% NaNO3 was used as the solvent, Shodex OHpack SB-806M HQ was used as the column, RID-20A was used as the detector, the solvent temperature was set at 40 °C, the flow rate was set at 0.6 ml / min, the PSS concentration in the sample was set at 0.1 mass%, and 100 μl of the sample filtered through a membrane filter with a pore size of 0.2 μm was injected, and the analysis was performed using the analysis software LabSolutions (manufactured by Shimadzu Corporation).

[0133] (Production Example 2) Production of Polystyrene Sulfonic Acid 2 206 g of sodium styrene sulfonate was dissolved in 1000 ml of ion-exchanged water, and while stirring at 80 °C, an oxidizing agent solution of 0.38 g of ammonium persulfate previously dissolved in 10 ml of water was added dropwise over 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 mass% was added, and approximately 1000 ml of the solvent of the obtained polystyrene sulfonic acid solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the residue, and approximately 2000 ml of the solvent was removed by ultrafiltration to wash the polystyrene sulfonic acid. This washing operation was repeated 3 times. The water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid. Next, 10 g of the obtained polystyrene sulfonic acid was dissolved in 90 g of ion-exchanged water to obtain a 10 mass% aqueous solution of polystyrene sulfonic acid. The weight average molecular weight of the polystyrene sulfonic acid (PSS) obtained above, measured using GPC in the same manner as in Production Example 1, was 540,000.

[0134] (Example 1) 3.0 g of 3,4-ethylenedioxythiophene (EDOT), 90 g of a 10% by mass aqueous PSS solution of Production Example 1, 0.75 g of imidazole, and 325 g of ion-exchanged water were mixed at 20°C. While maintaining the obtained mixed solution at 20°C and stirring, 1.2 g of ferric sulfate was added. Next, an oxidizing agent solution (25°C) prepared by dissolving 6.6 g of sodium persulfate in 293.4 g of ion-exchanged water was slowly added over 4 hours, and the reaction solution (25°C) obtained after adding all of the oxidizing agent solution was stirred for 8 hours to cause a reaction. By the above reaction, a conductive polymer-containing liquid containing a conductive composite (PEDOT-PSS) containing poly(3,4-ethylenedioxythiophene), which is a π-conjugated conductive polymer, and polystyrene sulfonic acid, water as a dispersion medium, and imidazole was obtained. To this conductive polymer-containing liquid, 39 g of Duolite C255LFH (manufactured by Sumika Chemtex Corporation, cation exchange resin) and 39 g of Duolite A368S (manufactured by Sumika Chemtex Corporation, anion exchange resin) were added, and the mixture was filtered to remove the ion exchange resin, obtaining 710 g of a conductive polymer-containing liquid (nonvolatile component concentration: 1.4% by mass) from which the oxidizing agent, the catalyst, and the imidazole had been removed. Next, ion-exchanged water was added to the obtained conductive polymer-containing liquid to adjust the nonvolatile component concentration to 1.0% by mass. After dispersing using a high-pressure homogenizer, it 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 results of measuring the surface resistance value R0 of this conductive film are shown in Table 1.

[0135] When the conductive polymer-containing liquid used for the above coating was analyzed with a gas chromatography mass spectrometer, unreacted EDOT was below the measurement limit. From this result, it was found that almost all of the EDOT had formed PEDOT. It was also confirmed that imidazole was not contained (below the measurement limit). The above gas chromatography measurement was performed using a GCMS-QP2010Plus manufactured by Shimadzu Corporation, helium as the carrier gas, a DB-5MS column, a secondary electron multiplier tube with a conversion diode as the detector, setting the vaporization temperature at 250 °C, the flow rate at 1.2 mL / min, injecting 1 μL of the sample, setting the PEDOT-PSS concentration in the sample at 1.0 mass%, and using the analysis software GCMSsolution.

[0136] The conductive polymer-containing liquid used for the above coating was filtered through a membrane filter with a pore size of 0.2 μm (manufactured by Membrane Solutions Japan, model number: NY-030022), trapping PEDOT-PSS on the membrane while allowing the single PSS (not forming PEDOT-PSS) contained in the conductive polymer-containing liquid to permeate and collecting it in the filtrate. When the weight-average molecular weight of the PSS contained in this filtrate was measured by GPC as described in Production Example 1, it was 128,000. Therefore, the weight-average molecular weight X of PSS before EDOT polymerization was 180,000, the weight-average molecular weight Y of the remaining PSS after PEDOT-PSS formation was 128,000, and Y / X ≈ 0.71.

[0137] (Example 2) A conductive polymer-containing liquid (nonvolatile component concentration: 1.4 mass%) of 710 g was obtained in the same manner as in Example 1, except that “0.75 g of imidazole” in Example 1 was changed to “1.5 g of imidazole”.

[0138] (Example 3) A conductive polymer-containing liquid (nonvolatile component concentration: 1.5 mass%) of 710 g was obtained in the same manner as in Example 1, except that “0.75 g of imidazole” in Example 1 was changed to “3.0 g of imidazole”.

[0139] (Example 4) A conductive polymer-containing liquid (710 g, non-volatile component concentration: 1.4% by mass) was obtained in the same manner as in Example 1, except that "0.75 g of imidazole" in Example 1 was changed to "0.75 g of triethylamine". The triethylamine in the polymerization reaction solution was removed with an ion exchange resin in the same manner as in the case of imidazole.

[0140] (Example 5) A conductive polymer-containing liquid (710 g, non-volatile component concentration: 1.4% by mass) was obtained in the same manner as in Example 1, except that "0.75 g of imidazole" in Example 1 was changed to "1.5 g of triethylamine". The triethylamine in the polymerization reaction solution was removed with an ion exchange resin in the same manner as in the case of imidazole.

[0141] (Comparative Example 1) A conductive polymer-containing liquid (710 g, non-volatile component concentration: 1.2% by mass) was obtained in the same manner as in Example 1, except that "0.75 g of imidazole" in Example 1 was not added.

[0142] (Example 6) A conductive polymer-containing liquid (710 g, non-volatile component concentration: 1.8% by mass) was obtained in the same manner as in Example 1, except that "90 g of a 10% by mass aqueous PSS solution of Production Example 1 and 325 g of ion-exchanged water were mixed at 20°C" in Example 1 was changed to "150 g of a 10% by mass aqueous PSS solution of Production Example 1 and 265 g of ion-exchanged water were mixed at 20°C".

[0143] (Comparative Example 2) A conductive polymer-containing liquid (710 g, non-volatile component concentration: 1.8% by mass) was obtained in the same manner as in Example 6, except that "0.75 g of imidazole" in Example 6 was not added.

[0144] (Example 7) A conductive polymer-containing liquid (710 g, non-volatile component concentration: 1.4% by mass) was obtained in the same manner as in Example 1, except that "90 g of a 10% by mass aqueous PSS solution of Production Example 1" in Example 1 was changed to "90 g of a 10% by mass aqueous PSS solution of Production Example 2".

[0145] (Comparative Example 3) A conductive polymer dispersion liquid (710 g, non-volatile component concentration: 1.3% by mass) was obtained in the same manner as in Example 7, except that "0.75 g of imidazole" in Example 7 was not added.

[0146] Using the conductive polymer-containing liquids obtained in the above examples, conductive films were produced in the same manner as in Example 1, and the surface resistance values were measured. Also, gas chromatography measurement was performed in the same manner as in Example 1 to measure the remaining amount of EDOT (remaining amount P) after the EDOT polymerization reaction. Further, in the same manner as in Example 1, the weight-average molecular weight Y of the remaining PSS after the formation of PEDOT-PSS was measured by GPC. The results are shown in Table 1.

[0147] [Measurement of surface resistance value] For the conductive films produced in each example, the surface resistance value R0 of the conductive layer was measured using a resistivity meter (Hi-Rester manufactured by Nitto Seiko Analytic Co., Ltd.) under the condition of an applied voltage of 10 V. In the table, "1.0E+05" means "1.0×10 5 ", and the same applies to others.

[0148] [Atmospheric exposure test] The conductive films for which the surface resistance value R0 was measured were left in the atmosphere at a temperature of 25°C and a humidity of 50% RH for 30 days, and then the surface resistance value R1 was measured again in the same manner as above. The results and the increase ratio of the surface resistance value (R1 / R0) are shown in Table 1.

[0149]

Table 1

[0150] (Example 8) To 100 g of the conductive polymer-containing liquid of Example 1 (nonvolatile component concentration: 1.0% by mass), 50 g of isopropanol and 10 g of trioctylamine were added, and the mixture was stirred for 1 hour to react trioctylamine with a part of the sulfonic acid groups of the conductive composite. As a result, all of the reaction products floated on the upper layer of the reaction solution. This reaction solution was filtered to obtain a powder of the reaction product of the conductive composite and trioctylamine. Isopropanol was added to this powder to make a 500 g mixed solution, which was dispersed using a high-pressure homogenizer to obtain 500 g of a conductive polymer-containing liquid. The results of measuring the nonvolatile component concentration of this containing liquid are shown in Table 2. Next, the obtained conductive polymer-containing liquid was applied onto a PET film using a #8 bar coater and dried at 100 °C for 1 minute to obtain a conductive film. The measurement results of its surface resistance value R0 are shown in Table 2.

[0151] (Comparative Example 4) A conductive polymer-containing liquid using isopropanol as a dispersion medium was obtained and a conductive film was produced 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). The results are shown in Table 2.

[0152] (Example 9) To 100 g of the conductive polymer-containing liquid of Example 1 (nonvolatile component concentration: 1.0% by mass), 25 g of an epoxy compound (manufactured by Kyoeisha Chemical Co., Ltd., Epolite M-1230, C12,13 mixed higher alcohol glycidyl ether) was added, and the mixture was heated and stirred at 60 °C for 4 hours to react the epoxy compound with a part of the sulfonic acid groups of the conductive composite. As a result, reaction products precipitated. These precipitates were filtered to recover the reaction product of the conductive composite and the epoxy compound. Methyl ethyl ketone was added to this reaction product to make a 300 g mixed solution, which was dispersed using a high-pressure homogenizer to obtain 300 g of a conductive polymer-containing liquid. The results of measuring the nonvolatile component concentration of this containing liquid are shown in Table 2. Next, the obtained conductive polymer-containing liquid was applied onto a PET film using a #8 bar coater and dried at 100 °C for 1 minute to obtain a conductive film.

[0153] (Comparative Example 5) A conductive polymer-containing liquid was obtained and a conductive film was produced in the same manner as in Example 9, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Comparative Example 1 (non-volatile component concentration: 1.0% by mass), using methyl ethyl ketone as a dispersion medium. The results are shown in Table 2.

[0154] (Example 10) To 100 g of the conductive polymer-containing liquid of Example 1 (non-volatile component concentration: 1.0% by mass), 25 g of an 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, whereby the epoxy compound and trioctylamine reacted with some of the sulfonic acid groups of the conductive composite. As a result, a reaction product precipitated. This precipitate was filtered to obtain a reaction product of the conductive composite with the epoxy compound and trioctylamine. Ethyl acetate was added to this reaction product to make a 800 g mixture, which was dispersed using a high-pressure homogenizer to obtain 800 g of a conductive polymer-containing liquid. The results of measuring the non-volatile component concentration of this containing liquid are shown in Table 2. Next, the obtained conductive polymer-containing liquid was applied onto a PET film using a #8 bar coater and dried at 100 °C for 1 minute to obtain a conductive film.

[0155] (Comparative Example 6) A conductive polymer-containing liquid was obtained and a conductive film was produced in the same manner as in Example 10, except that 100 g of the conductive polymer-containing liquid of Example 1 was changed to 100 g of the conductive polymer-containing liquid of Comparative Example 1 (non-volatile component concentration: 1.0% by mass), using ethyl acetate as a dispersion medium. The results are shown in Table 2.

[0156] For the conductive films obtained in each of the above examples, an air exposure test was conducted in the same manner as in Example 1, and the surface resistance value R1 was measured. These results are shown in Table 2.

Table 2

[0157] <Result> The electrical conductivity polymer-containing liquid formed using an example in which the ratio represented by (Y / X) of the weight average molecular weight X of PSS before EDOT polymerization and the weight average molecular weight Y of PSS that did not form PEDOT-PSS remaining after PEDOT-PSS formation in the above polymerization reaction liquid is 0.67 or more had better atmospheric exposure resistance than the conductive film formed using the comparative example's electrical conductivity polymer-containing liquid with a Y / X ratio of less than 0.67. Also, it is clear that adding a basic compound to the polymerization reaction liquid is effective for making Y / X 0.67 or more.

[0158] <Action mechanism> The mechanism by which the atmospheric exposure resistance of the conductive layer is improved by using an electrical conductivity polymer-containing liquid with a Y / X ratio of 0.67 or more as described above is presumed as follows. When the Y / X ratio is 0.67 or more, the molecular weight of the polyanion that has not formed a conductive complex is large, and the polyanion is likely to be arranged on the coating surface, so the oxidative degradation of the π-conjugated system conductive polymer is suppressed and the atmospheric exposure resistance is increased. When the Y / X ratio is less than 0.67, the molecular weight of the polyanion that has not formed a conductive complex is small, and the polyanion is less likely to be arranged on the coating surface, so the oxidative degradation of the π-conjugated system conductive polymer cannot be suppressed and the atmospheric exposure resistance is low.

Claims

1. A reaction solution containing a polyanion, a basic compound, and an aqueous dispersion medium is used to polymerize a monomer that forms a π-conjugated conductive polymer (excluding the basic compound). By this polymerization, a conductive polymer-containing liquid is obtained, which 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. The manufacturing method of the conductive polymer-containing liquid includes a polymerization step. When starting the polymerization by adding an oxidizing agent solution containing an oxidizing agent pre-dissolved in ion-exchanged water to a mixed liquid containing the monomer, the polyanion, the basic compound, and a catalyst, the volume ratio represented by V1 / V2, where V1 is the volume of the mixed liquid before adding the oxidizing agent solution and V2 is the volume of the oxidizing agent solution, is 1.0 to 2.

0. The concentration of the oxidizing agent contained in the oxidizing agent solution is 1.0 mass% or more and 3.0 mass% or less. When adding all of the oxidizing agent solution to the mixed liquid, it is slowly added over 1 to 8 hours from the start of addition to the end of addition. A manufacturing method of a conductive polymer-containing liquid, wherein the ratio represented by Y / X, where Y is the weight average molecular weight of the polyanion that does not form the conductive composite after polymerization and X is the weight average molecular weight of the polyanion before polymerization, is 0.67 or more.

2. The content ratio of the basic compound in the mixed liquid is 1 part by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyanion in the mixed liquid. The manufacturing method of the conductive polymer-containing liquid according to Claim 1.

3. The manufacturing method of the conductive polymer-containing liquid according to Claim 1 or 2, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene), or the polyanion is polystyrene sulfonic acid.

4. After polymerizing the monomer by adding the oxidizing agent, the basic compound, and the catalyst to the reaction solution, the oxidizing agent, the basic compound, and the catalyst are removed from the conductive polymer-containing liquid. The manufacturing method of the conductive polymer-containing liquid according to any one of Claims 1 to 3.

5. The manufacturing method of the conductive polymer-containing liquid according to Claim 4, wherein the oxidizing agent, the catalyst, and the basic compound are removed by bringing the conductive polymer-containing liquid into contact with at least one of a cation exchange resin and an anion exchange resin.

6. The method for producing a conductive polymer-containing liquid according to any one of claims 1 to 5, wherein an epoxy compound is reacted with the conductive polymer-containing liquid obtained in the polymerization step to obtain a conductive polymer-containing liquid containing the obtained reaction product and an organic solvent.

7. The method for producing a conductive polymer-containing liquid according to any one of claims 1 to 5, wherein an amine compound or a quaternary ammonium compound is reacted with the conductive polymer-containing liquid obtained in the polymerization step to obtain a conductive polymer-containing liquid containing the obtained reaction product and an organic solvent.

8. The method for producing a conductive polymer-containing liquid according to any one of claims 1 to 5, wherein an epoxy compound and an amine compound or a quaternary ammonium compound are reacted with the conductive polymer-containing liquid obtained in the polymerization step to obtain a conductive polymer-containing liquid containing the obtained reaction product and an organic solvent.

9. A method for producing a conductive laminate, comprising: a step of obtaining a conductive polymer-containing liquid by the production method according to any one of claims 1 to 8; and a step of coating at least a part of the surface of a substrate with the conductive polymer-containing liquid.

10. The method for producing a conductive laminate according to claim 9, wherein the substrate is a film substrate.

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