JP2022092872A - Conductive polymer dispersion and method for producing the same, and conductive laminate - Google Patents

Abstract

To provide a conductive polymer dispersion containing a conductive composite with a reduced diameter and a method for producing the same, and a conductive laminate produced with the conductive polymer dispersion.SOLUTION: (1) A conductive polymer dispersion contains a conductive composite that contains a π-conjugated conductive polymer and an anionic polymer having a monomer unit derived from a compound represented by a specific chemical formula, and a dispersion medium. (2) A method for producing a conductive polymer dispersion includes a process in which: in a reaction solution containing a monomer compound, which forms a π-conjugated conductive polymer by polymerization, the anionic polymer and an aqueous dispersion medium, the monomer compound is polymerized to obtain a conductive polymer dispersion that contains a conductive composite containing the π-conjugated conductive polymer and the anionic polymer, and the aqueous dispersion medium.SELECTED DRAWING: None

Description

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

The π-conjugated conductive polymer having a π-conjugated backbone forms a conductive complex by doping with a polyanion having an anionic group, and dispersibility in water is generated. By applying a conductive polymer dispersion liquid containing a conductive composite to a base material, a conductive laminate provided with a conductive layer can be manufactured. Further, in the production of an electrolytic capacitor provided with a conductive composite as an electrolyte of a capacitor element, a conductive polymer dispersion liquid may be used (Patent Document 1).

Japanese Patent No. 6527271

As disclosed in Patent Document 1, when a fine particle conductive composite contained in a conductive polymer dispersion is introduced into an etching pit on the surface of an anode foil, the average particle size (particle size) thereof is 100 nm or less. It is said that the range is preferable. Further, even when the thickness of the conductive layer formed by applying the conductive polymer dispersion liquid to the base material is about 200 nm or less, the particle size of the conductive composite is adjusted from the viewpoint of reducing the unevenness of the surface of the conductive layer. It may be required to make it smaller.

The present invention provides a conductive polymer dispersion liquid containing a conductive composite having a reduced diameter, a method for producing the same, and a conductive laminate manufactured using the conductive polymer dispersion liquid.

[1] A conductive composite containing a π-conjugated conductive polymer and an anionic polymer having a monomer unit derived from the compound 1 represented by the following formula (1), and a dispersion medium. Conductive polymer dispersion.
[2] The conductive polymer dispersion liquid according to [1], wherein the anionic polymer is a homopolymer of the compound 1.
[3] The conductive polymer dispersion liquid according to [1], wherein the anionic polymer is a copolymer of styrene sulfonic acid and the compound 1.
[4] The conductive polymer dispersion liquid according to any one of [1] to [3], wherein the conductive composite further contains a polyanion having no monomer unit derived from the compound 1.
[5] The conductive polymer according to any one of [1] to [4], wherein the anionic group of the conductive composite is modified by a reaction with an amine compound or a quaternary ammonium compound. Dispersion solution.
[6] The conductive polymer dispersion liquid according to any one of [1] to [4], wherein the anionic group contained in the conductive composite is modified by a reaction with an epoxy compound.
[7] The item according to any one of [1] to [4], wherein the anionic group of the conductive composite is modified by reaction with an amine compound, a quaternary ammonium compound, and an epoxy compound. Conductive polymer dispersion.
[8] The conductive polymer dispersion liquid according to any one of [1] to [7], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[9] A reaction solution containing a monomer compound forming a π-conjugated conductive polymer, an anionic polymer having a monomer unit derived from the compound 1 represented by the following formula (1), and an aqueous dispersion medium. In the above, by polymerizing the monomer compound, a conductive polymer dispersion liquid containing the π-conjugated conductive polymer, the conductive composite containing the anionic polymer, and the aqueous dispersion medium is obtained. , A method for producing a conductive polymer dispersion.
[10] The method for producing a conductive polymer dispersion liquid according to [9], wherein the anionic polymer is a homopolymer of the compound 1.
[11] The method for producing a conductive polymer dispersion according to [9], wherein the anionic polymer is a copolymer of styrene sulfonic acid and the compound 1.
[12] The conductive composite is further contained with the polyanion by polymerizing the monomer compound in a state where the reaction solution further contains a polyanion other than the anionic polymer [9] to The method for producing a conductive polymer dispersion liquid according to any one of [11].
[13] To the conductive polymer dispersion liquid containing the aqueous dispersion medium, one or more selected from an epoxy compound, an amine compound and a quaternary ammonium compound is added and reacted with the conductive composite. To precipitate the conductive composite modified by the reaction in the aqueous dispersion medium, and to recover the precipitated conductive composite and add an organic solvent, the conductive composite and the organic solvent are added. The method for producing a conductive polymer dispersion according to any one of [9] to [12], which comprises obtaining a conductive polymer dispersion containing the above.
[14] The conductive polymer dispersion according to any one of [1] to [8], comprising a base material and a conductive layer formed on at least one surface of the base material. A conductive laminate that is a cured product of liquid.

［式中、Ｒは炭素数４～２０の直鎖状又は分岐鎖状アルキル基であり、ｎは４～１００の整数である。］

[In the formula, R is a linear or branched alkyl group having 4 to 20 carbon atoms, and n is an integer of 4 to 100. ]

According to the production method of the present invention, a conductive polymer dispersion liquid containing a conductive composite having a small particle size can be easily obtained. Further, by using the conductive polymer dispersion liquid of the present invention, it is possible to reduce the unevenness of the surface even when a thin conductive layer having a thickness of 200 nm or less is formed.

The present invention is considered to contribute to SDGs Goal 12, "Responsibility to Create and Responsibility to Use".

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

≪Conductive polymer dispersion liquid≫
The first aspect of the present invention is a conductive composite containing a π-conjugated conductive polymer and an anionic polymer having a monomer unit derived from the compound 1 represented by the following formula (1), and a dispersion medium. It is a conductive polymer dispersion liquid containing and.
In the conductive polymer dispersion liquid of this embodiment, the conductive composite may be in a dispersed state or a dissolved state.

The conductive composite of this embodiment includes the π-conjugated conductive polymer and an anionic polymer having a monomer unit derived from compound 1.
The anionic polymer may be a homopolymer or a copolymer.
The homopolymer is a homopolymer obtained by polymerizing only compound 1.
The copolymer is a copolymer of compound 1 and an anionic compound having a polymerizable functional group and an anionic group (excluding compound 1).

The mass average molecular weight Mw of the homopolymer is preferably 10,000 to 1,000,000 from the viewpoint of improving the doping effect on the π-conjugated conductive polymer and the dispersity of the conductive composite, and is preferably 0.5. 10,000 to 100,000 is more preferable, and 10,000 to 50,000 is even more preferable.
Here, the mass average molecular weight is a mass-based average molecular weight measured by gel permeation chromatography (GPC method) using pullulan as a standard substance.

The polymerizable functional group of the anionic compound is not particularly limited as long as it can be copolymerized with the vinyl group of the compound 1, and examples thereof include a vinyl group and a vinylidene group.
The anionic group of the anionic compound is preferably one that can be dissociated in water and doped into a π-conjugated conductive polymer, and examples thereof include a sulfo group and a carboxy group.
The counter cation of the anion group may be a proton, an alkali metal cation such as sodium ion or potassium ion, or an alkaline earth metal cation. However, since the anionic polymer is likely to be doped into the π-conjugated conductive polymer, the counter cation of the anionic group is preferably a proton.
Specific examples of the anionic compound include known compounds constituting the monomer unit of the polyanion described later.

In the copolymer, the ratio of the content A of the monomer unit derived from the compound 1 to the content B of the other monomer units is when the total number of monomer units of the copolymer is 100 mol%. Content A: Content B is based on mol%, for example, 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and 40:60 to 40:60. 60:40 is more preferable.
Within the above-mentioned preferable range, the balance between the improvement of the conductivity of the conductive layer formed by using the conductive polymer dispersion liquid of this embodiment and the reduction in the diameter of the conductive composite is excellent.

The mass average molecular weight Mw of the copolymer is preferably 5,000 to 2,000,000 to 10,000 to 2,000,000 from the viewpoint of improving the doping effect on the π-conjugated conductive polymer and the dispersibility of the conductive composite. One million is more preferable, and 100,000 to 500,000 is even more preferable.
Here, the mass average molecular weight is a mass-based average molecular weight measured by gel permeation chromatography (GPC method) using pullulan as a standard substance.

Examples of the other monomer unit constituting the copolymer include the monomer unit constituting the polyanion described later.

The conductive complex may further contain a polyanion having no monomer unit derived from compound 1. Specific examples of polyanions will be described later.
When the polyanion is further contained in the conductive composite, the conductivity of the conductive layer formed by the conductive polymer dispersion liquid of this embodiment can be further enhanced.
From the viewpoint of reducing the particle size (particle size) of the conductive composite contained in the conductive polymer dispersion liquid of this embodiment, it is preferable that the polyanion is not contained in the conductive composite.

The content of the anionic polymer in the conductive composite is preferably 1 part by mass or more and 1000 parts by mass or less, preferably 10 parts by mass or more and 700 parts by mass or less, with respect to 100 parts by mass of the π-conjugated conductive polymer. Is more preferable, and 100 parts by mass or more and 500 parts by mass or less are further preferable.
When it is at least the lower limit of the above range, the doping effect of the anionic polymer on the π-conjugated conductive polymer becomes strong, the dispersibility of the conductive complex is improved, and the particle size of the conductive complex is sufficient. The diameter is reduced and the conductivity is higher.
When it is not more than the upper limit of the above range, the decrease in conductivity due to the decrease in the content ratio of the π-conjugated conductive polymer can be suppressed.

When the polyanion is contained in the conductive composite, the content of the polyanion is preferably 1 part by mass or more and 1000 parts by mass or less, preferably 10 parts by mass or more, with respect to 100 parts by mass of the π-conjugated conductive polymer. 700 parts by mass or less is more preferable, and 100 parts by mass or more and 500 parts by mass or less is further preferable.
When it is at least the lower limit of the above range, the doping effect of the polyanion on the π-conjugated conductive polymer becomes strong, the dispersibility of the conductive complex is improved, and the conductivity becomes higher.
When it is not more than the upper limit of the above range, the decrease in conductivity due to the decrease in the content ratio of the π-conjugated conductive polymer can be suppressed.

When the polyanion is contained in the conductive composite, the content ratio of the polyanion is preferably 1 part by mass or more and 1000 parts by mass or less, and 10 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the anionic polymer. Is more preferable, and 50 parts by mass or more and 200 parts by mass or less are further preferable.
When it is at least the lower limit of the above range, the conductivity of the conductive layer becomes higher.
When it is not more than the upper limit of the above range, the effect of reducing the particle size of the conductive complex can be sufficiently obtained.

The anion group of the conductive composite, that is, the anion group of the monomer unit derived from compound 1 and / or the anion group of the polyanion is from an epoxy compound, an amine compound, and a quaternary ammonium compound, as described later. It may be modified by reaction with one or more selected species. Details of this modification will be described later.

The content of the conductive composite with respect to the total mass of the conductive polymer dispersion is, for example, preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 5% by mass or less, and 0. .3% by mass or more and 2% by mass or less is more preferable.
Within the above-mentioned preferable range, the dispersibility of the conductive complex in the conductive polymer dispersion can be further enhanced.

<Pi-conjugated conductive polymer>
The π-conjugated conductive polymer may be an organic polymer whose main chain is composed of a π-conjugated system. For example, a polypyrrole-based conductive polymer, a polythiophene-based conductive polymer, and a polyacetylene-based conductive polymer have high conductivity. Examples thereof include molecules, polyphenylene-based conductive polymers, polyphenylene vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophenine-based conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-hexylthiophene). , Poly (3-heptylthiophene), Poly (3-octylthiophene), Poly (3-decylthiophene), Poly (3-dodecylthiophene), Poly (3-octadecylthiophene), Poly (3-bromothiophene), Poly (3-Chlorothiophene), Poly (3-iodothiophene), Poly (3-cyanothiophene), Poly (3-phenylthiophene), Poly (3,4-dimethylthiophene), Poly (3,4-dibutylthiophene) , Poly (3-hydroxythiophene), Poly (3-methoxythiophene), Poly (3-ethoxythiophene), Poly (3-butoxythiophene), Poly (3-hexyloxythiophene), Poly (3-Heptyloxythiophene) , Poly (3-octyloxythiophene), Poly (3-decyloxythiophene), Poly (3-dodecyloxythiophene), Poly (3-octadecyloxythiophene), Poly (3,4-dihydroxythiophene), Poly (3) , 4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene) , Poly (3,4-diheptyloxythiophene), Poly (3,4-dioctyloxythiophene), Poly (3,4-didecyloxythiophene), Poly (3,4-didodecyloxythiophene), Poly (3,4-didodecyloxythiophene) 3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butylenedioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3- Methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl-4-carboxyphene) Butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and poly (3-butyl). Pyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3) -Carboxypyrrole), Poly (3-Methyl-4-carboxypyrrole), Poly (3-Methyl-4-carboxyethylpyrrole), Poly (3-Methyl-4-carboxybutylpyrrole), Poly (3-Hydroxypyrrole) , Poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole).
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), and poly (3-aniline sulfonic acid).
Among these π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable because it is excellent in conductivity, transparency, and heat resistance.
The π-conjugated conductive polymer contained in the conductive composite may be of one type or two or more types.

<Anionic polymer>
The compound 1 represented by the following formula (1), which is the monomer material of the anionic polymer, is a compound in which a sulfonic acid group and a vinyl group are linked by a polyoxyethylene chain (CH ₂ CH ₂ O) _n . be.
The compound 1 constituting the anionic polymer may be one kind or two or more kinds.

［式中、Ｒは炭素数４～２０の直鎖状又は分岐鎖状アルキル基であり、ｎは４～１００の整数である。］

[In the formula, R is a linear or branched alkyl group having 4 to 20 carbon atoms, and n is an integer of 4 to 100. ]

The anionic polymer can be bonded to the π-conjugated conductive polymer as a dopant in the same manner as the conventional polyanion. When functioning as a dopant, the sulfonic acid group is considered to be doped as an anionic group. By doping the π-conjugated conductive polymer with the anionic polymer, it is considered that the conductivity of the π-conjugated conductive polymer is improved and the diameter of the π-conjugated conductive polymer is reduced, which will be described later.

The anionic polymer may be simply contained in the conductive polymer dispersion as an additive without being doped with the π-conjugated conductive polymer, but the π-conjugated polymer is inherently poor in dispersibility in water. In order for the based conductive polymer (for example, PEDOT) to exhibit dispersibility with respect to the aqueous dispersion medium, it is preferable that the anionic polymer is doped with the π-conjugated conductive polymer.

The alkyl group represented by R in the formula (1) is preferably linear.
The alkyl group has 4 to 20 carbon atoms, preferably 6 to 18, more preferably 8 to 16, still more preferably 10 to 14, and particularly preferably 10 to 12.
When the number of carbon atoms is in the above-mentioned preferable range, the particle size of the conductive complex can be made smaller.

The degree of polymerization n of the polyoxyethylene chain is 4 to 100, preferably 5 to 80, more preferably 6 to 50, further preferably 7 to 30, and particularly preferably 8 to 20.
Within the above-mentioned preferable range, the particle size of the conductive composite can be made smaller, and the conductivity of the conductive layer formed by using the conductive polymer dispersion liquid of this embodiment can be further enhanced.

Suitable specific examples of the compound 1 include, for example, ammonium α- [1- (allyloxy) dodecane-2-yl] -ω- (sulfonatooxy) poly (oxy) registered in CAS No. 352661-91-7. A sulfonic acid compound in which ammonium of (ethylene) is replaced with a proton; ammonium α- [1- (allyloxy) tetradecane-2-yl] -ω- (sulfonatooxy) poly registered at CAS No. 224646-44-0 (sulfonatooxy) Examples thereof include a sulfonic acid body in which ammonium of (oxyethylene) is replaced with a proton.
These ammonium salts are Aqualon KH-05 (n = 8 to 11, R = linear alkyl group having 10 or 12 carbon atoms), Aqualon KH-10 (n = 22 to 25,) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. It can be obtained as R = a linear alkyl group having 10 or 12 carbon atoms) and Aqualon KH-1025 (n = 68 to 71, R = a linear alkyl group having 10 or 12 carbon atoms).

When the anionic polymer forms a conductive composite by doping the π-conjugated conductive polymer, in the anionic polymer, some anionic groups are doped into the π-conjugated conductive polymer. It does not have a surplus anionic group that does not participate in doping. Since this excess anion group is a hydrophilic group, the conductive complex has high water dispersibility and low organic solvent dispersibility in the state before modification as described later.
When the number of all anionic groups contained in the anionic polymer is 100 mol%, the excess anionic group is preferably 30 mol% or more and 90 mol% or less, and more preferably 45 mol% or more and 75 mol% or less.

<Polyanion>
The conductive polymer dispersion liquid of this embodiment may contain a polyanion having no monomer unit derived from compound 1. However, if the polyanion is contained, the conductivity of the conductive layer is improved, but the particle size of the conductive complex tends to be large. Therefore, if priority is given to reducing the particle size, it is preferable not to contain the polyanion. ..
The polyanion is a polymer having two or more, preferably 10 or more monomer units having an anion group in the molecule. The anionic group of this polyanion functions as a dopant for the π-conjugated conductive polymer, and can improve the conductivity of the π-conjugated conductive polymer.

The anion group of the polyanion is preferably a sulfo group or a carboxy group because it has an excellent doping effect on a π-conjugated conductive polymer.
Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ester having a sulfo group, and polymethacrylic acid ester having a sulfo group (for example, poly (4-sulfobutyl methacrylate). , Polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprenesulfonic acid and other polymers with sulfo groups, polyvinylcarboxylic acid, polystyrenecarboxylic acid, etc. Examples thereof include polymers having a carboxy group such as polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly (2-acrylamide-2-methylpropanecarboxylic acid), and polyisoprenecarboxylic acid. These are homopolymers. It may be a copolymer composed of two or more kinds of monomers.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be made higher.
The polyanion constituting the conductive complex may be one kind or two or more kinds.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1 million or less, and more preferably 100,000 or more and 500,000 or less.
Here, the mass average molecular weight is a mass-based average molecular weight measured using pullulan as a standard substance using a gel filtration chromatograph method.

When the polyanion forms a conductive composite by doping the π-conjugated conductive polymer, in the polyanion, some anionic groups do not dope the π-conjugated conductive polymer and dope it. It has a surplus anionic group that is not involved. Since this excess anion group is a hydrophilic group, the conductive complex has high water dispersibility and low organic solvent dispersibility in the state before modification as described later.
When the number of all anion groups contained in the polyanion is 100 mol%, the excess anion group is preferably 30 mol% or more and 90 mol% or less, and more preferably 45 mol% or more and 75 mol% or less.

<Modification of anion group>
The excess anion group (hereinafter, also referred to as "partial anion group") contained in the conductive composite and which does not participate in the doping of the anionic polymer and the polyanion is an epoxy compound, an amine compound and a quaternary. It may be modified by reaction with one or more selected from ammonium compounds.

When a part of the anion group of the polyanion reacts with the epoxy compound, it is considered that the following substituent (A) is formed. It is considered that a similar group is formed when the sulfonic acid group of the anionic polymer reacts with the epoxy compound.
When a part of the anion group of the polyanion reacts with the amine compound, it is considered that the following substituent (B) is formed. It is considered that a similar group is formed when the sulfonic acid group of the anionic polymer reacts with the amine compound.
When a part of the anion group of the polyanion reacts with the quaternary ammonium compound, it is considered that the following substituent (C) is formed. It is considered that a similar group is formed when the sulfonic acid group of the anionic polymer reacts with the amine compound.

(Substituent A)
It is presumed that the substituent (A) is a group represented by the following formula (A1) or a group represented by the following formula (A2).

[In the formula (A1), R ¹ , R ² , R ³ and R ⁴ are independently hydrogen atoms or arbitrary substituents. ]

[ ^In the formula (A2), m is an integer of ² or more, and a plurality of R5, a plurality of R6, a plurality of ^R7 , and a plurality of ^R8 are independently, each of which is a hydrogen atom or an arbitrary substituent. Yes, a plurality of R ^5s may be the same or different, a plurality of R ^6s may be the same or different, a plurality of R ^7s may be the same or different, and a plurality of R ^8s may be the same or different. You may. ]

In the formulas (A1) and (A2), the leftmost bond represents that the substituent (A) is substituted with the proton of the anion group. Examples of the anion group having a proton to be substituted include an anion group having an active proton bonded to an oxygen atom such as "-SO ₃ H".

In the formula (A1), as any substituent of R ¹ , R ² , R ³ , and R ⁴ , an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent may be used. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be possessed. R ¹ and R ³ may be bonded to form a ring which may have a substituent. For example, R ¹ and R ³ are the above-mentioned hydrocarbon groups, and a divalent hydrogen group excluding any one hydrogen atom of the monovalent hydrogen group of R ¹ and a monovalent carbon of R ³ are used. Examples thereof include a case where a divalent hydrocarbon group excluding any one hydrogen atom of a hydrogen group is bonded to each other by carbon atoms from which the hydrogen atom has been removed to form a ring.
In the formula (A2), as any substituent of R ⁵ , R ⁶ , R ⁷ and R ⁸ , an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a substituent which may have a substituent may be used. Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which may be possessed. R ⁵ and R ⁷ may be bonded to form a ring which may have a substituent. The example of forming a ring is the same as above.
In the present specification, "may have a substituent" means that the hydrogen atom (-H) is substituted with a monovalent group and the methylene group ( _-CH2- ) is substituted with a divalent group. Includes both cases of replacement.
The monovalent group as a substituent includes an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), and a trialkoxysilyl group. (Trimethoxysilyl group, etc.), etc. may be mentioned.
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 complex becomes sufficiently high. When m is not more than the upper limit value, it is possible to suppress that the hydrophobicity becomes too high or the conductivity decreases.

The epoxy compound is a compound having one or more epoxy groups in one molecule (epoxy group-containing compound). From the viewpoint of preventing aggregation or gelation, the epoxy compound is preferably a compound having one epoxy group in one molecule.
The epoxy compound that reacts with the conductive complex may be one kind or two or more kinds.

Examples of the monofunctional epoxy compound having one epoxy group in one molecule include ethylene oxide, propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, and 1 , 2-Epoxy Heptane, 1,2-Epoxy Pentan, 1,2-Epoxy Octane, 1,2-Epoxy Decane, 1,3-butadiene Monooxide, 1,2-Epoxy Tetradecane, Glycidyl Methyl Ether, 1,2- Epoxy octadecane, 1,2-epoxy hexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxy eikosan, 2- (chloromethyl) -1,2-epoxy propane, 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, glycidylmethacrylate, 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-epoxytetralate, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxynorbornene, Benzyl glycidyl ether, diethoxy (3-glycidyloxypropyl) methylsilane, 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane, 1,1,1,3,5,5,5-heptamethyl- 3- (3-glycidyloxypropyl) trisiloxane, 9,10-epoxy-1,5-cyclododecadien, 4-tert-butyl glycidyl benzoate, 2,2-bis (4-glycidyloxyphenyl) propane, 2 -Tert-Butyl-2- [2- (4-chlorophenyl) )] Ethyloxylane, styrene oxide, glycidyltrityl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α, 6α-epoxide, stillbenoxide, glycidyl p-toluenesulfonate , 3-Methyl-3-phenylglycidate ethyl, N-propyl-N- (2,3-epoxypropyl) perfluoro-n-octylsulfonamide, (2S, 3S) -1,2-epoxy-3-( tert-Butoxycarbonylamino) -4-phenylbutane, 3-nitrobenzene sulfonic acid (R) -glycidyl, 3-nitrobenzene sulfonic acid-glycidyl, parthenolide, N-glycidyl phthalimide, endolin, dyrdoline, 4-glycidyl oxycarbazole, 7, Examples thereof include 7-dimethyloctanoic acid [oxylanylmethyl], 1,2-epoxide-4-vinylcyclohexane, and higher alcohol glycidyl ethers having 10 to 16 carbon atoms.

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

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, and 4-butanediol. Diglycidyl ether, 1,2: 3,4-diepoxybutane, 1,2-cyclohexanedicarboxylate diglycidyl, triglycidyl isocyanurate, neopentylglycol 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, Trimethylol Propane Triglycidyl Ether, Trimethylol Propane Polyglycidyl Ether, Hydrogenated Bisphenol A Diglycidyl Ether, Hexahydrophthalic Acid Diglycidyl Ether, Glycerin Polyglycidyl Ether, Diglycerin Polyglycidyl Ether, Polyglycerin Polyglycidyl Ether, Solbitol Poly Examples thereof include glycidyl ether and ethylene oxide lauryl alcohol glycidyl ether.

The epoxy compound preferably has a molecular weight of 50 or more and 2000 or less because it has high dispersibility in an organic solvent. Further, since the dispersibility in a low-polarity hydrocarbon solvent and an ester solvent is high, the epoxy compound preferably has 4 or more and 120 or less carbon atoms, and more preferably 7 or more and 100 or less. Those of 80 or more and 80 or less are more preferable, and those of 15 or more and 50 or less are particularly preferable.

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

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

In the substituent (B), the leftmost bond indicates that the negative charge of the anionic group and the positive charge of the amine compound are bonded. Examples of the anion group that can be negatively charged include an anion group in which an active proton is bonded to an oxygen atom ^, such as "-SO _3- ".

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

The amine compound is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. The amine compound that reacts with the conductive complex 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.
Of the amine compounds, tertiary amines are preferable, and at least one of trioctylamine and tributylamine is more preferable, because the conductivity of the conductive complex of this embodiment can be enhanced.

The amine compound may have a substituent having 4 or more carbon atoms on the nitrogen atom because the dispersibility in the organic solvent, particularly the dispersibility in the low-polarity hydrocarbon solvent and the ester solvent is high. It is more preferable to have a substituent of 6 or more, and further preferably to have a substituent having 8 or more carbon atoms on the nitrogen atom. The upper limit of the number of carbon atoms of the substituent on the nitrogen atom is not particularly limited, and for example, 50 or less is preferable, 40 or less is more preferable, and 30 or less is further preferable in consideration of solubility in a solvent and reactivity. ..

When the conductive composite has a substituent (A) and a substituent (B), the mass ratio represented by [substituent (A)]: [substituent (B)] (hereinafter, A / B ratio). Also referred to as), 10:90 to 90:10 is preferable, 20:80 to 80:20 is more preferable, and 25:75 to 75:25 is even more preferable. When the A / B ratio is within the above range, it becomes easy to balance dispersibility and conductivity. The mass of [substituent (A)] is [(mass of reactant A obtained by reacting epoxy compound with conductive composite)-(mass of conductive composite before reacting with epoxy compound). )] Can be calculated. Further, the mass of [substituent (B)] can be calculated from [(mass of reactant B obtained by reacting the reactant A with the amine compound)-(mass of the reactant A)]. can.

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

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

In the substituent (C), the leftmost bond indicates that the negative charge of the anion group and the positive charge of the quaternary ammonium cation are bonded. Examples of the anion group that can be negatively charged include an anion group in which an active proton is bonded to an oxygen atom ^, such as "-SO _3- ".

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

The quaternary ammonium compound preferably has a substituent having 4 or more carbon atoms on the nitrogen atom, more preferably 6 or more, and more preferably nitrogen, because the dispersibility in the organic solvent is high. It is more preferable to have a substituent having 8 or more carbon atoms on the atom. The upper limit of the number of carbon atoms of the substituent on the nitrogen atom is not particularly limited, and for example, 50 or less is preferable, 40 or less is more preferable, and 30 or less is further preferable in consideration of solubility in a solvent and reactivity. ..
The total carbon number of R ¹¹ to R ¹⁴ contained in the quaternary ammonium compound 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.

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

When the conductive composite has a substituent (A) and a 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 easy to balance dispersibility and conductivity. The mass of [substituent (A)] is [(mass of reactant A obtained by reacting epoxy compound with conductive composite)-(mass of conductive composite before reacting with epoxy compound). )] Can be calculated. Further, the mass of [substituent (C)] is calculated from [(mass of reactant C obtained by reacting the reactant A with the quaternary ammonium compound)-(mass of the reactant A)]. can do.

<Dispersion medium>
The dispersion medium contained in the conductive polymer dispersion liquid of this embodiment is a liquid agent that disperses or dissolves the above-mentioned conductive composite. In the present specification, it may be simply referred to as dispersion without distinguishing between dispersion and dissolution, and may be simply referred to as a dispersion medium without distinguishing between a dispersion medium and a solvent. Therefore, the dispersion medium may be paraphrased as a solvent.

The dispersion medium contains at least one of water and an organic solvent.
Since the π-conjugated conductive polymer contained in the conductive polymer dispersion liquid of this embodiment forms a conductive composite bonded to the anionic polymer and the polyanion, it tends to exhibit water dispersibility. This conductive complex may be hydrophobized by modification of the substituents (A) to (C) as described above. When hydrophobized, it is preferable to use an organic solvent as the dispersion medium. When it is not hydrophobized, it is preferable to use an aqueous dispersion medium as the dispersion medium.

(Aqueous dispersion medium)
The aqueous dispersion medium is water or a mixed solution of water and a water-soluble organic solvent. Here, the water-soluble organic solvent is an organic solvent having a dissolution amount of 1 g or more in 100 g of water at 20 ° C. Examples of the water-soluble organic solvent include alcohol-based solvents, ketone-based solvents, and ester-based solvents. One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination.
The content of water with respect to the total mass of the aqueous dispersion medium is 50% by mass or more, preferably 60% by mass or more, more preferably 80% by mass or more, and may be 100% by mass.

(Organic solvent)
The organic solvent in this embodiment may be a water-soluble organic solvent, a water-insoluble organic solvent, or a mixed solvent of a water-soluble organic solvent and a water-insoluble organic solvent. Here, the water-soluble organic solvent is an organic solvent having a dissolution amount of 1 g or more in 100 g of water at 20 ° C., and the water-insoluble organic solvent is an organic solvent having a dissolution amount of less than 1 g in 100 g of water at 20 ° C.

Examples of the water-soluble organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, nitrogen atom-containing solvents, ester-based solvents and the like.
Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and allyl alcohol. Examples thereof include ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether.
Examples of the ether solvent include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, diethylene glycol diethyl ether and the like.
Examples of the ketone solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
Examples of the nitrogen atom-containing solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.
One type of water-soluble organic solvent may be used alone, or two or more types may be used in combination.
As the water-soluble organic solvent, an alcohol-based solvent, a ketone-based solvent, or an ester-based solvent is preferable because the coating property of the conductive polymer dispersion liquid on the film substrate is improved.

Examples of the water-insoluble organic solvent include hydrocarbon solvents and the like. Examples of the hydrocarbon solvent include an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent.
Examples of the aliphatic hydrocarbon solvent include hexane, cyclohexane, pentane, heptane, octane, nonane, decane, dodecane and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
One kind of water-insoluble organic solvent may be used alone, or two or more kinds may be used in combination.

When the anionic polymer and the polyanion have any of the substituents (A) to (C) and are hydrophobic, the content of the organic solvent with respect to the total mass of the dispersion medium of the conductive polymer dispersion. Is preferably more than 50% by mass, more preferably 70% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 99.9% by mass or less. When the content ratio of the organic solvent is in the above range, the hydrophobized conductive complex can be easily dispersed, and the conductive layer can be easily formed.

(Ester solvent)
The ester solvent is an ester group-containing compound having an ester group (-C (= O) -O-).
When the conductive polymer dispersion liquid of this embodiment contains an ester solvent, it contains one or more ester group-containing compounds represented by the following formula 1z from the viewpoint of enhancing the dispersibility of the π-conjugated conductive polymer. Is preferable.
Equation 1z: R ²¹ -C (= O) -OR ²²
[In the formula, R ²¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ²² represents a linear or branched alkyl group having 1 to 6 carbon atoms. ]

From the viewpoint of enhancing the dispersibility of the π-conjugated conductive polymer of this embodiment, R ²¹ is preferably a methyl group or an ethyl group, and more preferably a methyl group. Further, the carbon number of R ²² is preferably 2 to 5, more preferably 2 to 4.

Preferable specific examples of the ester solvent include, for example, ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate and the like.

The content of the ester-based solvent contained in the conductive polymer dispersion liquid of this embodiment is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more, based on the total mass of the dispersion medium. It is preferable that 70% by mass or more is more preferable, 80% by mass or more is particularly preferable, 90% by mass or more is most preferable, and 100% by mass may be used. When the content of the ester solvent is within the above range, the dispersibility of the conductive complex can be enhanced.

When the conductive polymer dispersion liquid of this embodiment contains an ester solvent, one or more organic solvents other than the ester solvent may be further contained.

When the conductive polymer dispersion liquid of this embodiment contains an ester solvent, the anionic polymer and the polyanion are the substituent (A) and the above from the viewpoint of enhancing the dispersibility of the π-conjugated conductive polymer. It is preferable to have a substituent (B), or the substituent (A) and the substituent (C).

Since the conductive polymer dispersion liquid of this embodiment contains an anionic polymer, the pH tends to be acidic. Specifically, the pH tends to be 3 or less, and the pH tends to be 2 or less.

When the dispersion medium of the conductive polymer dispersion liquid of this embodiment is an aqueous dispersion medium, the particle size of the conductive composite in the aqueous dispersion medium at 25 ° C. is the conductive composite with respect to the total mass of the conductive polymer dispersion liquid. When the concentration of the above is adjusted to 0.1 to 0.2% by mass, it is preferably 200 nm or less, more preferably 10 nm or more and 100 nm or less, further preferably 15 nm or more and 85 nm or less, and particularly preferably 20 nm or more and 70 nm or less. Within these suitable ranges, the dispersion stability of the conductive complex is further improved.
The above particle size is obtained as a value obtained by measuring the average cumulant particle size by a dynamic light scattering method.

When the dispersion medium of the conductive polymer dispersion liquid of this embodiment is an organic dispersion medium containing more than 50% by mass of an organic solvent, the particle size of the conductive composite in the organic dispersion medium at 25 ° C. is the above-mentioned conductive polymer. When the concentration of the conductive composite with respect to the total mass of the dispersion is adjusted to 0.01 to 0.1% by mass, 250 nm or less is preferable, 50 nm or more and 200 nm or less is more preferable, 70 nm or more and 170 nm or less is further preferable, and 90 nm or more. 140 nm or less is particularly preferable. Within these suitable ranges, the dispersion stability of the conductive complex is further improved.
The above particle size is obtained as a value obtained by measuring the average cumulant particle size by a dynamic light scattering method.

<Binder component>
The conductive polymer dispersion liquid of this embodiment may contain one or more binder components. The binder component is a resin other than the anionic polymer, the π-conjugated conductive polymer and the polyanion, or a precursor thereof, and is a thermoplastic resin or a curable monomer or oligomer that cures when the conductive layer is formed. be. The thermoplastic resin becomes a binder resin as it is, and the curable monomer or oligomer is a binder resin formed by curing.

Specific examples of the binder resin derived from the binder component include epoxy resin, acrylic resin (acrylic compound), polyester resin, polyurethane resin, polyimide resin, polyether resin, melamine resin, silicone and the like.
When the dispersion medium of the conductive polymer dispersion liquid of this embodiment is an aqueous dispersion medium, the binder resin contained is preferably a water-dispersible emulsion resin or a water-soluble resin, and more preferably a water-dispersible emulsion resin.

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

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

The acid group such as the carboxy group and the sulfo group of the water-dispersible resin may form a salt with a cation such as a sodium ion or a potassium ion.

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

When a curable monomer or oligomer is contained, it is preferable to further contain a curing catalyst. For example, when a thermocurable monomer or oligomer is contained, it is preferable to contain a thermal polymerization initiator that generates a radical by heating, and when a photocurable monomer or oligomer is contained, a radical is generated by light irradiation. It is preferable to include a photopolymerization initiator to cause the reaction.

The content ratio of the binder component (however, excluding the silicone compound described later) contained in the conductive polymer dispersion liquid of this embodiment is, for example, 1 part by mass or more and 10,000 parts by mass with respect to 1 part by mass of the conductive composite. It is preferably 10 parts by mass or more, more preferably 5000 parts by mass or less, and further preferably 100 parts by mass or more and 1000 parts by mass or less.
When it is at least the lower limit of the above range, the characteristics of the binder component contained in the conductive layer formed by the conductive polymer dispersion liquid of this embodiment can be fully exhibited.
When it is not more than the upper limit of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer dispersion liquid of this embodiment can be ensured.

(Silicone compound)
When the conductive polymer dispersion liquid of this embodiment contains an organic solvent as a dispersion medium, preferably a water-insoluble organic solvent, a low-polarity silicone compound is added as a binder component to sufficiently disperse the liquid. be able to. When the organic solvent contains a hydrocarbon solvent or an ester solvent, the dispersibility of the silicone compound is further enhanced, which is preferable.
Examples of the silicone compound include curable silicone. When the binder component is a curable silicone, the conductive layer can be imparted with releasability by curing the curable silicone.

The curable silicone may be either an addition curable silicone or a condensation curable silicone. In this embodiment, even if addition-curable silicone is used, curing inhibition is unlikely to occur, which is preferable.

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

The content ratio of the silicone compound contained in the conductive polymer dispersion liquid of this embodiment is preferably 10 parts by mass or more and 10,000 parts by mass or less, and 100 parts by mass or more and 5000 parts by mass or less with respect to 100 parts by mass of the conductive composite. Is more preferable, and more preferably 500 parts by mass or more and 3000 parts by mass or less.
When it is at least the lower limit of the above range, sufficient releasability can be imparted to the conductive layer formed by the conductive polymer dispersion liquid of this embodiment.
When it is not more than the upper limit of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer dispersion liquid of this embodiment can be ensured.

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

The degree of adhesiveness of the pressure-sensitive adhesive of this embodiment is not particularly limited, and the adhesiveness may be such that it can be easily peeled off by hand after being applied, or it may be difficult to be peeled off after being applied. It may be sticky. Adhesiveness that is difficult to peel off can be rephrased as adhesiveness. That is, the adhesiveness may be such that it can be adhered semi-permanently.

As the pressure-sensitive adhesive, a known pressure-sensitive adhesive can be applied. Acrylic adhesives are preferable from the viewpoint of exhibiting good adhesiveness while maintaining conductivity.

(Acrylic adhesive)
The acrylic pressure-sensitive adhesive can be integrated by laminating the faces of the same or different kinds of solids. The acrylic pressure-sensitive adhesive contains an acrylic resin (acrylic polymer).

Specific examples of the acrylic monomer forming the acrylic resin include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, and ditri. Methylolpropantetraacrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A / ethylene oxide modified diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, dipropylene glycol diacrylate, Trimethylol propanetriacrylate, glycerin propoxytriacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, pentaerythritol Acrylate such as triacrylate, tetrahydrofurfuryl acrylate, tripropylene glycol diacrylate; tetraethylene glycol dimethacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate. , Benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate. , Trimethylol propanetrimethacrylate and the like; diacetone acrylamide, N, N-dimethylacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylate, methacrylicamide, N-methylolacrylamide, acryloylformorin, N-methylacrylamide, N -Isopropylacrylamide, Nt-butylacrylamide, N-phenylacrylamide, acryloylpiperidin, 2-hydroxye Examples thereof include (meth) acrylamide such as chill acrylamide.
The acrylic monomer forming the acrylic resin may be one kind or two or more kinds. The adhesiveness can be adjusted by combining two or more kinds of acrylic monomers.

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

The glass transition temperature of the acrylic resin is preferably 80 ° C. or lower, more preferably 50 ° C. or lower, still more preferably 0 ° C. or lower. Acrylic resins having a glass transition temperature of more than 80 ° C. have low adhesiveness. The glass transition temperature of the acrylic resin is −80 ° C. or higher, and it is difficult to obtain a resin having a glass transition temperature lower than that. The glass transition temperature of the acrylic resin can be determined by differential scanning calorimetry or dynamic viscoelasticity measurement.
Examples of the acrylic monomer having a tendency to lower the glass transition temperature of the acrylic resin include ethyl acrylate, butyl acrylate (particularly 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.

The mass average molecular weight of the acrylic resin is preferably 10,000 or more and 2 million or less, and more preferably 30,000 or more and 1 million or less. When the mass average molecular weight of the acrylic resin is at least the above lower limit value, sufficient cohesive force can be secured. If it is not more than the upper limit value, the adhesiveness can be further improved.

When the acrylic resin has an acrylic monomer unit having a reactive functional group, it may be cured by reacting with a curing agent. When the acrylic resin is cured, the cohesive force of the conductive layer containing the adhesive can be improved and the strength can be improved. Further, by improving the cohesive force of the conductive layer, it is possible to obtain a removable conductive layer capable of repeating adhesion and peeling.
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 and 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-methylolacrylamide, N-methylolmethacrylamide and the like.
Examples of the acrylic monomer having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
When a polyfunctional isocyanate is used as a curing agent, among the acrylic monomers having a reactive functional group, an acrylic monomer having a hydroxy group is preferable in consideration of curability and cost, 2-hydroxyethyl acrylate, 2-. Hydroxyethyl methacrylate is more preferred.
The acrylic monomer having the reactive functional group forming the acrylic resin may be one kind or two or more kinds.

The content ratio of the pressure-sensitive adhesive contained in the conductive polymer dispersion liquid of this embodiment is preferably 10 parts by mass or more and 10,000 parts by mass or less, and 100 parts by mass or more and 5000 parts by mass or less with respect to 1 part by mass of the conductive composite. More preferably, it is more preferably 300 parts by mass or more and 1000 parts by mass or less.
When it is at least the lower limit of the above range, sufficient adhesiveness can be imparted to the conductive layer formed by the conductive polymer dispersion liquid of this embodiment.
When it is not more than the upper limit of the above range, sufficient conductivity of the conductive layer formed by the conductive polymer dispersion liquid of this embodiment can be ensured.

(Hardener)
When the pressure-sensitive adhesive contained in the conductive polymer dispersion liquid of this embodiment has a reactive functional group, it is preferable that the conductive polymer dispersion liquid of this embodiment contains a curing agent.
Examples of the curing agent include isocyanate-based curing agents such as polyfunctional isocyanate 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 isocyanate is preferable from the viewpoint of reactivity. In particular, when the pressure-sensitive adhesive has an acrylic monomer unit having a hydroxy group, it is preferable that the curing agent is a polyfunctional isocyanate.

Examples of the polyfunctional isocyanate include an aliphatic polyfunctional isocyanate, an alicyclic polyfunctional isocyanate and an aromatic polyfunctional isocyanate.
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, and polyphenylene. Polymethylene polyisethylene, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, p-phenylenediisocyanate, transcyclohexane1,4-diisocyanate, 4,4'-dicyclomethanediisocyanis, 3,3 ′ -Dimethyl-4,4'-diphenylmethane diisocyanate, dianisidine diisocyanate, m-xylylene diisocyanate, isophoron diisocyanate, 1,5-naphthalenediisocyanis, 1,4-cyclohexanediisocyanis, lysine diisocyanate, lysine ester triisocyanate, tetramethyl Examples thereof include xylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptatriisocyanate, and trimethylhexamethylene diisocyanate.
The polyfunctional isocyanate may be a modified diisocyanate formed from the 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. The modified polyisocyanate includes, for example, a polyurethane polyisocyanate obtained by reacting the polyfunctional isocyanate with a polyvalent alcohol, a polyisocyanate containing an isocyanurate ring obtained by polymerizing the polyfunctional isocyanate, and a polyfunctional isocyanate. Examples thereof include polyisocyanates containing a bullet bond, which are obtained by reacting with water.
The type of the curing agent contained in the conductive polymer dispersion liquid of this embodiment may be one type or two or more types.

The content ratio of the curing agent contained in the conductive polymer dispersion liquid of this embodiment is preferably 1 part by mass or more and 100 parts by mass or less, and 2 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pressure-sensitive adhesive. Is more preferable, and 3 parts by mass or more and 10 parts by mass or less are further preferable.
Within the above range, sufficient adhesiveness can be imparted to the conductive layer formed by the conductive polymer dispersion liquid of this embodiment.

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

(Other additives)
The conductive polymer dispersion liquid of this embodiment may contain other known additives.
The additive is not particularly limited as long as the effect of the present invention can be obtained, and for example, a surfactant, an inorganic conductive agent, a defoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber and the like can be used.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferable from the viewpoint of storage stability. Further, a polymer-based surfactant such as polyvinylpyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving the metal salt in water.
Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and the like.
Examples of the coupling agent include a silane coupling agent having a vinyl group or an amino group.
Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, saccharides and the like.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, hindered amine-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, etc. Can be mentioned.
When the conductive polymer dispersion liquid of this embodiment contains the above additive, the content ratio thereof is appropriately determined depending on the type of the additive, and is, for example, 0 with respect to 100 parts by mass of the conductive composite. The range may be 001 parts by mass or more and 5 parts by mass or less.

≪Manufacturing method of anionic polymer≫
The anionic polymer can be obtained by polymerizing compound 1 in a reaction solution containing compound 1 and an aqueous dispersion medium. As a method for polymerizing compound 1, a known method for polymerizing a vinyl compound can be applied. For example, a radical polymerization method using an oxidizing agent or a catalyst described later can be mentioned.
The compound 1 contained in the reaction solution may be a salt containing a sodium ion or an ammonium ion as a counter cation of a sulfonic acid group.

As the dispersion medium contained in the reaction solution, the aqueous dispersion medium is preferable, and water is more preferable.
When the dispersion medium contains water, the polymerization reaction of the compound 1 proceeds stably, and it is easy to obtain an anionic polymer in a state of being stably dispersed in the dispersion medium.
It is preferable to remove the counter cation bonded to the sulfonic acid group of the compound 1 polymerized in the reaction solution, and the catalyst and oxidizing agent added to the reaction solution from the reaction solution after the polymerization of the compound 1. Removing the counter cation means removing the counter cation bonded to the sulfonic acid group of the anionic polymer obtained by the polymerization and replacing it with a proton.

Examples of the method for removing the counter cation and the like from the reaction solution include a method of bringing the reaction solution into contact with the ion exchange resin and adsorbing the reaction solution to the ion exchange resin, and ultrafiltration of the reaction solution while adding ion exchange water. Examples thereof include a method of treating and removing the dispersion medium together with the replacement. Of these, the method using an ion exchange resin is preferable because it is simple. As the ion exchange resin, it is preferable to use a cation exchange resin and an anion exchange resin in combination.

<< Manufacturing method of conductive polymer dispersion >>
<Synthesis of π-conjugated conductive polymer in the presence of anionic polymer>
The second aspect of the present invention is a monomer compound that forms a π-conjugated conductive polymer by polymerization, an anionic polymer having a monomer unit derived from the compound 1 represented by the above formula (1), and an aqueous dispersion. By polymerizing the monomer compound in a reaction solution containing the medium, the conductive composite containing the π-conjugated conductive polymer and the anionic polymer and the aqueous dispersion medium are contained. This is a method for producing a conductive polymer dispersion to obtain a conductive polymer dispersion.
By the production method of this aspect, the conductive polymer dispersion liquid of the first aspect can be produced.

The synthesis of the π-conjugated conductive polymer in the reaction solution can be carried out in the same manner as the synthesis of the conventional π-conjugated conductive polymer except that the reaction solution contains the anionic polymer. ..

As the dispersion medium contained in the reaction solution, the aqueous dispersion medium is preferable, and water is more preferable.
When the dispersion medium contains water, the polymerization reaction of the monomer proceeds stably, and the π-conjugated conductive polymer forms a conductive composite bonded to the anionic polymer and is stable in the dispersion medium. It is easy to obtain in a dispersed state.

The monomers can be polymerized with each other by chemically oxidizing the monomers. Chemical oxidative polymerization can be carried out using known catalysts and oxidizing agents. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate and ferric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidant can restore the reduced catalyst to its original oxidized state.

The content of the anionic polymer with respect to the total mass of the reaction solution is, for example, preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less, and more preferably 0.75% by mass. % Or more and 2% by mass or less are more preferable.
When it is in the above-mentioned suitable range, it becomes easy to adjust the content ratio of the π-conjugated conductive polymer and the anionic polymer in the above-mentioned suitable range in the target conductive polymer dispersion liquid.

The content of the monomer with respect to the total mass of the reaction solution immediately before the start of the polymerization reaction is, for example, preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 5% by mass or less, and 0. It is more preferably 3% by mass or more and 2% by mass or less.

In the reaction solution, from the viewpoint of binding the anionic polymer to the π-conjugated conductive polymer to form a conductive composite having excellent water dispersibility, the anionic property contained in the reaction solution immediately before the start of the polymerization reaction. The content ratio of the polymer is preferably 50 parts by mass or more and 5000 parts by mass or less, more preferably 100 parts by mass or more and 1000 parts by mass or less, and further preferably 150 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the monomer. ..

By synthesizing a π-conjugated conductive polymer by chemical oxidative polymerization of the monomer, the conductive polymer dispersion liquid of the first aspect of interest can be obtained.

It is preferable to remove the catalyst and the oxidizing agent added to the reaction solution from the conductive polymer dispersion after the chemical oxidative polymerization of the monomer.
Examples of the method for removing the dispersion medium include a method in which the conductive polymer dispersion is brought into contact with the ion exchange resin and the catalyst and the oxidizing agent are adsorbed on the ion exchange resin, and a method in which the conductive polymer dispersion is ultrafiltered. Examples thereof include a method of removing with replacement of. Of these, the method using an ion exchange resin is preferable because it is simple. As the ion exchange resin, it is preferable to use a cation exchange resin and an anion exchange resin in combination.

When manufactured by the method of the second aspect of the present invention, since the anionic polymer is present at the time of chemical oxidation polymerization of the π-conjugated conductive polymer, the anionic polymer is bonded or doped with the π-conjugated conductive polymer. Therefore, a conductive composite having a small water-dispersible particle size can be obtained.

<Addition of polyanion>
In the production method of this embodiment, the monomer may be polymerized after further adding the polyanion (polyanion having no monomer unit derived from compound 1) to the reaction solution before polymerization. By polymerizing the π-conjugated conductive polymer in the presence of the anionic polymer and the polyanion, at least one of the anionic polymer and the polyanion is bonded or doped with the π-conjugated conductive polymer. Complexes can be formed.

The content of the polyanion with respect to the total mass of the reaction solution immediately before the start of the polymerization reaction is, for example, preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less, and 0. It is more preferably 75% by mass or more and 2% by mass or less.
By setting the above-mentioned preferable range, it is possible to suppress an increase in the particle size of the π-conjugated conductive polymer, and the conductivity of the conductive layer formed by using the conductive polymer dispersion liquid of this embodiment is further improved. Can be enhanced.

In the reaction solution, the polyanion is bound to the π-conjugated conductive polymer to form a conductive complex having excellent water dispersibility and conductivity, and the reaction solution is contained in the reaction solution immediately before the start of the polymerization reaction. The content ratio of the polyanion is preferably 50 parts by mass or more and 5000 parts by mass or less, more preferably 100 parts by mass or more and 1000 parts by mass or less, and further in the range of 150 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the monomer. preferable.

A binder component or other additives may be further added to the conductive polymer dispersion obtained as described above. It is preferable to apply the suitable range described in the first aspect to the type and content of the binder component and the additive.

<Precipitation recovery process>
A reaction containing the conductive complex by adding one or more selected from an epoxy compound, an amine compound and a quaternary ammonium compound to the conductive polymer dispersion liquid containing the aqueous dispersion medium obtained above. The product may be precipitated, the precipitated reaction product may be recovered and a solvent may be added to obtain a conductive polymer dispersion. The method for recovering the precipitate is not particularly limited, and examples thereof include filtration.
The above-mentioned added compound reacts with the anion group of the conductive complex obtained in this step to form any of the above-mentioned substituents (A) to (C) and make it hydrophobic.

When one or more of the epoxy compounds are added to the conductive polymer dispersion, the epoxy groups of the epoxy compound react with the anionic polymer and / or some of the anionic groups of the polyanion. As a result, the substituent (A) is formed and the conductive complex becomes hydrophobic, which makes it difficult to stably disperse in the aqueous dispersion, and precipitates to form a precipitate.
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.
The amount of the epoxy compound added 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 5000 parts by mass or less, and 500 parts by mass or more and 3000 parts by mass or less with respect to 100 parts by mass of the conductive composite. Is even more preferable.
When it is at least the lower limit of the above range, the hydrophobicity of the conductive composite becomes sufficiently high, and the dispersibility in an organic solvent, particularly a hydrocarbon solvent and an ester solvent is improved.
When it is not more than the upper limit of the above range, the decrease in conductivity due to the unreacted epoxy compound can be prevented.

An organic solvent may be added before, at the same time as, or after the addition of one or more selected from the epoxy compound, the amine compound and the quaternary ammonium compound to the conductive polymer dispersion liquid. As the organic solvent, a water-soluble organic solvent is preferable. Here, the water-soluble organic solvent is an organic solvent having a dissolution amount of 1 g or more with respect to 100 g of water at a temperature of 20 ° C. Examples of the water-soluble organic solvent include alcohol-based solvents, ketone-based solvents, and ester-based solvents. The organic solvent to be added may be one kind or two or more kinds.

When one or more amine compounds are added to the conductive polymer dispersion, the amine compound reacts with the anionic polymer and / or some anionic groups of the polyanion. As a result, the substituent (B) is formed and the conductive complex becomes hydrophobic, which makes it difficult to stably disperse in the aqueous dispersion, and precipitates to form a precipitate.
The amount of the amine compound added is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, and 100 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the conductive complex. More preferred.
When it is at least the lower limit of the above range, the hydrophobicity of the conductive composite becomes sufficiently high, and the dispersibility in an organic solvent, particularly a hydrocarbon solvent and an ester solvent is improved.
When it is not more than the upper limit of the above range, the decrease in conductivity due to the unreacted amine compound can be prevented.

When one or more of the quaternary ammonium compounds are added to the conductive polymer aqueous dispersion, the quaternary ammonium compounds react with the anionic polymer and / or some anionic groups of the polyanion. Since the substituent (C) is formed and the conductive complex becomes hydrophobic, stable dispersion in the aqueous dispersion becomes difficult, and the precipitate becomes a precipitate.
The amount of the quaternary ammonium compound added is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less, and 50 parts by mass or more and 1000 parts by mass with respect to 100 parts by mass of the conductive composite. Less than a portion is more preferable.
When it is at least the lower limit of the above range, the hydrophobicity of the conductive complex becomes sufficiently high, and the dispersibility in an organic solvent is improved.
When it is not more than the upper limit of the above range, the decrease in conductivity due to the unreacted quaternary ammonium compound can be prevented.
The quaternary ammonium compound has a reaction mechanism similar to that of the amine compound, and exhibits good reactivity with the conductive complex with a smaller addition amount than the amine compound. The conductivity of the conductive layer containing the conductive complex modified with the quaternary ammonium compound tends to be better than when modified with the amine compound.

When both the epoxy compound and the amine compound or the quaternary ammonium compound are added to the conductive polymer dispersion, the order of addition is not particularly limited. Since the synthetic intermediate (reaction intermediate) is easy to handle, an epoxy compound is first added and reacted with some anionic groups of the polyanion, and then an amine compound or a quaternary ammonium compound is added. It is preferable to react with an anionic group in another part of the polyanion.

The water content of the precipitate obtained in this step is preferably as small as possible, and most preferably it does not contain water at all, but from a practical point of view, the water content may be contained in the range of 10% by mass or less.
Examples of the method for reducing the water content include a method of washing away the precipitate separated from the solvent in a solid state such as powder with an organic solvent, a method of drying the precipitate, and the like.

<Washing>
The reaction product (precipitate) recovered in this step may be washed with an organic solvent for washing. This washing removes residual water, unreacted epoxy compounds, unreacted amine compounds, unreacted quaternary ammonium compounds, reactants of epoxy and amine compounds, and hydrolysates of epoxy compounds. be able to.
As the cleaning organic solvent, a solvent that can be washed without dissolving the precipitate is preferably used. The organic solvent for cleaning may be one kind or two or more kinds.
The cleaning method is not particularly limited. For example, the organic solvent for cleaning may be poured over the precipitate to clean the precipitate, or the precipitate may be stirred in the organic solvent for cleaning to clean the precipitate. You may.

<Addition of solvent>
A solvent is added to the obtained reaction product to obtain a conductive polymer dispersion. The solvent to be added may be an aqueous dispersion medium or an organic solvent as long as it can disperse the reaction product. When the reaction product is highly hydrophobic, it is preferable to use an organic solvent.
As the organic solvent, the organic solvent contained in the conductive polymer dispersion liquid of the first aspect can be applied. Among them, one or more selected from an alcohol solvent, a ketone solvent, and an ester solvent are preferable, and one or more selected from isopropanol, methyl ethylton, and ethyl acetate are more preferable. By using these suitable organic solvents, the dispersibility of the conductive complex contained in the conductive polymer dispersion can be further enhanced.
The content of each solvent contained in the organic solvent is preferably in the preferable range exemplified in the first aspect.

After adding the solvent to the reaction product, the conductive polymer dispersion may be stirred to perform the dispersion treatment. The stirring method is not particularly limited, and stirring may be performed with a weak shearing force such as a stirrer, or may be stirred using a disperser (homogenizer or the like) having a high shearing force.

A binder component or other additives may be further added to the conductive polymer dispersion obtained as described above. It is preferable to apply the suitable range described in the first aspect to the type and content of the binder component and the additive.

≪Conductive laminate≫
A third aspect of the present invention is a conductive laminate comprising a base material and a conductive layer formed on at least one surface of the base material. The conductive layer is made of a cured product of the conductive polymer dispersion liquid of the first aspect.

[Conductive layer]
The average thickness of the conductive layer provided on at least one surface of the substrate is, for example, preferably 10 nm or more and 100 μm or less, more preferably 20 nm or more and 50 μm or less, and 30 nm or more and 30 μm or less. Is even more preferable.
When the average thickness of the conductive layer is at least the lower limit value, sufficiently high conductivity can be exhibited, and when it is at least the upper limit value, the adhesion of the conductive layer to the substrate is further improved.

The conductive layer included in the conductive laminate of this embodiment contains the conductive composite.
When the conductive polymer dispersion applied to the substrate contains a binder component, the conductive layer contains a binder component or a cured product of the binder component.

[Base material]
The base material constituting the conductive laminate of this embodiment may be a base material made of an insulating material or a base material made of a conductive material. The shape of the base material is not particularly limited, and examples thereof include a shape mainly composed of a flat surface such as a film or a substrate.
Examples of the insulating material include glass, synthetic resin, and ceramics.
Examples of the conductive material include metals, conductive metal oxides, carbon and the like.

(Film base material)
When a film base material is used as the base material, the conductive laminate becomes a conductive film.
Examples of the film base material include a plastic film made of a synthetic resin. Examples of the synthetic resin include ethylene-methylmethacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyacrylate. , Polycarbonate, polyvinylidene fluoride, polyarylate, styrene-based elastomer, polyester-based elastomer, polyether sulfone, polyetherimide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate and the like.
From the viewpoint of enhancing the adhesion between the film base material and the conductive layer, the synthetic resin for the film base material is preferably a resin of the same type as the binder resin, and among them, a polyester resin such as polyethylene terephthalate is preferable.

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

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. When the average thickness of the film substrate is at least the lower limit value, it is difficult to break, and when it is at least the upper limit value, sufficient flexibility as a film can be ensured.
The average thickness of the film substrate is a value obtained by measuring the thickness at 10 randomly selected points and averaging the measured values.

(Glass substrate)
Examples of the glass substrate include a non-alkali glass substrate, a soda-lime glass substrate, a borosilicate glass substrate, a quartz glass substrate and the like. When the base material contains an alkaline component, the conductivity of the conductive layer tends to decrease. Therefore, among the glass base materials, non-alkali glass is preferable. Here, the non-alkali glass is a glass composition in which the content of the alkaline component is 0.1% by mass or less with respect to the total mass of the glass composition.

The average thickness of the glass substrate is preferably 50 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 at least the lower limit value, it is less likely to be damaged, and if it is at least the upper limit value, it can contribute to thinning the conductive laminate.
The average thickness of the glass substrate is a value obtained by measuring the thickness at 10 randomly selected points and averaging the measured values.

<< Manufacturing method of conductive laminate >>
A fourth aspect of the present invention is a method for producing a conductive laminate, which comprises a step of applying the conductive polymer dispersion liquid of the first aspect to at least one surface of a base material. By the production method of this aspect, the conductive laminate of the third aspect can be produced.

As a method of applying (applying) the conductive polymer dispersion liquid to any surface of the substrate, for example, a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a knife coater, a fountain coater, etc. Methods using coaters such as rod coaters, air doctor coaters, knife coaters, blade coaters, cast coaters, screen coaters, methods using atomizers such as air spray, airless spray, rotor dampening, dipping methods such as dips, etc. Can be applied.

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

By drying a coating film made of a conductive polymer dispersion liquid coated on a substrate and removing the dispersion medium, a conductive layer (conductive film) formed by curing the coating film is formed. A laminate can be obtained.
Examples of the method for drying the coating film include heat drying and vacuum drying. As the heat drying, for example, a method such as hot air heating or infrared heating can be adopted.
When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium used, but is usually in the range of 50 ° C. or higher and 150 ° C. or lower. Here, the heating temperature is a set temperature of the drying device. The suitable drying time in the above heating temperature range is preferably 1 minute or more and 30 minutes or less, and more preferably 5 minutes or more and 15 minutes or less.

When the conductive polymer dispersion liquid contains an active energy ray-curable binder component, it may further have an active energy ray irradiation step of irradiating the dried coating film with the active energy ray. By having the active energy ray irradiation step, the formation speed of the conductive layer can be increased, and the productivity of the conductive film is improved.
When the active energy ray irradiation step is provided, examples of the active energy ray used include ultraviolet rays, electron beams, and visible light. As the light source of ultraviolet rays, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used.
The illuminance in ultraviolet irradiation is preferably 100 mW / cm ² or more. If the illuminance is less than 100 mW / cm ² , the active energy ray-curable binder component may not be sufficiently cured. The integrated light intensity is preferably 50 mJ / cm ² or more. If the integrated light intensity is less than 50 mJ / cm ² , the cross-linking may not be sufficient. The illuminance and integrated light amount in the present specification are determined by using Topcon UVR-T1 (industrial UV checker, receiver; UD-T36, measurement wavelength range; 300 nm or more and 390 nm or less, peak sensitivity wavelength; about 355 nm). It is a measured value.

(Manufacturing Example 1)
Aqualon KH-05 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., n = 8-11 of the above formula (1), R = linear alkyl group having 10 or 12 carbon atoms, ammonium salt), 90 g of ion-exchanged water, and 0.1 g of ammonium persulfate was added, and the reaction was carried out at 80 ° C. for 8 hours.
Next, 10 g of Duolite C255LFH (made by Sumika Chemtex Co., Ltd., cation exchange resin) was added and stirred for 16 hours. The obtained solution was filtered to remove Duolite C255LFH to obtain 100 g of a sulfonic acid compound (10% by mass aqueous solution) of the aquaron KH-05 polymer, which is an anionic polymer. The mass average molecular weight Mw of this polymer was 12000.

(Manufacturing Example 2)
Aqualon KH-05 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 10 g, Aquaron KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., n = 22 to 25 of the above formula (1), R = linear chain having 10 or 12 carbon atoms 100 g of a sulfonic acid compound (10% by mass aqueous solution) of the aqualon KH-10 polymer, which is an anionic polymer, was obtained in the same manner as in Production Example 1 except that the alkyl group (ammonium salt) was changed to 10 g. The mass average molecular weight Mw of this polymer was 15,000.

(Manufacturing Example 3)
Aqualon KH-05 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 10 g, Aquaron KH-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., n = 68 to 71, R = 10 or 12 carbon atoms in the above formula (1)) 100 g of a sulfonic acid compound (10% by mass aqueous solution) of the aqualon KH-1025 polymer, which is an anionic polymer, was obtained in the same manner as in Production Example 1 except that the alkyl group (ammonium salt) was changed to 10 g. The mass average molecular weight Mw of this polymer was 20000.

(Manufacturing Example 4)
Anion in the same manner as in Production Example 1 except that 10 g of Aqualon KH-05 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was changed to 5 g of Aquaron KH-05 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 5 g of sodium styrene sulfonate. 100 g of a copolymer (10 mass% aqueous solution) of a sulfonic acid compound of aqualon KH-05, which is a sex polymer, and a styrene sulfonic acid was obtained. The mass average molecular weight Mw of this polymer was 200,000.

(Production Example 5) Production of polystyrene sulfonic acid The weight of styrene sulfonic acid is the same as in Production Example 1 except that 10 g of Aqualon KH-05 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is changed to 10 g of sodium styrene sulfonate. 100 g of a coalescence (10 mass% aqueous solution) was obtained. The mass average molecular weight Mw of this polymer was 200,000.

(Example 1)
A reaction solution was obtained by mixing 0.5 g of 3,4-ethylenedioxythiophene, 15 g of a sulfonic acid compound (10 mass% aqueous solution) of the Aqualon KH-05 polymer of Production Example 1, and 84.5 g of ion-exchanged water. ..
The obtained reaction solution was kept at 20 ° C., and while stirring, 0.03 g of ferric sulfate was dissolved in 4.97 g of ion-exchanged water, and 1.1 g of ammonium persulfate was dissolved in 8.9 g of ion-exchanged water. The oxidant solution was slowly added, and the obtained reaction solution was stirred for 24 hours to react.
By the above reaction, a conductive composite containing a sulfonic acid compound of poly (3,4-ethylenedioxythiophene) which is a π-conjugated conductive polymer and an aqualon KH-05 polymer, water as a dispersion medium, and water A conductive polymer dispersion containing an oxidizing agent and a catalyst was obtained.
To this conductive polymer dispersion, add 13.2 g of Duolite C255LFH (made by Sumika Chemtex, cation exchange resin) and 13.2 g of Duolite A368S (manufactured by Sumika Chemtex, anion exchange resin), and filter. The ion exchange resin was removed to obtain a conductive polymer dispersion from which the oxidizing agent and the catalyst were removed. Table 1 shows the results of measuring the mass, pH and particle size of the solid content (nonvolatile component) of the obtained conductive polymer dispersion.
Next, the obtained conductive polymer dispersion was applied onto a PET film using a # 4 bar coater and dried at 120 ° C. for 1 minute to obtain a conductive film.

(Example 2)
A reaction solution was obtained by mixing 0.5 g of 3,4-ethylenedioxythiophene, 10 g of a sulfonic acid compound (10 mass% aqueous solution) of the Aqualon KH-05 polymer of Production Example 1, and 89.5 g of ion-exchanged water. .. Using this reaction solution, a conductive polymer dispersion was obtained in the same manner as in Example 1, and a conductive film was prepared and evaluated.

(Example 3)
A reaction solution was obtained by mixing 0.5 g of 3,4-ethylenedioxythiophene, 20 g of a sulfonic acid compound (10 mass% aqueous solution) of the Aqualon KH-05 polymer of Production Example 1, and 79.5 g of ion-exchanged water. .. Using this reaction solution, a conductive polymer dispersion was obtained in the same manner as in Example 1, and a conductive film was prepared and evaluated.

(Example 4)
Conductivity is the same as in Example 1 except that 15 g of the Aqualon KH-05 polymer of Production Example 1 is changed to 15 g of a sulfonic acid compound (10% by mass aqueous solution) of the Aqualon KH-10 polymer of Production Example 2. A polymer dispersion was obtained to prepare a conductive film.

(Example 5)
Conductivity is the same as in Example 1 except that 15 g of the Aqualon KH-05 polymer of Production Example 1 is changed to 15 g of a sulfonic acid compound (10 mass% aqueous solution) of the Aqualon KH-1025 polymer of Production Example 3. A polymer dispersion was obtained to prepare a conductive film.

(Example 6)
Example 1 except that 15 g of the Aqualon KH-05 polymer of Production Example 1 was changed to 15 g of a copolymer (10 mass% aqueous solution) of the sulfonic acid compound of Aqualon KH-05 of Production Example 4 and styrene sulfonic acid. In the same manner as above, a conductive polymer dispersion was obtained to prepare a conductive film.

(Example 7)
Example 1 except that 15 g of the Aqualon KH-05 polymer was changed to a mixed solution of 7.5 g of the Aqualon KH-05 polymer (10 mass% aqueous solution) and 7.5 g of polystyrene sulfonic acid (10 mass% aqueous solution). In the same manner as above, a conductive polymer dispersion was obtained to prepare a conductive film.

(Comparative Example 1)
An attempt was made to prepare a conductive polymer dispersion in the same manner as in Example 1 except that 15 g of the Aqualon KH-05 polymer was not added and the amount of ion-exchanged water added was changed from 84.5 g to 99.5 g. However, the study was discontinued because all the conductive polymers were precipitated.

(Comparative Example 2)
A conductive polymer dispersion was obtained in the same manner as in Example 1 except that 15 g of the Aqualon KH-05 polymer was changed to 15 g of polystyrene sulfonic acid (10% by mass aqueous solution) to prepare a conductive film.

[Measurement of surface resistance value]
For the conductive films produced in each example, the surface resistance value of the conductive layer was measured using a resistivity meter (High Restor manufactured by Nittoseiko Analytech Co., Ltd.) under the condition of an applied voltage of 10 V. In the table, "1.0E + ⁰⁷ " means "1.0 × 107", and the same applies to the others.

[Measurement of pH]
The pH of the conductive polymer dispersion prepared in each example was measured at a temperature of 20 ° C. by a conventional method using a commercially available pH meter. The measurement results are shown in Table 1.

[Measuring method of particle size]
Samples prepared by diluting the conductive polymer dispersions (solid content concentration is described in the table) prepared in Examples 1 to 7 and Comparative Example 2 with distilled water to adjust the conductive composite concentration to 0.1%. Using a zeta potential / particle size / molecular weight measurement system (ELSZ-2000ZS, manufactured by Otsuka Electronics Co., Ltd.), the value obtained by measuring the average particle size of the cumland at 25 ° C. by a dynamic light scattering method was used as the particle size.

<Result 1>
The particle size of the conductive complex contained in the conductive polymer dispersions of Examples 1 to 7 was smaller than the particle size of the conductive complex of Comparative Example 2, and was 200 nm or less in the aqueous dispersion medium. The conductivity of the conductive film produced using this dispersion was such that it could exhibit an antistatic function.
Since the conductive composites of Examples 1 to 5 are dopants of an anionic polymer having only a monomer unit derived from compound 1, the particle size is significantly reduced.
Since the dopant of the conductive composites of Examples 6 to 7 has a monomer unit derived from styrene sulfonic acid, the particle size was larger than that of Examples 1 to 5, but the conductivity was improved.

(Example 8)
To 100 g of the conductive polymer dispersion liquid of Example 1, 50 g of isopropanol and 10 g of trioctylamine were added, and the mixture was stirred for 1 hour. Here, it was confirmed that the reaction products of the conductive complex containing the π-conjugated conductive polymer and the Aqualon KH-5 polymer and the trioctylamine were precipitated, and all of them were suspended in the upper layer of the solution. The obtained reaction solution was filtered to obtain the reaction product as a powder.
Isopropanol was added to the obtained powder to prepare a solution of 500 g, which was dispersed using a high-pressure homogenizer to obtain 500 g of an amine-modified conductive polymer dispersion. After measuring the solid content and the particle size, the film was applied onto a PET film using a # 8 bar coater and dried at 100 ° C. for 1 minute to obtain a conductive film, and the conductivity was evaluated.

(Example 9)
A conductive film was obtained in the same manner as in Example 8 except that 100 g of the conductive polymer dispersion liquid of Example 1 was changed to 100 g of the conductive polymer dispersion liquid of Example 6.

(Example 10)
A conductive film was obtained in the same manner as in Example 8 except that 100 g of the conductive polymer dispersion liquid of Example 1 was changed to 100 g of the conductive polymer dispersion liquid of Example 7.

(Comparative Example 3)
A conductive film was obtained in the same manner as in Example 8 except that 100 g of the conductive polymer dispersion liquid of Example 1 was changed to 100 g of the conductive polymer dispersion liquid of Comparative Example 2.

(Example 11)
To 100 g of the conductive polymer dispersion of Example 1, 25 g of an epoxy compound (Epolite M-1230, C12, C13 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. Here, a reaction product of a conductive complex containing a π-conjugated conductive polymer and an Aqualon KH-5 polymer and an epoxy compound was precipitated. This precipitate was collected by filtration.
Methyl ethyl ketone was added to the obtained precipitate to prepare a 300 g solution, which was dispersed using a high-pressure homogenizer to obtain 300 g of an epoxy-modified conductive polymer dispersion. After measuring the solid content and the particle size, the film was applied onto a PET film using a # 8 bar coater and dried at 100 ° C. for 1 minute to obtain a conductive film.

(Example 12)
A conductive film was obtained in the same manner as in Example 11 except that 100 g of the conductive polymer dispersion liquid of Example 1 was changed to 100 g of the conductive polymer dispersion liquid of Example 6.

(Example 13)
A conductive film was obtained in the same manner as in Example 11 except that 100 g of the conductive polymer dispersion liquid of Example 1 was changed to 100 g of the conductive polymer dispersion liquid of Example 7.

(Comparative Example 4)
A conductive film was obtained in the same manner as in Example 11 except that 100 g of the conductive polymer dispersion liquid of Example 1 was changed to 100 g of the conductive polymer dispersion liquid of Comparative Example 2.

(Example 14)
To 100 g of the conductive polymer dispersion liquid of Example 1, 25 g of an epoxy compound (Epolite M-1230, C12, C13 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. Here, a reaction product of a conductive composite containing a π-conjugated conductive polymer and an Aqualon KH-5 polymer and an epoxy compound and an amine compound was precipitated. This precipitate was collected by filtration.
Ethyl acetate was added to the obtained precipitate to prepare an 800 g solution, which was dispersed using a high-pressure homogenizer to obtain 800 g of an epoxy-amine-modified conductive polymer dispersion. After measuring the solid content and the particle size, the film was applied onto a PET film using a # 8 bar coater and dried at 100 ° C. for 1 minute to obtain a conductive film.

(Example 15)
A conductive film was obtained in the same manner as in Example 14 except that 100 g of the conductive polymer dispersion liquid of Example 1 was changed to 100 g of the conductive polymer dispersion liquid of Example 6.

(Example 16)
A conductive film was obtained in the same manner as in Example 14 except that 100 g of the conductive polymer dispersion liquid of Example 1 was changed to 100 g of the conductive polymer dispersion liquid of Example 7.

(Comparative Example 5)
A conductive film was obtained in the same manner as in Example 14 except that 100 g of the conductive polymer dispersion liquid of Example 1 was changed to 100 g of the conductive polymer dispersion liquid of Comparative Example 2, and the conductivity was evaluated. ..

[Measuring method of particle size]
The conductive polymer dispersions (solid content concentration is described in the table) prepared in Examples 8 to 16 and Comparative Examples 3 to 5 are diluted with the dispersion medium (organic solvent) of each dispersion to concentrate the conductive composite. Using a zeta potential / particle size / molecular weight measurement system (ELSZ-2000ZS, manufactured by Otsuka Denshi Co., Ltd.) as a sample adjusted to 0.05% by mass, the average particle size of the cumland was measured at 25 ° C by a dynamic light scattering method. The measured value was used as the particle size.

<Result 2>
The particle size of the conductive composite contained in the conductive polymer dispersions of Examples 8 to 16 was smaller than the particle size of the conductive composite of Comparative Examples 3 to 5, and was 200 nm or less in the organic solvent. The conductivity of the conductive film produced using this dispersion was such that it could exhibit an antistatic function.
The conductive composites of Examples 8, 11 and 14 had a smaller particle size than the other Examples because the dopant was an anionic polymer having only a monomer unit derived from Compound 1.
The conductive composites of Examples 9 to 10, 12 to 13, 15 to 16 have a slightly larger particle size than Examples 8, 11 and 14 because the dopant has a monomer unit derived from styrene sulfonic acid. However, the conductivity was improved.

Claims (14)

Highly conductive, containing a conductive composite containing a π-conjugated conductive polymer and an anionic polymer having a monomer unit derived from compound 1 represented by the following formula (1), and a dispersion medium. Molecular dispersion.

[In the formula, R is a linear or branched alkyl group having 4 to 20 carbon atoms, and n is an integer of 4 to 100. ] The conductive polymer dispersion liquid according to claim 1, wherein the anionic polymer is a homopolymer of the compound 1. The conductive polymer dispersion liquid according to claim 1, wherein the anionic polymer is a copolymer of styrene sulfonic acid and the compound 1. The conductive polymer dispersion liquid according to any one of claims 1 to 3, wherein the conductive composite further contains a polyanion having no monomer unit derived from the compound 1. The conductive polymer dispersion liquid according to any one of claims 1 to 4, wherein the anionic group contained in the conductive composite is modified by a reaction with an amine compound or a quaternary ammonium compound. The conductive polymer dispersion liquid according to any one of claims 1 to 4, wherein the anionic group contained in the conductive composite is modified by a reaction with an epoxy compound. The conductive polymer dispersion according to any one of claims 1 to 4, wherein the anionic group contained in the conductive composite is modified by a reaction with an amine compound, a quaternary ammonium compound, and an epoxy compound. liquid. The conductive polymer dispersion liquid according to any one of claims 1 to 7, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene). In a reaction solution containing a monomer compound forming a π-conjugated conductive polymer, an anionic polymer having a monomer unit derived from the compound 1 represented by the following formula (1), and an aqueous dispersion medium. By polymerizing the monomer compound,
A method for producing a conductive polymer dispersion, which comprises obtaining a conductive polymer dispersion containing the π-conjugated conductive polymer, the conductive composite containing the anionic polymer, and the aqueous dispersion medium.

[In the formula, R is a linear or branched alkyl group having 4 to 20 carbon atoms, and n is an integer of 4 to 100. ] The method for producing a conductive polymer dispersion liquid according to claim 9, wherein the anionic polymer is a homopolymer of the compound 1. The method for producing a conductive polymer dispersion according to claim 9, wherein the anionic polymer is a copolymer of styrene sulfonic acid and the compound 1. By polymerizing the monomer compound in a state where the reaction solution further contains a polyanion other than the anionic polymer.
The method for producing a conductive polymer dispersion liquid according to any one of claims 9 to 11, wherein the polyanion is further contained in the conductive composite. The conductive polymer dispersion liquid containing the aqueous dispersion medium is added with one or more selected from an epoxy compound, an amine compound and a quaternary ammonium compound and reacted with the conductive composite to cause the above. Precipitating the conductive composite modified by the above reaction in the aqueous dispersion medium,
The present invention according to any one of claims 9 to 12, wherein the precipitated conductive composite is recovered and an organic solvent is added to obtain a conductive polymer dispersion liquid containing the conductive composite and the organic solvent. The method for producing a conductive polymer dispersion according to the above method. A substrate and a conductive layer formed on at least one surface of the substrate are provided.
A conductive laminate in which the conductive layer is a cured product of the conductive polymer dispersion liquid according to any one of claims 1 to 8.