JP7116628B2 - Conductive polymer dispersion, method for producing same, and method for producing conductive film - Google Patents

Description

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

As a paint for forming a conductive layer, an aqueous dispersion of a conductive polymer in which poly(3,4-ethylenedioxythiophene) is doped with polystyrenesulfonic acid is sometimes used. For example, Patent Document 1 discloses a method for producing an antistatic film, in which polyvinyl alcohol is added to a conductive polymer dispersion, coated on a plastic film substrate, and stretched as necessary. disclosed.
Further, Patent Document 2 discloses a dispersion obtained by dispersing a conductive polymer in an organic solvent containing an amine compound, and Patent Document 3 discloses that a cyclic ether compound having an oxirane or oxetane group is , discloses a conductive polymer dispersion in which the dispersibility of the conductive polymer in an organic solvent is improved.

JP 2016-047501 A JP 2011-032382 A WO2014/125827

However, there is a problem that the conductivity of a conductive film produced using a conventional conductive polymer dispersion is lower than that immediately after production after several days in contact with air after production. For this reason, conventional conductive films have been required to suppress deterioration in conductivity over time.

The present invention provides a conductive polymer dispersion, a method for producing the same, and a method for producing a conductive film, which can easily produce a conductive film in which a decrease in conductivity over time in the air is suppressed.

［式（Ｂ’）中、Ｒ^１は水素原子、又は任意の置換基であり、Ｒ^２はフェノール性水酸基を有する任意の置換基である。］
［５］ 前記有機溶剤がメチルエチルケトンを含有する、［１］～［４］のいずれか一項に記載の導電性高分子分散液。
［６］ 前記有機溶剤がトルエンを含有する、［１］～［５］のいずれか一項に記載の導電性高分子分散液。
［７］ 前記π共役系導電性高分子が、ポリ（３，４－エチレンジオキシチオフェン）である、［１］～［６］のいずれか一項に記載の導電性高分子分散液。
［８］ 前記ポリアニオンが、ポリスチレンスルホン酸である、［１］～［７］のいずれか一項に記載の導電性高分子分散液。
［９］ バインダ成分をさらに含有する、［１］～［８］のいずれか一項に記載の導電性高分子分散液。
［１０］ 前記バインダ成分が、シリコーン化合物である、［９］に記載の導電性高分子分散液。
［１１］ 前記シリコーン化合物が、付加硬化型シリコーンである、［１０］に記載の導電性高分子分散液。
［１２］ π共役系導電性高分子及びポリアニオンを含有する導電性複合体が水系分散媒中に含まれる水分散液にエポキシ基含有化合物を添加し、前記ポリアニオンと反応させて析出物を得た後、前記析出物を回収する析出回収工程と、
回収した前記析出物に、第１有機溶剤、及び、エステル形成性化合物を添加して前記析出物と前記エステル形成性化合物とを反応させて第１調製液を得るエステル形成性化合物添加工程と、を有し、
前記エステル形成性化合物は、少なくとも１つのフェノール性水酸基を有する、導電性高分子分散液の製造方法。
［１３］ 前記析出回収工程と前記エステル形成性化合物添加工程との間に、水酸基及びカルボキシ基のいずれも有さない有機溶剤を含む洗浄用有機溶剤で前記析出物を洗浄する洗浄工程をさらに有する、［１２］に記載の導電性高分子分散液の製造方法。
［１４］ π共役系導電性高分子及びポリアニオンを含有する導電性複合体が水系分散媒中に含まれる水分散液を乾燥して導電性複合体の乾燥物を得る乾燥工程と、
前記乾燥物にエポキシ基含有化合物及び第１有機溶剤を添加して前記乾燥物と前記エポキシ基含有化合物とを反応させて反応物を得、さらにエステル形成性化合物を添加して前記反応物と反応させて第１調製液を得る第１調製液調製工程と、を有する、導電性高分子分散液の製造方法。
［１５］ 前記第１調製液にバインダ成分を添加するバインダ成分添加工程をさらに有する、［１４］に記載の導電性高分子分散液の製造方法。
［１６］ フィルム基材の少なくとも一方の面に、［１］～［１１］のいずれか一項に記載の導電性高分子分散液を塗工する塗工工程と、塗工した導電性高分子分散液を乾燥する乾燥工程とを有する、導電性フィルムの製造方法。 The present invention includes the following aspects.
[1] Containing a conductive composite containing a π-conjugated conductive polymer and a polyanion and an organic solvent,
The polyanion further has a substituent (B) formed by reacting an ester-forming compound with a substituent (A) formed by reacting a part of an anion group with an epoxy group-containing compound, together with an anion group. ,
The conductive polymer dispersion, wherein the ester-forming compound has at least one phenolic hydroxyl group.
[2] The conductive compound according to [1], wherein the ester-forming compound is at least one selected from the group consisting of carboxy group-containing compounds, carboxylic acid halides, carboxylic acid anhydrides, and one-terminal carboxy-modified silicones. flexible polymer dispersion.
[3] The conductive polymer dispersion according to [1] or [2], wherein the ester-forming compound is at least one selected from the group consisting of gallic acid and 4-hydroxybenzoic acid.
[4] Containing a conductive composite containing a π-conjugated conductive polymer and a polyanion and an organic solvent,
The polyanion is a conductive polymer dispersion in which some anionic groups have substituents (B') represented by the following general formula (B').

[In formula (B′), R ¹ is a hydrogen atom or an arbitrary substituent, and R ² is an arbitrary substituent having a phenolic hydroxyl group. ]
[5] The conductive polymer dispersion according to any one of [1] to [4], wherein the organic solvent contains methyl ethyl ketone.
[6] The conductive polymer dispersion according to any one of [1] to [5], wherein the organic solvent contains toluene.
[7] The conductive polymer dispersion according to any one of [1] to [6], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene).
[8] The conductive polymer dispersion according to any one of [1] to [7], wherein the polyanion is polystyrenesulfonic acid.
[9] The conductive polymer dispersion according to any one of [1] to [8], further containing a binder component.
[10] The conductive polymer dispersion according to [9], wherein the binder component is a silicone compound.
[11] The conductive polymer dispersion according to [10], wherein the silicone compound is addition-curable silicone.
[12] An epoxy group-containing compound was added to an aqueous dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion in an aqueous dispersion medium, and reacted with the polyanion to obtain a precipitate. After that, a precipitation recovery step of recovering the precipitate;
an ester-forming compound addition step of adding a first organic solvent and an ester-forming compound to the collected precipitate to react the precipitate with the ester-forming compound to obtain a first preparation liquid; has
A method for producing a conductive polymer dispersion, wherein the ester-forming compound has at least one phenolic hydroxyl group.
[13] Further comprising a washing step of washing the precipitate with an organic solvent for washing containing an organic solvent having neither a hydroxyl group nor a carboxyl group, between the precipitation recovery step and the ester-forming compound addition step. , the method for producing a conductive polymer dispersion according to [12].
[14] a drying step of drying an aqueous dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion in an aqueous dispersion medium to obtain a dried conductive composite;
An epoxy group-containing compound and a first organic solvent are added to the dried product, the dried product and the epoxy group-containing compound are reacted to obtain a reaction product, and an ester-forming compound is added to react with the reaction product. and a first preparation liquid preparation step of obtaining a first preparation liquid.
[15] The method for producing a conductive polymer dispersion according to [14], further comprising adding a binder component to the first prepared liquid.
[16] A coating step of coating the conductive polymer dispersion according to any one of [1] to [11] on at least one surface of a film substrate; A method for producing a conductive film, comprising a drying step of drying the dispersion.

The conductive polymer dispersion of the present invention can easily produce a conductive film in which deterioration in conductivity over time in air is suppressed. According to the method for producing a conductive polymer dispersion of the present invention, An effective conductive polymer dispersion can be easily produced.
According to the method for producing a conductive film of the present invention, it is possible to easily produce a conductive film in which deterioration in conductivity over time in air is suppressed.

<Conductive Polymer Dispersion>
A conductive polymer dispersion according to the first aspect of the present invention contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, and an organic solvent.

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

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

(polyanion)
A polyanion is a polymer having two or more monomer units having an anionic group in its molecule. The anion group of this polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
The anionic group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyacrylic acid esters having a sulfo group, polymethacrylic acid esters having a sulfo group (e.g., poly(4-sulfobutyl methacrylate) , polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polymers having a sulfo group such as polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, Polymers having a carboxyl group such as polyallylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, etc. These homopolymers are It may be a copolymer of two or more kinds.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be further increased.
One of the polyanions may be used alone, or two or more thereof may be used in combination.
The weight average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, more preferably 100,000 or more and 500,000 or less.

A polyanion forms a conductive complex by doping a π-conjugated conductive polymer. However, in the polyanion, all the anion groups do not dope the π-conjugated conductive polymer and have excess anion groups that do not participate in the doping. Since this surplus anionic group is a hydrophilic group, the conductive composite has high water dispersibility and low organic solvent dispersibility before being reacted with an epoxy group-containing compound as described later.

The polyanion used in this embodiment is a substituent (B ). Here, the ester-forming compound is a compound having a functional group capable of forming an ester by reaction with a hydroxyl group.
Detailed analysis of the conductive composite is not necessarily easy, but it is assumed that the substituent (A) is a group represented by the following chemical formula (A), and the substituent (B) is a group represented by the following chemical formula (B). be done. That is, in this aspect, it is presumed that protons in some of the anionic groups of the polyanion are replaced with the substituent (B).

[In formula (A), R ¹ is a hydrogen atom or an arbitrary substituent. ]

[In formula (B), R ¹ is a hydrogen atom or an arbitrary substituent, and R ² is an arbitrary substituent having a phenolic hydroxyl group. ]

R ¹ in chemical formula (A) and chemical formula (B) is a hydrogen atom or an arbitrary substituent. The hydroxyl group in chemical formula (A) is a group formed by ring-opening of the epoxy group of the epoxy group-containing compound, and R ¹ is a substituent derived from the epoxy group-containing compound described later.
^R2 in chemical formula (B) is an arbitrary substituent having a phenolic hydroxyl group.
Substituent (A) binds to the oxygen atom of the anionic group. The secondary hydroxyl group of the substituent (A) is esterified and converted to the substituent (B).

The optional substituents for R ¹ include an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms and an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. and the like.
As used herein, the term “optionally having a substituent” refers to cases in which a hydrogen atom (—H) is substituted with a monovalent group, and cases in which a methylene group (—CH ₂ —) is substituted with a divalent group. Including both when to replace.
Examples of monovalent groups as substituents include alkenyl groups having 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), trialkoxysilyl groups (trimethoxysilyl group, etc.), and the like. is mentioned.
The divalent group as a substituent includes an oxygen atom (--O--), --C(=O)--, --C(=O)--O-- and the like.

As an optional substituent having a phenolic hydroxyl group in R ² , an aliphatic hydrocarbon having 1 to 20 carbon atoms which has an aromatic hydrocarbon having a hydroxyl group as a substituent and may have other substituents Examples thereof include aromatic hydrocarbon groups having 6 to 20 carbon atoms which have a hydrogen group and a hydroxyl group as substituents and which may have other substituents. Examples of the other substituents include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, and hydroxyl groups.

As the substituent (B), a substituent (B1) represented by the chemical formula (B1) and a substituent (B2) represented by the chemical formula (B2) are preferable.

[In formula (B1), R ¹ is a hydrogen atom or an arbitrary substituent, R ³ to R ⁷ are each independently a hydrogen atom or an arbitrary substituent, provided that at least R ³ to R ⁷ One is a hydroxyl group. ]

[In the formula (B2), R ¹ is a hydrogen atom or an arbitrary substituent, Y is a divalent linking group, and R ⁸ to R ¹² are each independently a hydrogen atom or an arbitrary substituent, , provided that at least one of R ⁸ to R ¹² is a hydroxyl group. ]

R ¹ in chemical formula (B1) and chemical formula (B2) is a hydrogen atom or an arbitrary substituent. Examples of R ¹ include the same as those described for chemical formula (A) and chemical formula (B).
R ³ to R ⁷ in chemical formula (B1) are each independently a hydrogen atom or an arbitrary substituent, provided that at least one of R ³ to R ⁷ is a hydroxyl group. Optional substituents for R ³ to R ⁷ include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, and hydroxyl groups.
Examples of alkyl groups having 1 to 4 carbon atoms in R ³ to R ⁷ include methyl group, ethyl group, propyl group and butyl group. Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy and butoxy groups. Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.
R ⁸ to R ¹² in chemical formula (B2) are each independently a hydrogen atom or an arbitrary substituent, provided that at least one of R ⁸ to R ¹² is a hydroxyl group. Optional substituents for R ⁸ to R ¹² include alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms and hydroxyl groups. Examples of the alkyl group having 1 to 4 carbon atoms, the alkoxy group having 1 to 4 carbon atoms, and the halogen atom in R ⁸ to R ¹² are the same as those described in the chemical formula (B1).
Y in chemical formula (B2) is a divalent linking group. Examples of divalent linking groups include linear or branched alkylene groups and phenylene groups having 1 to 14 carbon atoms. The linear or branched alkylene group having 1 to 14 carbon atoms includes methylene group, ethylene group, propylene group, butylene group and the like.

Among them, the substituent (B) is preferably represented by the chemical formula (B1), more preferably R ¹ in the chemical formula (B1) is an alkoxyalkyl group having 10 to 15 carbon atoms, and the chemical formula (B1 ) in which R ¹ is an alkoxyalkyl group having 10 to 15 carbon atoms and R ⁵ is a hydroxyl group is more preferable.

An epoxy group-containing compound is a compound having one or more epoxy groups in one molecule. From the viewpoint of preventing aggregation or gelation, the epoxy group-containing compound is preferably a compound having one epoxy group in one molecule.
Epoxy group-containing compounds may be used alone or in combination of two or more.

Examples of monofunctional epoxy group-containing compounds having one epoxy group in one molecule include ethylene oxide, propylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-butylene oxide, and 1,2-epoxyhexane. , 1,2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monoxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1, 2-epoxyoctadecane, 1,2-epoxyhexadecane, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2-(chloromethyl)-1,2-epoxypropane, glycidol, epichlorohydrin, epibromohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2-(chloromethyl)-1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1, 2-epoxy-1H,1H,2H,2H,3H,3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclo dodecane, 1-methyl-1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H,1H,2H,2H, 3H,3H-heptadecafluorobutane, 3,4-epoxytetrahydrofuran, glycidyl stearate, 3-glycidyloxypropyltrimethoxysilane, epoxysuccinic acid, glycidylphenyl ether, isophorone oxide, α-pinene oxide, 2,3-epoxy norbornene, benzyl glycidyl ether, diethoxy(3-glycidyloxypropyl)methylsilane, 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane, 1,1,1,3,5,5,5- Heptamethyl-3-(3-glycidyloxypropyl)trisiloxane, 9,10-epoxy-1,5-cyclododecadiene, glycidyl 4-tert-butylbenzoate, 2,2-bis(4-glycidyloxyphenyl)propane , 2-tert-butyl-2-[2-(4-chloroph phenyl)]ethyloxirane, styrene oxide, glycidyltrityl ether, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-phenylpropylene oxide, cholesterol-5α,6α-epoxide, stilbene oxide, p-toluenesulfonic acid glycidyl, ethyl 3-methyl-3-phenylglycidate, N-propyl-N-(2,3-epoxypropyl) perfluoro-n-octylsulfonamide, (2S,3S)-1,2-epoxy-3- (tert-butoxycarbonylamino)-4-phenylbutane, (R)-glycidyl 3-nitrobenzenesulfonate, glycidyl 3-nitrobenzenesulfonate, parthenolide, N-glycidylphthalimide, endrin, deildrin, 4-glycidyloxycarbazole, 7 ,7-dimethyloctanoic acid [oxiranylmethyl], 1,2-epoxy-4-vinylcyclohexane, C12, C13 mixed higher alcohol glycidyl ether and the like.

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

Since the epoxy group-containing compound has a higher solubility in organic solvents, it preferably has a molecular weight of 50 or more and 2,000 or less. Those of 7 or more are preferable, and those of 10 or more are more preferable.

The ester-forming compound has a phenolic hydroxyl group and a functional group capable of reacting with the hydroxyl group to form an ester. The functional group capable of reacting with a hydroxyl group to form an ester includes a carboxy group, a carboxylic acid anhydride group, a carboxylic acid chloride group, a sulfo group, a phosphoric acid group, and the like.
The ester-forming compound is preferably at least one selected from the group consisting of carboxy group-containing compounds, carboxylic acid halides, carboxylic acid anhydrides, and one-terminal carboxy-modified silicones. The above preferred ester-forming compounds can readily react with hydroxyl groups to readily hydrophobize polyanions.
A carboxy group-containing compound is an organic compound having a phenolic hydroxyl group and a carboxy group, and includes, for example, those in which some hydrogen atoms of an aromatic hydrocarbon are substituted with a carboxy group and a hydroxyl group.
Carboxy group-containing compounds include 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 4-hydroxy-3,5-dimethylbenzoic acid, 4-hydroxy-3-methylbenzoic acid, 3,4,5-tri Hydroxybenzoic acid (gallic acid), 2,4-dihydroxybenzoic acid, 4-hydroxy-2-methylbenzoic acid, 2,4,6-trihydroxybenzoic acid, 4-hydroxy-3-methoxybenzoic acid, 3-chloro -4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoic acid, 4-hydroxy-3,5-dimethoxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid , 3,5-tert-butyl-4-hydroxybenzoic acid, 3-fluoro-4-hydroxybenzoic acid, 3,5-dibromo-4-hydroxybenzoic acid, 2-fluoro-4-hydroxybenzoic acid, 2,3 ,4-trihydroxybenzoic acid, 2,6-difluoro-4-hydroxybenzoic acid and the like. Among them, 4-hydroxybenzoic acid and gallic acid are preferred.
Carboxylic acid halides include chlorides, fluorides, bromides and iodides of the carboxy group-containing compounds.
Examples of carboxylic acid anhydrides include acid anhydrides formed by dehydrating and condensing two molecules of the carboxy group-containing compound.
In terms of improving the dispersibility of the conductive composite in an organic solvent while improving the hydrophobicity of the conductive composite, the number of carbon atoms in the carboxy group-containing compound is preferably 7 or more and 24 or less, and 7 or more and 14 or less. is more preferable, and 7 or more and 10 or less is even more preferable.
The single-end carboxy-modified silicone is obtained by introducing a carboxy group to one end of linear silicone. Examples of silicone include dimethylsilicone, methylhydrogensilicone, and the like. The carboxy group equivalent weight of the one-end carboxy-modified silicone is preferably 1000 g/mol or more and 2000 g/mol or less. Specific examples of the one-terminal carboxy-modified silicone include X-22-3710 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
Ester-forming compounds may be used alone or in combination of two or more.

The content of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the π-conjugated conductive polymer, and is 10 parts by mass or more and 700 parts by mass or less. and more preferably in the range of 100 parts by mass or more and 500 parts by mass or less. If the polyanion content is at least the above lower limit, the doping effect on the π-conjugated conductive polymer tends to be stronger, resulting in higher conductivity. On the other hand, if the polyanion content is equal to or less than the above upper limit, the amount of anionic groups that do not participate in doping is appropriately suppressed, and the anionic groups can be easily converted to hydrophobicity when reacting the epoxy group-containing compound.

The content of the conductive composite relative to the total mass of the conductive polymer dispersion is, for example, preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, 1.0% by mass or more and 5.0% by mass or less is more preferable.

(Organic solvent)
Examples of the organic solvent used in this embodiment include hydrocarbon-based solvents, ketone-based solvents, alcohol-based solvents, ester-based solvents, nitrogen atom-containing compound-based solvents, and the like. An organic solvent may be used individually by 1 type, and may use 2 or more types together.
Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of aliphatic hydrocarbon solvents include pentane, hexane, heptane, octane, decane, cyclohexane, and methylcyclohexane. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
Ketone solvents include, for example, diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol and the like.
Examples of alcohol solvents include methanol, ethanol, isopropanol, n-butanol, t-butanol, and allyl alcohol.
Examples of ester-based solvents include ethyl acetate, propyl acetate, and butyl acetate.
Examples of nitrogen atom-containing compound solvents include N-methylpyrrolidone, dimethylacetamide, dimethylformamide and the like.

Among the above organic solvents, hydrocarbon-based solvents are preferable in that the wettability of the conductive polymer dispersion to the plastic film substrate is increased and the low-polarity binder component can be easily solubilized. Among the hydrocarbon-based solvents, toluene is preferred because it is versatile. Moreover, when a silicone compound is used as the binder component, at least one of heptane and toluene is preferable because of its excellent silicone solubility.
The organic solvent used in this embodiment preferably contains methyl ethyl ketone because the dispersibility of the conductive composite becomes higher.

(binder component)
The conductive polymer dispersion of this embodiment may contain a binder component in order to improve the film formability of the resulting conductive layer.
Since the conductive polymer dispersion of this embodiment uses an organic solvent as a dispersion medium, a low-polarity silicone compound can be suitably used as a binder component.

Examples of silicone compounds include curable silicones. When the binder component is a curable silicone, the conductive layer can exhibit releasability by curing the curable silicone.
The curable silicone may be either an addition curable silicone or a condensation curable silicone. This embodiment is suitable because even if addition-curing silicone is used, curing inhibition is less likely to occur.
Examples of addition-curable silicones include linear polymers having siloxane bonds and having polydimethylsiloxane having vinyl groups at both ends of the linear chain and hydrogensilane. Such addition-curable silicone forms a three-dimensional crosslinked structure through an addition reaction and cures. A platinum-based curing catalyst may be used to accelerate curing.
Specific examples of addition-curable silicones include KS-3703T, KS-847T, KM-3951, X-52-151, X-52-6068, and X-52-6069 (manufactured by Shin-Etsu Chemical Co., Ltd.). .
Addition-curable silicone dissolved or dispersed in an organic solvent is preferably used.

In addition, as the binder component, thermoplastic resins (e.g., polyesters, etc.), thermosetting compounds (e.g., polyfunctional epoxy compounds, etc.), active energy ray-curable compounds (e.g., acrylic compounds, etc.) other than silicone compounds are used. good too. When using a thermosetting compound, it is preferable to further contain a thermal polymerization initiator, and when using an active energy ray-curable compound, it is preferable to further contain a photopolymerization initiator.

The content of the binder component is preferably 1000 parts by mass or more and 100000 parts by mass or less, more preferably 3000 parts by mass or more and 50000 parts by mass or less with respect to 100 parts by mass of the conductive composite. If the content of the binder component is at least the above lower limit, the strength and hardness of the obtained conductive layer can be sufficiently improved, and if it is at most the above upper limit, sufficient conductivity can be ensured.

(high conductivity agent)
The conductive polymer dispersion may contain a conductivity enhancing agent in order to further improve the conductivity.
Here, the above-described π-conjugated conductive polymer, organic solvent, polyanion, and binder component are not classified as high-conductivity agents. However, the epoxy group-containing compound and the ester-forming compound may correspond to the high-conductivity agent described here.
Conductive agents include sugars, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxyl groups, compounds having one or more hydroxyl groups and one or more carboxyl groups, compounds having an amide group, and imide groups. is preferably at least one compound selected from the group consisting of compounds having
The conductivity enhancing agent contained in the conductive polymer dispersion may be one type or two or more types.
The content of the conductive agent is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 5000 parts by mass or less with respect to 100 parts by mass of the conductive composite. More preferably, the amount is not less than 2500 parts by mass.
If the content of the high-conductivity agent is at least the above lower limit, the effect of improving conductivity by adding the high-conductivity agent is sufficiently exhibited, and if it is at or below the above upper limit, the concentration of the π-conjugated conductive polymer decreases. It is possible to prevent a decrease in conductivity caused by

(Other additives)
The conductive polymer dispersion may contain other known additives.
Additives are not particularly limited as long as the effects of the present invention can be obtained, and for example, surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, ultraviolet absorbers and the like can be used. However, the additive comprises a compound other than the π-conjugated conductive polymer, polyanion, epoxy group-containing compound, ester-forming compound, binder component, and high-conductivity agent described above.
Examples of surfactants include nonionic, anionic, and cationic surfactants, with nonionic surfactants being preferred from the standpoint of storage stability. A polymeric surfactant such as polyvinylpyrrolidone may also be added.
Examples of inorganic conductive agents include metal ions and conductive carbon. Metal ions can be generated by dissolving a metal salt in water.
Antifoaming agents include silicone resins, polydimethylsiloxane, silicone oils and the like.
Examples of coupling agents include silane coupling agents having a vinyl group or an amino group.
Examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. is mentioned.
When the conductive polymer dispersion contains the above additives, the content ratio thereof can be appropriately determined according to the type of the additive. 001 parts by mass or more and 5 parts by mass or less.

A conductive polymer dispersion according to the second aspect of the present invention contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, and an organic solvent.
The same π-conjugated conductive polymer, polyanion, and organic solvent as described in the first aspect can be used.
In the conductive polymer dispersion according to the second aspect of the present invention, some anionic groups have a substituent (B') represented by the following general formula (B').

[In formula (B′), R ¹ is a hydrogen atom or an arbitrary substituent, and R ² is an arbitrary substituent having a phenolic hydroxyl group. ]

In formula (B'), R ¹ and R ² are the same as those described for chemical formula (B) above.

As the substituent (B'), the substituent (B1') represented by the chemical formula (B1') and the substituent (B2') represented by the chemical formula (B2') are preferable.

[In the formula (B1′), R ¹ is a hydrogen atom or an arbitrary substituent, and R ³ to R ⁷ are each independently a hydrogen atom or an arbitrary substituent, provided that among R ³ to R ⁷ At least one is a hydroxyl group. ]

[In the formula (B2′), R ¹ is a hydrogen atom or an arbitrary substituent, Y is a divalent linking group, R ⁸ to R ¹² are each independently a hydrogen atom or an arbitrary substituent, with the proviso that at least one of R ⁸ to R ¹² is a hydroxyl group. ]

Examples of R ¹ in chemical formula (B1′) and chemical formula (B2′) are the same as those described in chemical formula (A) and chemical formula (B).
Examples of R ³ to R ⁷ in chemical formula (B1′) are the same as those described in chemical formula (B1).
Examples of R ⁸ to R ¹² in chemical formula (B2′) are the same as those described in chemical formula (B2).
Examples of Y in the chemical formula (B2') include those similar to those described in the chemical formula (B2).

Among them, the substituent (B') is preferably represented by the chemical formula (B1'), more preferably one in which R ¹ is an alkoxyalkyl group having 10 to 15 carbon atoms in the chemical formula (B1'), More preferably, in the chemical formula (B1′), R ¹ is an alkoxyalkyl group having 10 to 15 carbon atoms and R ⁵ is a hydroxyl group.

The method for forming the substituent (B') is not particularly limited. For example, an anion group of a monomer constituting a polyanion is reacted with an epoxy group-containing compound to form a substituent (A), and the substituent (A) is reacted with an ester-forming compound to form a substituent (B'). ) is formed, the monomer having the substituent (B′) and the monomer not having the substituent (B′) are subjected to a polymerization reaction to form a polyanion in which some of the anionic groups have the substituent (B′). You may Alternatively, a halogenating agent such as phosphorus pentachloride is reacted with an anion group of a polyanion to form a halide, which is then reacted with a compound in which a hydroxyl group is bonded to the terminal methylene group of the substituent (B') to obtain an anion. A method of introducing a substituent (B') into a group is also included.

The conductive polymer dispersion of the second aspect of the present invention may contain a binder component, a conductivity enhancer, and other additives as in the conductive polymer dispersion of the first aspect. .

(Method for producing conductive polymer dispersion)
[First manufacturing method]
A first method for producing a conductive polymer dispersion of this embodiment for obtaining the conductive polymer dispersion has a precipitation recovery step and an ester-forming compound addition step.
Moreover, the first method for producing a conductive polymer dispersion of this aspect may further include a washing step between the precipitation recovery step and the ester-forming compound addition step. Moreover, at least one of the second organic solvent addition step and the binder component addition step may be further provided after the ester-forming compound addition step.

[Precipitation recovery step]
The deposition and collection step is a step of adding an epoxy group-containing compound to the conductive polymer aqueous dispersion to precipitate a conductive composite to obtain a precipitate, and then collecting the precipitate by filtration.
When the epoxy group-containing compound is added to the conductive polymer aqueous dispersion, at least part of the epoxy groups of the epoxy group-containing compound reacts with some of the anion groups of the polyanion. As a result, the substituent (A) is formed and the conductive composite becomes hydrophobic, so that it becomes difficult to stably disperse in the aqueous dispersion, and precipitates to form a deposit.
The amount of the epoxy group-containing compound added is preferably 0.1 or more and 1000 or less, more preferably 1.0 or more and 100 or less in mass ratio to the polyanion. If the amount of the epoxy group-containing compound added is above the lower limit, the hydrophobicity of the conductive composite will be sufficiently high, and if it is below the above upper limit, the decrease in conductivity due to the unreacted epoxy group-containing compound will be prevented. can.
An organic solvent may be added before, at the same time as, or after adding the epoxy group-containing compound to the conductive polymer aqueous dispersion. As the organic solvent, a water-soluble organic solvent is preferred. Examples of water-soluble organic solvents include alcohol-based solvents, ketone-based solvents, and ester-based solvents. When a water-soluble organic solvent is included, one type may be used alone, or two or more types may be used in combination.

The aqueous conductive polymer dispersion to which the epoxy group-containing compound is added is a dispersion in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium. Here, the content of water in the aqueous dispersion medium is preferably 20% by mass or more, more preferably 50% by mass or more, and may be 100% by mass.
The conductive polymer aqueous dispersion can be obtained, for example, by chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous polyanion solution. A commercially available conductive polymer aqueous dispersion may also be used.
A known catalyst may be applied to the chemical oxidation polymerization. For example, catalysts and oxidants can be used. Examples of catalysts include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate. The oxidizing agent can return the reduced catalyst to its original oxidation state.

It is preferable that the amount of water in the precipitate obtained by the precipitation recovery step is as small as possible, and it is most preferable that the precipitate does not contain any water.
Methods for reducing the water content include, for example, a method of washing away the precipitate with an organic solvent, a method of drying the precipitate, and the like.

[Washing process]
The washing step between the precipitation recovery step and the ester-forming compound addition step is a step of washing the precipitate with an organic solvent for washing. This washing step removes residual water, unreacted epoxy group-containing compound, and hydrolyzate of the epoxy group-containing compound.
The cleaning organic solvent includes an organic solvent having neither a hydroxyl group nor a carboxyl group. An organic solvent having a hydroxyl group may react with an epoxy group-containing compound to produce a useless ester. Moreover, when the organic solvent having a hydroxyl group or a carboxyl group remains in the precipitate, it may react with the ester-forming compound used in the next step. Therefore, the cleaning organic solvent used in the cleaning step includes an organic solvent having neither a hydroxyl group nor a carboxyl group and having low reactivity with the epoxy group-containing compound and the ester-forming compound. The cleaning organic solvent may contain an organic solvent having a hydroxyl group. Organic solvents with hydroxyl groups are suitable for removing water.
If an organic solvent containing hydroxyl groups is used as the organic solvent for washing, the residue may react with the ester-forming compound. Washing with an organic solvent that does not have any carboxy groups is preferred.
Also, the organic solvent for washing is preferably one that can wash without dissolving the precipitate. Therefore, ketone-based solvents, ester-based solvents, and nitrogen atom-containing compound-based solvents are preferable as the organic solvent for cleaning. The organic solvents for washing may be used singly or in combination of two or more.
The washing method is not particularly limited. For example, the precipitate may be washed by pouring an organic washing solvent over the precipitate, or the precipitate may be washed by stirring the precipitate in the organic washing solvent. You may

[Step of adding ester-forming compound]
The ester-forming compound addition step is a step of adding a first organic solvent and an ester-forming compound to the precipitate to obtain a first preparation liquid.
To the precipitate, the first organic solvent and the ester-forming compound may be added at the same time, or the ester-forming compound may be added after adding the first organic solvent.
By adding the ester-forming compound to the precipitate, the substituent (A) formed by the reaction between the anionic group and the epoxy group-containing compound can be reacted with the ester-forming compound. When the substituent (A) is reacted with an ester-forming compound, the substituent (B) is formed and the hydrophobicity of the conductive composite is increased.
The amount of the ester-forming compound to be added is preferably from 0.1 to 100, more preferably from 1 to 20, in mass ratio to the polyanion. If the amount of the ester-forming compound added is at least the above lower limit, the hydrophobicity of the conductive composite will be sufficiently high, and if it is below the above upper limit, the decrease in conductivity due to the unreacted ester-forming compound will be prevented. can.
In the step of adding the ester-forming compound, heating is preferred in order to promote the reactivity of the ester-forming compound. The heating temperature is preferably 40° C. or higher and 100° C. or lower. The heating time is preferably 1 hour or more and 12 hours or less, more preferably 2 hours or more and 8 hours or less.

As the first organic solvent, the above-described organic solvents can be used. However, when a second organic solvent addition step, which will be described later, is included, it is preferable to use methyl ethyl ketone as the first organic solvent. The use of methyl ethyl ketone as the first organic solvent can improve the dispersibility of the precipitate in the first preparation liquid, and the dispersibility of the conductive composite in the conductive polymer dispersion obtained by adding the second organic solvent. can be further improved.

After adding the first organic solvent and the ester-forming compound to the precipitate, the first preparation liquid may be stirred to perform a dispersion treatment. In particular, when the present production method does not have the step of adding the second organic solvent, it is preferable to subject the first preparation liquid to a dispersion treatment. The stirring method is not particularly limited, and may be stirring with a weak shearing force such as a stirrer, or may be stirred using a high shearing force disperser (such as a homogenizer).

When the first method for producing a conductive polymer dispersion according to this aspect does not have the step of adding the second organic solvent, the first prepared liquid obtained in the step of adding the ester-forming compound is the conductive polymer dispersion. becomes liquid.

[Second organic solvent addition step]
The second organic solvent adding step is a step of adding a second organic solvent different from the first organic solvent to the first prepared liquid to obtain a second prepared liquid. After adding the second organic solvent to the first prepared liquid, it is preferable to agitate the second prepared liquid for dispersion treatment. The stirring method is not particularly limited, and may be stirring with a weak shearing force such as a stirrer, or may be stirred using a high shearing force disperser (such as a homogenizer).
When methyl ethyl ketone is used as the first organic solvent, it is preferable to use a low-polarity hydrocarbon solvent as the second organic solvent. It is more preferable to use
In the case where the first method for producing a conductive polymer dispersion of this aspect includes the second organic solvent addition step, the second prepared liquid obtained in the second organic solvent addition step is the conductive polymer dispersion. Become.

[Binder component addition step]
The binder component addition step is a step of adding a binder component to the first preparation liquid or the second preparation liquid. You may add a 2nd organic solvent with a binder component in this process. In the case of not having the second organic solvent addition step, it is preferable to add the binder component to the first preparation liquid, and in the case of having the second organic solvent addition step, the binder component is added to the second preparation liquid. is preferred.
After adding the binder component to the first preparation liquid or the second preparation liquid, it is preferable to stir to enhance the dispersibility of the binder component.
When the binder component is an addition-curable silicone, it is preferable to add a platinum-based curing catalyst at the same time as or after the addition of the binder component.

[Addition of high-conductivity agent and additive]
When the conductive polymer dispersion contains a conductive agent, an additive, etc., in any one or more of the step of adding an ester-forming compound, the step of adding a second organic solvent and the step of adding a binder component, A conductive agent, an additive, or the like may be added.

[Second manufacturing method]
The second method for producing a conductive polymer dispersion of this aspect for obtaining the conductive polymer dispersion has a drying step and a first prepared liquid preparing step.
Moreover, the second method for producing a conductive polymer dispersion according to this aspect may further include a washing step between the drying step and the first preparation liquid preparing step. Moreover, at least one of the second organic solvent addition step and the binder component addition step may be further included after the first preparation liquid preparation step. The washing step, the second organic solvent addition step and the binder component addition step in the second manufacturing method are the same as the washing step, the second organic solvent addition step and the binder component addition step in the first manufacturing method.
In the present production method, when the conductive polymer dispersion contains a conductive agent, an additive, or the like, any one of the first preparation liquid preparation step, the second organic solvent addition step, and the binder component addition step In the above steps, a highly conductive agent, an additive, and the like may be added.

[Drying process]
The drying step is a step of drying an aqueous dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion in an aqueous dispersion medium to obtain a dried conductive composite.
As a drying method in the drying step, known methods such as freeze drying, vacuum drying, spray drying, air drying, warm air drying, and heat drying can be applied.
In the freeze-drying, the water content in the conductive polymer aqueous dispersion is frozen and dried in a vacuum.
The temperature during freeze-drying is preferably -60 to 60°C, more preferably -40 to 40°C. If the freeze-drying temperature is equal to or higher than the lower limit, the temperature can be easily adjusted, and if it is equal to or lower than the upper limit, the aqueous conductive polymer dispersion can be easily freeze-dried.
In the vacuum drying, in order to sufficiently volatilize the aqueous dispersion medium, the composition may be heated to, for example, 40° C. or higher after reaching the freeze-drying temperature.
In the spray-drying, the aqueous conductive polymer dispersion is sprayed into a vacuum vessel to evaporate water and dry.
The temperature during spray drying is preferably -20 to 40°C, more preferably 0 to 30°C. If the spray-drying temperature is equal to or higher than the lower limit, the aqueous conductive polymer dispersion can be easily dried, and if it is equal to or lower than the upper limit, thermal deterioration of the conductive composite can be prevented.
It is preferable that the amount of water in the dried product obtained by the drying step is as small as possible, and it is most preferable that the product does not contain water at all.
In order to reduce the water content, for example, the drying time should be increased, the drying temperature should be increased, and the degree of vacuum should be increased.

[First preparation liquid preparation step]
In the first preparation liquid preparation step, an epoxy group-containing compound and a first organic solvent are added to the dried product to obtain a reaction product, and an ester-forming compound is added to the obtained reaction product to obtain a first preparation liquid. It is a process.
As the first organic solvent, the organic solvents described above can be used without particular limitation. In particular, in this production method, since the dried product contains almost no water, a low-polarity solvent such as a hydrocarbon solvent can be used as the first organic solvent, and at least one of heptane and toluene can be preferably used.
In the above step, by adding the epoxy group-containing compound to the dried product, the anion group of the polyanion and the epoxy group-containing compound can be reacted to form the substituent (A). Moreover, by adding an ester-forming compound thereafter, the substituent (A) can be reacted with the ester-forming compound to form the substituent (B). During the addition of the epoxy group-containing compound and the ester-forming compound, heating may be performed to promote the reaction. The heating temperature is preferably 40° C. or higher and 100° C. or lower.
Also in the second manufacturing method, the conductive polymer dispersion may be used as the first prepared liquid, or the second prepared liquid obtained in the second organic solvent addition step may be used as the conductive polymer dispersion.

(Effect)
According to the conductive polymer dispersion of this aspect, the polyanion has the substituent (B), so that the dispersibility of the conductive composite in the organic solvent can be improved. In the conductive layer formed from such a conductive polymer dispersion, the dispersibility of the conductive composite is high, so that the conductivity is sufficiently improved despite the use of an organic solvent as a dispersion medium. be able to. Moreover, it is possible to suppress deterioration of the conductivity of the conductive layer over time in the air.
In addition, the conductive polymer dispersion of this embodiment can easily dissolve or disperse the binder component, particularly the low-polarity organic solvent such as a silicone compound, and can improve the dispersibility of the binder component. When a silicone compound is used as a binder component to make the conductive layer exhibit releasability, the dispersibility of the silicone in the conductive layer formed from the conductive polymer dispersion increases, thereby improving releasability. can be made

<Method for producing conductive film>
The method for producing a conductive film of this embodiment includes a coating step of coating the conductive polymer dispersion on at least one surface of a film substrate, and a coating film made of the coated conductive polymer dispersion. and a drying step of drying the (conductive layer).

(Conductive film)
The conductive film obtained by the production method of this aspect comprises a film substrate and a conductive layer formed on at least one surface of the film substrate. The conductive layer contains a conductive composite containing a π-conjugated conductive polymer and a polyanion. Some of the hydrogen atoms of the anionic groups of the polyanion contained in the conductive layer are substituted with the substituent (B).
When the conductive polymer dispersion contains a binder component, the conductive layer contains the binder component or a cured product obtained by curing the binder component.
The average thickness of the conductive layer is preferably 10 nm or more and 20000 nm or less, more preferably 20 nm or more and 10000 nm or less, and even more preferably 30 nm or more and 5000 nm or less. If the average thickness of the conductive layer is at least the lower limit, sufficiently high conductivity can be exhibited, and if the average thickness is at most the upper limit, the conductive layer can be easily formed.

Examples of film substrates used in the production method of this embodiment include plastic films and paper.
Examples of film substrate resins constituting plastic films include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, and polybutylene terephthalate. , polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene elastomer, polyester elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio nate and the like. Among these film substrate resins, polyethylene terephthalate and cellulose triacetate are preferable because they are inexpensive and have excellent mechanical strength.
The film substrate resin may be amorphous or crystalline.
Moreover, the film substrate may be unstretched or stretched.
In addition, the film substrate may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc., in order to further improve the adhesion of the conductive layer formed from the conductive polymer dispersion.

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

(Coating process)
Examples of methods for applying the conductive polymer dispersion in the coating step include gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, fountain coaters, rod coaters, and air doctors. Coating methods using coaters such as coaters, knife coaters, blade coaters, cast coaters, and screen coaters; spraying methods using atomizers such as air spray, airless spray, and rotor dampening; and immersion methods such as dipping. be able to.
Among the above, a bar coater may be used because it can be applied easily. In the bar coater, the coating thickness varies depending on the type. Commercially available bar coaters are numbered for each type, and the larger the number, the thicker the coating.
The coating amount of the conductive polymer dispersion onto the film substrate is not particularly limited, but the solid content is preferably in the range of 0.1 g/m ² or more and 10.0 g/m ² or less.

(Drying process)
Examples of the drying method in the drying step include heat drying and vacuum drying. As heat drying, for example, a normal method such as hot air heating or infrared heating can be used. When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium to be used, and can be set to, for example, 50° C. or higher and 150° C. or lower. Here, the heating temperature is the set temperature of the drying device.
When the conductive polymer dispersion contains an active energy ray-curable binder component, an active energy ray irradiation step of irradiating the dried conductive polymer coating film with an active energy ray is performed after the drying step. You may have more. If the active energy ray irradiation step is included, the formation speed of the conductive layer can be increased, and the productivity of the conductive film is improved.
When having an active energy ray irradiation step, the active energy ray used includes ultraviolet rays, electron beams, visible rays, and the like. Ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps, and the like can be used as the ultraviolet light source.
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. In addition, the integrated amount of light is preferably 50 mJ/cm ² or more. If the integrated amount of light is less than 50 mJ/cm ² , sufficient cross-linking may not be achieved. In addition, the illuminance and the integrated amount of light in this specification are measured using Topcon UVR-T1 (industrial UV checker, light 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.

(Effect)
In the method for producing a conductive film of this aspect, the conductivity of the conductive layer formed from the conductive polymer dispersion of the above aspect tends to increase, and the conductivity of the conductive layer over time in the air Decrease can be suppressed.
Further, in the conductive polymer dispersion of the above aspect, since the conductive composite is highly dispersed in the organic solvent, the conductive composite is also dispersed in the conductive layer formed from the conductive polymer dispersion. can be contained in a highly dispersed manner. Therefore, the conductivity of the conductive layer can be sufficiently increased.
Further, when the conductive polymer dispersion contains a silicone compound, the silicone compound is highly dispersed in the conductive polymer dispersion. It is possible to increase the dispersibility of the compound. Therefore, the releasability of the conductive layer, which is exhibited by the silicone compound, can be sufficiently enhanced.

(Production example 1)
206 g of sodium styrenesulfonate is dissolved in 1000 ml of ion-exchanged water, and while stirring at 80° C., 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water is added dropwise for 20 minutes, and this solution is allowed to stand for 12 hours. Stirred.
1000 ml of sulfuric acid diluted to 10% by mass was added to the obtained solution containing sodium styrenesulfonate, about 1000 ml of the polystyrene sulfonic acid-containing solution was removed by ultrafiltration, and 2000 ml of ion-exchanged water was added to the remaining solution. , about 2000 ml solution was removed by ultrafiltration. The above ultrafiltration operation was repeated three times. Further, about 2000 ml of ion-exchanged water was added to the obtained polystyrene sulfonic acid solution, and about 2000 ml of the solution was removed by ultrafiltration. This ultrafiltration operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.

(Production example 2)
14.2 g of 3,4-ethylenedioxythiophene and a solution of 36.7 g of polystyrenesulfonic acid dissolved in 2000 ml of deionized water were mixed at 20°C.
The mixed solution thus obtained was kept at 20° C., and while stirring, 29.64 g of ammonium persulfate and 8.0 g of ferric sulfate oxidation catalyst solution dissolved in 200 ml of ion-exchanged water were slowly added, The mixture was stirred for 3 hours to react.
2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of the solution was removed by ultrafiltration. This operation was repeated three times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the obtained solution, about 2000 ml of the solution is removed by ultrafiltration, and 2000 ml of ion-exchanged water is added to this, and Approximately 2000 ml of solution was removed by extrafiltration. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the resulting solution, and about 2000 ml of the solution was removed by ultrafiltration. This operation was repeated five times to obtain a 1.2% polystyrenesulfonic acid-doped poly(3,4-ethylenedioxythiophene) (PEDOT-PSS aqueous dispersion) solution. The content of PSS with respect to the PEDOT-PSS solid content is 75% by mass.

(Production example 3)
To 100 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2, 300 g of methanol and 25 g of an epoxy group-containing compound (manufactured by Kyoeisha Chemical Co., Ltd., Epolite M-1230, C12, C13 mixed higher alcohol glycidyl ether) were added, and the mixture was heated to 60°C. and stirred for 4 hours. As a result, a deposit of a conductive composite formed from a π-conjugated conductive polymer, a polyanion, and an epoxy group-containing compound was obtained. The precipitate was collected by filtration and washed by pouring 100 g of methanol and then 100 g of ethyl acetate over it to obtain 1.6 g of a conductive composite.

(Production example 4)
Addition-curable silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KS-3703T, solid content concentration 30% by mass, toluene solution) 2.25 g, toluene 38.25 g, methyl ethyl ketone 90.0 g and a platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) was mixed to obtain a silicone solution (solid concentration: 0.52% by mass).

(Example 1)
100 g of methyl ethyl ketone and 0.125 g of gallic acid were mixed with 0.6 g of the conductive composite obtained in Production Example 3, and the mixture was stirred at 60° C. for 4 hours for reaction to obtain a conductive polymer dispersion.
The conductive polymer dispersion thus obtained was subjected to No. No. 8 bar coater was used to coat a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) and dried at 100° C. for 1 minute to obtain a conductive film.
Further, 2.95 g of the resulting conductive polymer dispersion was mixed with 14.3 g of the silicone solution obtained in Production Example 4 to obtain a silicone-containing conductive polymer dispersion.
The silicone-containing conductive polymer dispersion thus obtained was subjected to No. No. 8 bar coater was used to coat a polyethylene terephthalate film (Lumirror T60 manufactured by Toray Industries, Inc.) and dried at 150° C. for 1 minute to obtain a conductive release film.

(Example 2)
A conductive film and a conductive release film were obtained in the same manner as in Example 1, except that the amount of gallic acid added was changed to 0.25 g.

(Example 3)
A conductive film and a conductive release film were obtained in the same manner as in Example 1, except that 0.125 g of gallic acid was changed to 0.25 g of 4-hydroxybenzoic acid.

(Comparative example 1)
A conductive film and a conductive release film were obtained in the same manner as in Example 1, except that heating at 60° C. for 4 hours was not performed.

(Comparative example 2)
A conductive film and a conductive release film were obtained in the same manner as in Example 2, except that heating at 60° C. for 4 hours was not performed.

(Comparative Example 3)
A conductive film and a conductive release film were obtained in the same manner as in Example 3, except that heating at 60° C. for 4 hours was not performed.

(Comparative Example 4)
A conductive film and a conductive release film were obtained in the same manner as in Example 1, except that gallic acid was not added.

<Evaluation>
[Measurement of surface resistance value of conductive film]
For the conductive film of each example, the surface resistance value (initial surface resistance value) R0 measured within 1 hour after production, and the surface of the conductive layer was exposed to air adjusted to a temperature of 25 ° C. and a humidity of 50%. The surface resistance value R1 after being left for 10 days in the state was measured. At the time of the measurement, a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used, and the applied voltage was set to 10V. Each measurement result is shown in Table 1.
[Measurement of surface resistance value of conductive release film]
For the conductive release film of each example, the surface resistance value (initial surface resistance value) R2 measured within 1 hour after production, and the surface of the conductive layer was exposed to air adjusted to a temperature of 25 ° C. and a humidity of 50%. The surface resistance value R3 after being left for 1 day in the state of being untouched was measured. At the time of the measurement, a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used, and the applied voltage was set to 10V. Each measurement result is shown in Table 1.
[Measurement of peel strength]
The release force of the conductive layer of the conductive release film of each example was measured by the following method to evaluate the releasability.
A 25 mm wide polyester adhesive tape (manufactured by Nitto Denko Co., Ltd., No. 31B) is placed on the surface of the conductive layer of the conductive release film of each example, and a load of 1976 Pa is placed on the adhesive tape and heated at 25 ° C. for 20 hours. pressure treated. Next, according to JIS Z0237, using a tensile tester, the adhesive tape attached to the conductive layer was peeled off at an angle of 180 ° (peeling speed 0.3 m / min), and the peel force (unit: N) was measured. It was measured. Table 1 shows the measurement results. It means that the lower the peeling force, the higher the releasability of the conductive layer.

The conductive film and conductive release film of each example had low surface resistance values and high conductivity not only immediately after production but also after exposure to the atmosphere. In addition, the conductive release film of each example had a small peeling force and high releasability.
In Comparative Examples 1 to 4, the surface resistance value increased after exposure to the air, and the electrical conductivity decreased. In Comparative Examples 1 to 3, since heating was not performed at 60° C. for 4 hours, the reaction between the substituent (A) and the ester-forming compound did not proceed, and it is presumed that the substituent (B) was not formed. . In Comparative Examples 1 to 4, the polyanion did not have the substituent (B), so it is considered that the decrease in conductivity over time in the air could not be suppressed.

Claims (16)

Containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, and an organic solvent,
The polyanion further has a substituent (B) formed by reacting an ester-forming compound with a substituent (A) formed by reacting a part of an anion group with an epoxy group-containing compound, together with an anion group. ,
The conductive polymer dispersion, wherein the ester-forming compound has at least one phenolic hydroxyl group. 2. The conductive polymer according to claim 1, wherein the ester-forming compound is at least one selected from the group consisting of carboxy group-containing compounds, carboxylic acid halides, carboxylic acid anhydrides, and one-terminal carboxy-modified silicones. dispersion. 3. The conductive polymer dispersion according to claim 1, wherein the ester-forming compound is at least one selected from the group consisting of gallic acid and 4-hydroxybenzoic acid. Containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, and an organic solvent,
A conductive polymer dispersion in which some of the anionic groups of the polyanion are modified with groups having a substituent (B') represented by the following general formula (B').

[In formula (B′), R ¹ is a hydrogen atom or an arbitrary substituent, and R ² is an arbitrary substituent having a phenolic hydroxyl group. ] The conductive polymer dispersion according to any one of claims 1 to 4, wherein the organic solvent contains methyl ethyl ketone. The conductive polymer dispersion according to any one of claims 1 to 5, wherein the organic solvent contains toluene. The conductive polymer dispersion according to any one of claims 1 to 6, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). The conductive polymer dispersion according to any one of claims 1 to 7, wherein the polyanion is polystyrenesulfonic acid. The conductive polymer dispersion according to any one of claims 1 to 8, further comprising a binder component. 10. The conductive polymer dispersion according to claim 9, wherein said binder component is a silicone compound. 11. The conductive polymer dispersion according to claim 10, wherein the silicone compound is an addition-curable silicone. An epoxy group-containing compound is added to an aqueous dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion in an aqueous dispersion medium, and reacted with the polyanion to obtain a precipitate. a precipitation recovery step of recovering the precipitate;
an ester-forming compound addition step of adding a first organic solvent and an ester-forming compound to the collected precipitate to react the precipitate with the ester-forming compound to obtain a first preparation liquid; has
A method for producing a conductive polymer dispersion, wherein the ester-forming compound has at least one phenolic hydroxyl group. 3. The method further comprises a washing step of washing the precipitate with an organic solvent for washing containing an organic solvent having neither a hydroxyl group nor a carboxyl group, between the precipitation recovery step and the ester-forming compound addition step. 13. The method for producing a conductive polymer dispersion according to 12. A drying step of drying an aqueous dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion in an aqueous dispersion medium to obtain a dried conductive composite;
An epoxy group-containing compound and a first organic solvent are added to the dried product , the polyanion contained in the dried product is reacted with the epoxy group-containing compound to obtain a reaction product, and an ester-forming compound is added. a first prepared liquid preparing step of reacting with the reactant to obtain a first prepared liquid. 15. The method for producing a conductive polymer dispersion according to claim 14, further comprising adding a binder component to said first prepared liquid. A coating step of applying the conductive polymer dispersion according to any one of claims 1 to 11 on at least one surface of the film substrate, and drying the coated conductive polymer dispersion. A method for producing a conductive film, comprising a drying step.