JP2017095589A - Conductive polymer aqueous solution, conductive polymer film, and article coated with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a novel conductive polymer aqueous solution, which can form a conductive coating film having excellent moisture resistance; a conductive polymer film having high conductivity; and an article coated with the same.SOLUTION: Provided is a conductive polymer aqueous solution, comprising: 0.01 to 10 wt.% of polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by formula (1) and a structural unit having a positively charged thiophene ring as a counter-cation of the sulfonic acid anion represented by the formula (1); and 0.001 to 10 wt.% of water-soluble polyurethane (B). [L represents an alkylene group or an alkylene oxymethylene group; and M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine, or a quaternary ammonium cation.]SELECTED DRAWING: None

Description

  The present invention is intended to provide a coating film having both conductivity and moisture resistance, and includes a specific self-doped conductive polymer having high conductivity and a specific water-soluble polyurethane. The present invention relates to a novel aqueous conductive composition solution, and further relates to a conductive polymer film obtained by drying them, and a coated article thereof.

  Conductive polymer materials have been developed by doping π-conjugated polymers such as polyacetylene, polythiophene, polyaniline, and polypyrrole with electron-accepting compounds as dopants. For example, antistatic agents, capacitor solid electrolytes, conductivity Applications to paints, electromagnetic shielding, electrochromic elements, electrode materials, thermoelectric conversion materials, transparent conductive films, chemical sensors, actuators, etc. are being studied. Among these conductive polymer materials, polythiophene-based conductive polymer materials are practically useful from the viewpoint of chemical stability.

  As a polythiophene-based conductive polymer material, a PEDOT / PSS aqueous dispersion solution obtained by polymerizing 3,4-ethylenedioxythiophene (EDOT) in an aqueous solution of polystyrene sulfonic acid (PSS) serving as a dopant, There are so-called self-doped conductive polymers having substituents (sulfo groups, sulfonate groups, etc.) having water solubility and doping action, either directly or via spacers in the polymer main chain, such as sulfonation Polyaniline, PEDOT-S and the like are known (see, for example, Patent Documents 1 and 2).

  Conductive polymers are not only used for solid electrolytes of antistatic agents and solid electrolytic capacitors, but in recent years, studies have been made on mounting them in various electronic devices as antistatic films and conductive films (for example, touch panels). In addition, from the viewpoint of extending the life of the device, the conductive composition itself that is used is also required to have durability (heat resistance and moisture resistance in a solid or coating state). . For this reason, the request | requirement of the highly durable conductive polymer film with a little raise of surface resistance is increasing.

Japanese Patent Laying-Open No. 2015-63652 Japanese Patent Laying-Open No. 2015-147834

  The present invention has been made in view of the above-described background art, and an object thereof is to provide a conductive polymer film in which the increase in surface resistance due to humidity is remarkably small.

  As a result of intensive studies to solve the above problems, the present inventors have found that the aqueous conductive polymer solution of the present invention characterized by containing a water-soluble polyurethane solves the above problems. Was completed.

That is, the present invention relates to a composition of a conductive polymer aqueous solution as shown below, a conductive polymer film, and a coated article thereof.
[1]
0.01 to 10% by weight of polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): A conductive polymer aqueous solution containing 0.001 to 10% by weight of the water-soluble polyurethane (B).

[In the above formulas (1) and (2), L represents the following formula (3) or formula (4), and M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. Represent. ]

[In said formula (3), l represents the integer of 6-12. ]

[In said formula (4), m represents the integer of 1-6. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ]
[2]
The aqueous conductive polymer solution according to [1], wherein the water-soluble polyurethane (B) is a nonionic water-soluble polyurethane.
[3]
[1] or [2], further comprising 0.001 to 10% by weight of at least one surfactant (C) selected from the group consisting of nonionic surfactants and amphoteric surfactants. Conductive polymer aqueous solution.
[4]
Surfactant (C) is polyvinyl pyrrolidone, polyvinyl pyrrolidone copolymer, polyethylene glycol type surfactant, acetylene glycol type surfactant, polyhydric alcohol type surfactant, betaine type amphoteric surfactant, fluorine-based interface The aqueous conductive polymer solution according to [3], which is at least one selected from the group consisting of an activator and a silicone-based surfactant.
[5]
The conductive polymer aqueous solution according to any one of [1] to [4], further comprising at least one water-soluble compound (D) selected from the group consisting of an alcohol and a water-soluble resin.
[6]
The conductive polymer according to [5], wherein the alcohol is at least one alcohol selected from the group consisting of a monovalent alcohol, a divalent alcohol, a trivalent alcohol, and a sugar alcohol. Aqueous solution.
[7]
The aqueous conductive polymer solution according to [5], wherein the water-soluble resin is at least one selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, and water-soluble polyester.
[8]
The conductive polymer aqueous solution according to [1] to [7], further comprising an amine compound (E) and having a pH of 9 or less.
[9]
[1] A method for producing a film, comprising drying the aqueous conductive polymer solution according to any one of [8].
[10]
A film comprising a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) and a water-soluble polyurethane (B) .

[In the above formulas (1) and (2), L represents the following formula (3) or formula (4), and M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. Represent. ]

[In said formula (3), l represents the integer of 6-12. ]

[In said formula (4), m represents the integer of 1-6. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ]
[11]
A coated article in which at least a part of the support is covered with the film according to [10].

  Since the conductive polymer film and the coated article prepared from the novel conductive polymer aqueous solution of the present invention have high conductivity and moisture resistance, the antistatic film, the solid electrolyte of the solid electrolytic capacitor, and the winding It can be expected to be used as a separator for revolving aluminum solid electrolytic capacitors.

  Hereinafter, the present invention will be described in detail. The present invention provides 0.01 to 10 polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). It is a conductive polymer aqueous solution containing 1% by weight and containing 0.001 to 10% by weight of water-soluble polyurethane (B).

[In the above formulas (1) and (2), L represents the following formula (3) or formula (4), and M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. Represent. ]

[In said formula (3), l represents the integer of 6-12. ]

[In said formula (4), m represents the integer of 1-6. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ]
In the above formula (1) or (2), M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation.

  As said alkali metal ion, Li ion, Na ion, and K ion are preferable, for example.

As the conjugate acid of the amine compound, an amine compound which is a cationic species by adding hydrone (H ⁺ ) to the amine compound may be used as long as it is a amine compound that reacts with a sulfonic acid group to form a conjugate acid. An amine compound represented by N (R ¹ ) ₃ having an sp3 hybrid orbital [represented by [NH (R ¹ ) ₃ ] ⁺ as the conjugate acid. Or a pyridine compound or an imidazole compound having a sp2 hybrid orbital.

Each of the substituents R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms having a substituent.

  Although it does not specifically limit as a C1-C6 alkyl group, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- A butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, cyclohexyl group and the like can be mentioned.

  Examples of the alkyl group having 1 to 6 carbon atoms having a substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an amino group, or an alkyl group having 1 to 6 carbon atoms having a hydroxy group. Specifically, a trifluoromethyl group, 2-hydroxyethyl group, etc. are illustrated.

Among these, as the substituent R ¹ , a hydrogen atom, a methyl group, an ethyl group, and a 2-hydroxyethyl group are preferable independently.

The amine compound that forms the conjugate acid of the amine compound is not particularly limited, and examples thereof include an amine compound represented by N (R ¹ ) ₃ and an amine compound not represented by N (R ¹ ) _3. .

The amine compound represented by N (R ¹ ) ₃ is not particularly limited, and examples thereof include ammonia, methylamine, dimethylamine, ethylamine, triethylamine, normal-propylamine, isopropylamine, normal butylamine, and tarsha. Libutylamine, hexylamine, ethanolamine compounds (for example, aminoethanol, dimethylaminoethanol, methylaminoethanol, diethanolamine, N-methyldiethanolamine, triethanolamine), 3-amino-1,2-propanediol, 3-methylamino -1,2-propanediol, 3-dimethylamino-1,2-propanediol, 1,4-butanediamine and the like.

In addition, the amine compound not represented by N (R ¹ ) ₃ is not particularly limited, and examples thereof include imidazole compounds (eg, imidazole, N-methylimidazole, 1,2-dimethylimidazole), pyridine picoline, Lutidine and the like. Of these, ethanolamine compounds and imidazole compounds are preferred.

  That is, as the conjugate acid of the amine compound, ammonium, monoethanolamine conjugate acid, diethanolamine conjugate acid, triethanolamine conjugate acid, or imidazole conjugate acid is preferable from the viewpoint of excellent conductivity.

  Examples of the quaternary ammonium cation include a tetramethyl ammonium cation, a tetraethyl ammonium cation, a tetra normal propyl ammonium cation, a tetra normal butyl ammonium cation, and a tetra normal hexyl ammonium cation. From the viewpoint of availability, a tetramethylammonium cation and a tetraethylammonium cation are preferable.

  In said formula (3), l represents the integer of 6-12, Preferably it is an integer of 6-8.

In the formula (4), R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom.

  Although it does not specifically limit as a C1-C6 linear or branched alkyl group, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, cyclohexyl group and the like.

R ^{2 in the} formula (4) is preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom from the viewpoint of film formability.

  In said formula (4), m represents the integer of 1-6, Preferably, m is an integer of 1-4, More preferably, it is 2.

  The structural unit represented by the above formula (2) represents the doping state of the structural unit represented by the above formula (1).

  The dopant causing the insulator-metal transition by doping is divided into an acceptor and a donor. The former enters near the polymer chain of the conductive polymer by doping and takes π electrons from the conjugated system of the main chain. As a result, since positive charges (holes, holes) are injected onto the main chain, it is also called a p-type dopant. The latter is also referred to as an n-type dopant because it gives electrons to the conjugated system of the main chain, which moves in the conjugated system of the main chain.

  The dopant in the present invention is a sulfo group or a sulfonate group that is covalently bonded in the polymer molecule, and is a p-type dopant. Such a polymer that exhibits conductivity without adding a dopant from the outside is called a self-doped polymer.

  The polythiophene (A) of the present invention can be produced by polymerizing a thiophene monomer represented by the following formula (5) in water or an alcohol solvent in the presence of an oxidizing agent.

[In the above formula (5), L has the same definition as above. M represents a metal ion. ]
Although it does not specifically limit as a metal ion represented by M in Formula (5), A transition metal ion, a noble metal ion, a nonferrous metal ion, an alkali metal ion (for example, Li ion, Na ion, and K ion) And alkaline earth metal ions.

Since the polymer after polymerization is a metal salt, M can be converted to a hydrogen ion by acid treatment of the obtained polymer, if necessary, and further reacted with an amine compound, whereby M is converted to an amine. As a thiophene monomer for obtaining the polythiophene of the present invention in which L is represented by the above formula (3) in the above formula (1) or formula (2), 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1-sulfonic acid, 6- (2,3-dihydro-thieno [3,4] -B] [1,4] dioxin-2-yl) sodium hexane-1-sulfonate, 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) Hexane-1-lithium sulfonate, 6- ( 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1-sulfonate potassium, 8- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) octane-1-sulfonic acid, 8- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) octane-1- Examples include sodium sulfonate and potassium 8- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) octane-1-sulfonate.

As the thiophene monomer for obtaining the polythiophene of the present invention in which L is represented by the above formula (4) in the above formula (1) or (2), specifically, 3-[(2,3- Sodium dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1, 4] dioxin-2-yl) methoxy] -1-propanesulfonic acid potassium, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1 -Sodium methyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-
b]-[1,4] dioxin-2-yl) methoxy] -1-ethyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] Dioxin-2-yl) methoxy] -1-propyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] Sodium 1-butyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-pentyl-1-propane Sodium sulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,
4] dioxin-2-yl) methoxy] -1-hexyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) Methoxy] -1-isopropyl-1-propanesulfonic acid sodium salt, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isobutyl-1 Sodium propanesulfonate, sodium 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isopentyl-1-propanesulfonate, 3- [(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-propanesulfonic acid sodium salt, 3-[(2,3-di Drothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b] -[1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonic acid, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2 -Yl) methoxy] -1-methyl-1-propanesulfonate ammonium, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1- Triethylammonium methyl-1-propanesulfonate, sodium 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-butanesulfonate, 4- [(2,3- Hydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-butanesulfonate potassium, 4-[(2,3-dihydrothieno [3,4-b]-[1, 4] Sodium dioxin-2-yl) methoxy] -1-methyl-1-butanesulfonate, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) Methoxy] -1-methyl-1-butanesulfonate, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1 -Sodium butanesulfonate, potassium 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-butanesulfonate, etc. Illustrated.

  In the present invention, the electrical conductivity of the polythiophene (A) is not particularly limited, but the electrical conductivity (electric conductivity) in the film state is preferably 10 S / cm or more.

  Although the water-soluble polyurethane in the present invention is not particularly limited, it is also referred to as a water-based urethane resin, and is generally obtained by imparting hydrophilicity to the originally hydrophobic urethane resin by various methods and water-dispersed. There are forced emulsification type and self-emulsification type. Also, it is classified into non-yellowing type / yellowing type, ester type, ether type, ester / ether type depending on the raw materials used, and classified into nonionic (nonionic), anionic, and cationic types according to the charge state of the particles. However, any of them may be used in the present invention.

  The water-soluble polyurethane used in the present invention is not particularly limited as long as it does not cause gelation, precipitation, precipitation, or the like when added to a conductive polymer aqueous solution, but more preferably nonionic (nonionic) ) Is preferred. Moreover, when the transparency of a coating film is calculated | required, a non-yellowing type thing is preferable.

  The aqueous conductive polymer solution of the present invention may further contain 0.001 to 10% by weight of at least one surfactant (C) selected from the group consisting of a nonionic surfactant and an amphoteric surfactant. .

  As the surfactant (C), for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a fluorosurfactant, or a silicone surfactant can be used. More preferably, it is at least one selected from the group consisting of a nonionic surfactant and an amphoteric surfactant.

  Although it does not specifically limit as a nonionic surfactant, For example, a polyethyleneglycol type surfactant, an acetylene glycol type surfactant, a polyhydric alcohol type surfactant, a polymeric nonionic surfactant etc. are mentioned. It is done.

  Examples of the polyethylene glycol surfactant include higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, Examples thereof include an ethylene oxide adduct of fats and oils or a polypropylene glycol ethylene oxide adduct.

  Examples of the acetylene glycol type surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, Surfynol (manufactured by Air Products), orphine (manufactured by Nissin Chemical Industry Co., Ltd.). Etc.

  Examples of the polyhydric alcohol surfactant include glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester, high alcohol alkyl ether, alkanolamine fatty acid amide and the like. Can be mentioned.

  The polymer type nonionic surfactant is not particularly limited, and examples thereof include polyvinylpyrrolidone and polyvinylpyrrolidone copolymers. The average molecular weight of polyvinylpyrrolidone used in the present invention is 1,000 to 2,000,000, preferably 10,000 to 1,500,000. The copolymer of polyvinyl pyrrolidone is not particularly limited, but a copolymer having a hydrophilic part and a hydrophobic part in the polymer chain is preferable. For example, a copolymer obtained by grafting polyvinyl pyrrolidone to polyvinyl alcohol, [vinyl pyrrolidone, -Vinyl acetate block copolymer, [vinyl pyrrolidone-methyl methacrylate] copolymer, [vinyl pyrrolidone-normal butyl methacrylate] copolymer, [vinyl pyrrolidone-acrylamide] copolymer, and the like.

  Although it does not specifically limit as an amphoteric surfactant, For example, a betaine type | mold amphoteric surfactant is mentioned. The betaine-type amphoteric surfactant is not particularly limited, and examples thereof include alkyldimethylbetaine, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.

The fluorosurfactant is not particularly limited as long as it has a perfluoroalkyl group, and examples thereof include perfluoroalkane, perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, and perfluoroalkylethylene oxide adduct. It is done.

  The silicone-based surfactant is not particularly limited, but polyether-modified polydimethylsiloxane, polyetherester-modified polydimethylsiloxane, hydroxyl group-containing polyether-modified polydimethylsiloxane, acrylic group-containing polyether-modified polydimethylsiloxane, acrylic group-containing Examples thereof include polyester-modified polydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, and silicone-modified acrylic compound.

  Fluorine-based surfactants and silicone-based surfactants are effective for improving the flatness of the coating film as leveling agents.

  In the present invention, the surfactant (C) has a solubility in water of preferably 0.01% by weight or more at 80 ° C., more preferably 0.01% by weight or more at 30 ° C. Is more preferably 0.01% by weight or more, and a surfactant having an HLB in the range of 7 to 20 is preferable.

  The Griffin method HLB (Hydrophile-Lipophile Balance) is a numerical value representing the hydrophilicity of the surfactant. It shows that hydrophilic property is so large that a value is large, and it represents with following Formula.

Griffin method HLB of nonionic surfactant
= (Molecular weight of hydrophilic group part) / (Molecular weight of surfactant) × 100/5
= (Weight of hydrophilic group) / (weight of hydrophobic group + weight of hydrophilic group) × 100/5
= (Weight% of hydrophilic group) / 5
In the present invention, the surfactant (C) is more preferably an acetylene glycol type surfactant or a polymer type surfactant.

  As a method for adding the surfactant (C) to the aqueous conductive polymer solution, it may be added as a solid, or a solution prepared in advance as an aqueous solution may be added. In that case, you may add independently to a conductive polymer aqueous solution, and may mix and add 2 or more types.

  When the conductive polymer aqueous solution of the present invention contains a surfactant (C), the conductive polymer aqueous solution contains 0.1 to 10% by weight of polythiophene (A) and 0.001 of water-soluble polyurethane (B). It is preferable to contain 10 to 10 weight% and surfactant (C) 0.001 to 10 weight%.

  The aqueous conductive polymer solution of the present invention may further contain at least one water-soluble compound (D) selected from the group consisting of alcohols and water-soluble resins.

  Although it does not specifically limit as alcohol, For example, at least 1 type of alcohol selected from the group which consists of monohydric alcohol, bivalent alcohol, trivalent alcohol, and sugar alcohol is mentioned.

  Although it does not specifically limit as monovalent alcohol, For example, methanol, ethanol, 1-propanol, isopropanol, a butanol etc. are mentioned, However, Ethanol is preferable from the point of operativity. The dihydric alcohol is not particularly limited, but ethylene glycol is preferable from the viewpoint of availability. Although it does not specifically limit as a trihydric alcohol, For example, glycerol is preferable. Although it does not specifically limit as sugar alcohol, For example, erythritol, sorbitol, arabitol etc. are preferable. More preferred is sorbitol.

  The water-soluble resin is not particularly limited, but for example, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone, poly (N-vinylacetamide), water-soluble polyester, water-soluble polyurethane, and the like are preferable. In addition, about these water-soluble resin, it is preferable to use the thing which performed the metal removal filter process using a granular form and a film-form cation exchange resin, and a zeta potential from a viewpoint of metal amount reduction.

  The molecular weight of the water-soluble resin is not particularly limited as long as water solubility is good, but preferably Mw = 1,000 to 2,000,000, more preferably 10,000 to 1,500,000, still more preferably Mw = 1,000 to 250,000, Preferably it is the range of 1,000-50,000.

  When the conductive polymer aqueous solution of the present invention contains a water-soluble compound (D), the water-soluble polymer aqueous solution contains 0.1 to 10% by weight of polythiophene (A) and 0.001 of water-soluble polyurethane (B). It is preferable to contain 10 to 10% by weight of the surfactant (C) and 0.001 to 10% by weight of the water-soluble compound (D).

  The method for preparing the aqueous conductive polymer solution of the present invention is not particularly limited. For example, the aqueous solution or solid of the polythiophene (A) of the present invention, the water-soluble polyurethane (B), and as necessary. A surfactant (C), a water-soluble compound (D) as necessary, water as necessary, and other additives as necessary can be used. By mixing these in any order, the conductive polymer aqueous solution of the present invention can be prepared.

  Here, the temperature at the time of mixing is not particularly limited, but can be performed, for example, from room temperature to warming. Preferably it is 0 degreeC or more and 100 degrees C or less.

  The atmosphere at the time of mixing is not particularly limited, but may be in the air or in an inert gas.

  The pH of the aqueous conductive polymer solution of the present invention is preferably 10 or less, and more preferably 9 or less. Furthermore, the pH of the aqueous conductive polymer solution of the present invention is preferably in the range of 1.5 or more and 9.5 or less, and more preferably in the range of 1.5 or more and 9 or less. Here, the procedure for adjusting the pH is not particularly limited. For example, the pH is adjusted by adding the amine compound (E) after mixing the polythiophene (A) and the water-soluble polyurethane (B). be able to. Further, the pH may be adjusted by adding the amine compound (E) in advance to the aqueous solution of polythiophene (A). Moreover, when using in the acidic region whose pH is 2 or less, it is not always necessary to add an amine.

  The amine compound (E) is not particularly limited, and examples thereof include ammonia, methylamine, dimethylamine, ethylamine, triethylamine, normal-propylamine, isopropylamine, normal butylamine, tertiary butylamine, hexylamine, and aminoethanol. , Dimethylaminoethanol, methylaminoethanol, diethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine, 3-amino-1,2-propanediol, 3-methylamino-1,2-propanediol 3-dimethylamino-1,2-propanediol, 1,4-butanediamine, imidazole, N-methylimidazole, 1,2-dimethylimidazole, pyridine, picoline, rutile Emissions, and the like. When adding, it may be neat or an aqueous solution.

  When mixing the aqueous conductive polymer solution of the present invention, in addition to general mixing and dissolving operations using a stirrer chip, a stirring blade, etc., ultrasonic irradiation, homogenization treatment (for example, mechanical homogenizer, ultrasonic homogenizer, high-pressure homogenizer) May be used). In the case of homogenizing treatment, it is preferable to carry out the treatment while cooling in order to prevent thermal degradation of the polymer.

  The concentration adjustment of the aqueous conductive polymer solution of the present invention may be adjusted by the mixing ratio, or may be adjusted by concentration after mixing. The concentration method may be a method of distilling off the solvent under reduced pressure, or a method using an ultrafiltration membrane.

  The concentration of polythiophene (A) in the aqueous conductive polymer solution of the present invention is not particularly limited as long as it is 0.001% by weight or more, but is preferably in the range of 0.01% by weight to 10% by weight. . In addition, since the conductive polymer aqueous solution containing the polythiophene (A) and the water-soluble polyurethane (B) of the present invention is dried and dehydrated after coating, a good uniform film can be obtained in the above concentration range.

  The particle size of the solid content in the aqueous conductive polymer solution of the present invention is not particularly limited, but the smaller the particle size, the better the water solubility, which is desirable from the viewpoint of conductivity and uniform film formation during film formation. . For example, when the solid content concentration of the aqueous conductive polymer solution prepared at room temperature or under heating is 10% by weight or less, the water solubility is better if the particle size (D50) of the solid content is 0.02 μm or less. Become.

  The viscosity (20 ° C.) of the aqueous conductive polymer solution of the present invention is not particularly limited as long as it is 200 mPa · s or less, but is preferably 100 mPa · s or less, more preferably 50 mPa · s or less.

  The method for forming the conductive polymer film from the conductive polymer aqueous solution of the present invention is not particularly limited. For example, the conductive polymer aqueous solution of the present invention is applied to a support and dried. A conductive polymer film can be easily obtained on a support (hereinafter, the support and the conductive polymer film are collectively referred to as “coated article”).

  The support is not particularly limited as long as the conductive polymer aqueous solution of the present invention can be applied, and examples thereof include a polymer substrate and an inorganic substrate. Examples of the polymer substrate include thermoplastic resins, nonwoven fabrics, paper, resist film substrates, and the like. Examples of the thermoplastic resin include polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polycarbonate, and the like. As a nonwoven fabric, any of a natural fiber, a synthetic fiber, or glass fiber may be sufficient, for example. The paper may be composed mainly of general cellulose. Examples of the inorganic substrate include glass, metal oxides such as ITO, ceramics, aluminum oxide, tantalum oxide, and the like.

  Examples of the coating method of the conductive polymer aqueous solution include casting method, dipping method, bar coating method, dispenser method, roll coating method, gravure coating method, flexographic printing method, spray coating method, spin coating method, and ink jet method. Can be mentioned. A bar coating method and a spin coating method are preferred.

  The drying temperature of the coating film is not particularly limited as long as it is equal to or lower than the temperature at which a uniform conductive polymer film can be obtained and the heat resistance temperature of the substrate, but it is in the range of room temperature to 300 ° C, preferably room temperature to 250 It is the range of ° C, and more preferably in the range of room temperature to 200 ° C.

  The dry atmosphere may be any of air, inert gas, vacuum, or reduced pressure. From the viewpoint of suppressing deterioration of the polymer film, it is preferably in an inert gas such as nitrogen or argon.

Although it does not specifically limit as a film thickness of the conductive polymer film obtained, The range of 10 < ^-3 > ^-10 < ² > micrometer is preferable. More preferably, it is 10 ⁻³ to 10 ⁻¹ μm. The conductivity of the conductive polymer film is not particularly limited but is preferably high. In addition, since the conductivity of the conductive polymer film varies depending on the type and amount of the surfactant or water-soluble resin to be added, it cannot be uniquely determined, but the surface resistance value of the obtained conductive polymer film Is not particularly limited, but is preferably 1.0E + 11Ω / □ or less, more preferably 1.0E + 9Ω / □ or less, and further preferably 1.0E + 7Ω / □ or less. Although the applied voltage at the time of measuring a surface resistance value is not specifically limited, it measures by 10V or 500V.

  The coated article of the present invention is used, for example, as an antistatic film, a solid electrolyte for a solid electrolytic capacitor, or a separator for a wound aluminum solid electrolytic capacitor.

  Examples relating to the present invention will be described below.

The analytical instruments and measurement methods used in this example are listed below.
[GC measurement]
Apparatus: Shimadzu, GC-2014
[NMR measurement]
Apparatus: VARIAN, Gemini-200
[Surface resistivity measurement]
Equipment: Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation
Equipment: Hiresta UX MCP-HT8000 manufactured by Mitsubishi Chemical Corporation
[Film thickness measurement]
Equipment: DEKTAK XT manufactured by BRUKER
[Viscosity measurement]
Complete Viscometer / BROOKFIELD VISCOMETER DV-1 Prime
Electrical conductivity [S / cm] = 10 ⁴ / (surface resistivity [Ω / □] × film thickness [μm])
[Particle size measurement]
Apparatus: Nikkiso Co., Ltd. Microtrac Nanotrac UPA-UT151
[Measurement of conductivity of self-doped conductive polymer]
0.5 ml of an aqueous solution containing a self-doped conductive polymer is applied to a 25 mm square non-alkali glass plate, dried at room temperature overnight, then on a hot plate at 120 ° C. for 20 minutes, and further at 160 ° C. for 10 minutes. A conductive polymer film was obtained by heating. It calculated based on the following formula | equation from the film thickness and the surface resistance value.
[Applicability & Antistatic evaluation]
(1) Evaluation of applicability to polymer substrate (thermoplastic resin).
After the conductive polymer aqueous solution was cast so as to spread over the entire PET film (2.5 cm square), it was formed by spin coating (manufactured by MIKASA: spinner 1H-D2) (1200 rpm × 40 seconds, then 100 ° C. × 60 seconds vacuum drying). The surface resistance value of the obtained coating film was measured. If the surface resistance value was stable, the coating property was good, and if the surface resistance value of the obtained conductive polymer film was 1.0E + 9Ω / □ or less, it was judged that the antistatic ability was good.
[Transparency evaluation of coating film (transmittance, haze ratio)]
-Equipment: Nippon Denshoku Co., Ltd. Haze meter NDH4000
・ Conditions: Base material blank [Evaluation of coating durability]
-Heat resistance evaluation device: Constant temperature dryer EOP-450B (natural convection method) manufactured by ETTAS
Conditions: 80 ° C., 300 hours Evaluation: A case where the rate of increase in surface resistivity after the test before the test was less than 10 times was considered good. Ten times or more was regarded as defective.
-Moisture resistance evaluation apparatus: SH-241 manufactured by ESPEC
Conditions: 60 ° C., 95% RH, 300 hours Evaluation: A case where the rate of increase in surface resistivity after the test before the test was less than 100 times was considered good. 100 times or more was regarded as defective.

Synthesis Example 1
3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonic acid sodium [represented by the following formula (6) Compound].
Under a nitrogen atmosphere, 0.437 g (10.9 mmol) of 60% sodium hydride and 37 ml of toluene were charged into a 100 ml eggplant type flask, and then (2,3-dihydrothieno [3,4-b] [1,4] dioxin- 2-yl) methanol 1.52 g (8.84 ml) was added. Thereafter, the reaction solution was heated to the reflux temperature and stirred at the same temperature for 1 hour. Then, the liquid mixture which consists of 1.21 g (8.89 mmol) of 2, 4- butane sultone and 10 ml of toluene was dripped, and it stirred at the same temperature for 2 hours. After cooling, the resulting reaction solution was added dropwise to 160 ml of acetone for reprecipitation. The obtained powder was filtered and vacuum-dried to obtain 1.82 g of a pale yellow powder with a yield of 62%. From NMR measurement, this is represented by the following formula (6): 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1 -Confirmed to be sodium propanesulfonate.

1H-NMR (D ₂ O) δ (ppm); 6.67 (s, 2H), 4.54 to 4.60 (m, 1H), 4.45 (dd, 1H, J = 12.0, 2 .2 Hz), 4.26 (dd, 1H, J = 12.0, 6.8 Hz), 3.90-3.81 (m, 4H), 3.10-3.18 (m, 1H), 2 .30-2.47 (m, 1H), 1.77-1.92 (m, 1H), 1.45 (d, 3H)
13C-NMR (D2O) δ (ppm); 14.91, 31.22, 53.13, 66.18, 69.18, 73.29, 73.36, 100.81, 100.94, 140.88 141.06
Synthesis Example 2
Synthesis of polythiophene (A) [polymer containing a structural unit represented by the following formula (7) or the following formula (8)].
3-[(2,3-Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1 synthesized according to Synthesis Example 1 in a 500 ml separable flask -10 g (30 mmol) of sodium propanesulfonate and 150 g of water were added. After dissolution, 2.94 g (18.1 mmol) of anhydrous iron (III) chloride was added at room temperature and stirred for 20 minutes. Thereafter, a mixed solution consisting of 14.5 g (60.4 mmol) of sodium persulfate and 100 g of water was added dropwise while maintaining the reaction solution temperature at 30 ° C. or lower. After stirring at room temperature for 3 hours, the reaction solution was dropped into 800 g of acetone to precipitate a black Na-type polymer. The polymer was filtered and vacuum-dried to obtain 18.0 g of 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1 -A crude polymer of sodium propanesulfonate was obtained.

  Next, 700 g of an aqueous solution prepared by adding water to 14.5 g of this crude polymer to prepare a 2% by weight solution was passed through a column packed with 200 ml of the cation exchange resin Lewatit MonoPlus S100 (H type) (space velocity = 1.1). ) To obtain 738 g of an H-type polymer aqueous solution. Furthermore, this polymer aqueous solution is expressed by the following formula (7) or formula (8) by purifying by cross-flow ultrafiltration (filter = Vivaflow 200, fractional molecular weight = 5,000, permeation rate = 5). As a result, 698 g of a deep blue aqueous solution of a polymer containing the structural unit was obtained. The amount of polymer contained in this aqueous polymer solution was 0.74% by weight. Further, iron ions and sodium ions were contained in 44 ppm and 12 ppm (vs. polymer), respectively.

Synthesis Example 3
Synthesis of polythiophene (A) [polymer containing a structural unit represented by the following formula (9) or the following formula (10)].
Polythiophene (A) obtained according to Synthesis Example 2 [Polymer containing structural unit represented by Formula (7) or Formula (8)] An aqueous solution of 50% by weight of N, N-dimethyl is stirred. An aqueous aminoethanol solution was added until the aqueous solution reached pH 7.8, and then water was evaporated so that the solid content was 2% by weight to obtain an aqueous polymer solution. The electrical conductivity of this aqueous polymer solution was 119 S / cm.

実施例１．
合成例３で得られたポリチオフェン（Ａ）［前記式（９）又は前記式（１０）で表される構造単位を含む重合体］［導電率１１９Ｓ／ｃｍ］を２．０重量％含む水溶液 １．８７４ｇに、界面活性剤として、高分子型非イオン界面活性剤のポリビニルピロリドンＫ９０（ＢＡＳＦ社製 ＳｏｋａｌａｎＫ９０ 分子量１４０万）を２．５重量％含む水溶液 ０．５６４ｇ、エタノール ０．７４１ｇ、水溶性ポリウレタンとしてスーパーフレックスＳＦＥ２０００（第一工業製薬社製）の５．０％水溶液 ０．２７４ｇ、 水 ６．５５０ｇを加えてよく攪拌混合した後、７．５％エタノール水溶液で５倍希釈した。このようにして得られた導電性高分子水溶液 ０．２ｇを、７ｃｍ×１４ｃｍにカットしたＰＥＴフィルム（東レ社製ルミラーＴ６０／３８μｍ）にバーコーター（オーエスジーシステムプロダクト社製セレクトローラーＯＳＰ−２２）を用いて一定速度で塗布した後、乾燥器で９０℃３分乾燥して積層フィルムを得た。得られた膜は斑の無い均一状態を示し、且つ当該膜の表面抵抗値は、測定箇所によらず安定的に４．００Ｅ＋７Ω／□を示した。また、本実施例で作製した積層フィルムの透過率は９７．３０％であった。本実施例で作製した積層フィルムの耐久性試験の結果を下表１に示す。

Example 1.
1. An aqueous solution containing 2.0% by weight of the polythiophene (A) obtained in Synthesis Example 3 [polymer containing the structural unit represented by the formula (9) or the formula (10)] [conductivity 119 S / cm] 0.574 g of an aqueous solution containing 2.5% by weight of a polymer type nonionic surfactant polyvinylpyrrolidone K90 (Sokalan K90 molecular weight 1.4 million by BASF) as a surfactant in 874 g, water-soluble polyurethane Then, 0.274 g of a 5.0% aqueous solution of Superflex SFE2000 (Daiichi Kogyo Seiyaku Co., Ltd.) and 6.550 g of water were added and mixed well with stirring, and then diluted 5-fold with a 7.5% aqueous ethanol solution. A bar coater (Select Roller OSP-22 manufactured by OSG System Products Co., Ltd.) is applied to a PET film (Lumilar T60 / 38 μm manufactured by Toray Industries, Inc.) obtained by cutting 0.2 g of the conductive polymer aqueous solution thus obtained into 7 cm × 14 cm. After being used and coated at a constant speed, it was dried in a dryer at 90 ° C. for 3 minutes to obtain a laminated film. The obtained film showed a uniform state without spots, and the surface resistance value of the film stably showed 4.00E + 7Ω / □ regardless of the measurement location. Moreover, the transmittance of the laminated film produced in this example was 97.30%. The results of the durability test of the laminated film produced in this example are shown in Table 1 below.

Example 2
In Example 1, it carried out based on Example 1 except having changed the water-soluble polyurethane into Superflex SF500M (Daiichi Kogyo Seiyaku Co., Ltd.). The results of the durability test of the laminated film produced in this example are shown in Table 1 below.

  As is apparent from Examples 1 and 2, the surface resistivity of the coating film is in the range of 1.30 times or less even after 300 hours at 60 ° C. and 95% RH in the moisture resistance test, and exhibits good moisture resistance. I understood. In addition, the transmittance of the coating film was not changed before and after the test and showed good moisture resistance.

  The conductive polymer aqueous solution of the present invention can further form a polymer film having good conductivity and moisture resistance. In addition to substrates such as glass and metal, it has good wettability to polymer substrates and can be applied without cissing or spots. Therefore, it can be used as a conductive coating agent (antistatic agent) on various substrates, a solid electrolyte (cathode material) of a solid electrolytic capacitor, and the like. Further, a coated article comprising a polymer substrate coated with this conductive polymer film can be used for an antistatic film, a solid electrolyte for a solid electrolytic capacitor, and a separator for a wound aluminum electrolytic capacitor. In addition, electrochromic elements, transparent electrodes, transparent conductive films, thermoelectric conversion materials, chemical sensors, actuators, electromagnetic shielding materials, surface coating materials for metal oxides such as ITO, which are electrode materials for organic EL and solar cells, etc. Applications can also be expected.

  Moreover, by covering the nonwoven fabric or paper with the conductive polymer film of the present invention, the coating can be used as a film having an antistatic function or as a separator for a solid electrolytic capacitor.

Claims (11)

0.01 to 10% by weight of polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): A conductive polymer aqueous solution containing 0.001 to 10% by weight of the water-soluble polyurethane (B).

[In the above formulas (1) and (2), L represents the following formula (3) or formula (4), M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. Represent. ]

[In said formula (3), l represents the integer of 6-12. ]

[In said formula (4), m represents the integer of 1-6. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ] The aqueous conductive polymer solution according to claim 1, wherein the water-soluble polyurethane (B) is a nonionic water-soluble polyurethane. Furthermore, 0.001-10 weight% of at least 1 sort (s) of surfactant (C) chosen from the group which consists of a nonionic surfactant and an amphoteric surfactant is included, either of Claim 1 or Claim 2 characterized by the above-mentioned. An aqueous conductive polymer solution according to claim 1. Surfactant (C) is polyvinyl pyrrolidone, polyvinyl pyrrolidone copolymer, polyethylene glycol type surfactant, acetylene glycol type surfactant, polyhydric alcohol type surfactant, betaine type amphoteric surfactant, fluorine-based interface The aqueous conductive polymer solution according to claim 3, which is at least one selected from the group consisting of an activator and a silicone-based surfactant. The conductive polymer aqueous solution according to any one of claims 1 to 4, further comprising at least one water-soluble compound (D) selected from the group consisting of alcohol and a water-soluble resin. The conductive polymer according to claim 5, wherein the alcohol is at least one alcohol selected from the group consisting of a monohydric alcohol, a dihydric alcohol, a trihydric alcohol, and a sugar alcohol. Aqueous solution. 6. The conductive polymer aqueous solution according to claim 5, wherein the water-soluble resin is at least one selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, and water-soluble polyester. The conductive polymer aqueous solution according to claim 1, further comprising an amine compound (E) and having a pH of 10 or less. A method for producing a film, comprising drying the aqueous conductive polymer solution according to any one of claims 1 to 8. A film comprising a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) and a water-soluble polyurethane (B) .

[In the above formulas (1) and (2), L represents the following formula (3) or formula (4), M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. Represent. ]

[In said formula (3), l represents the integer of 6-12. ]

[In said formula (4), m represents the integer of 1-6. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ] A coated article in which at least a part of the support is covered with the film according to claim 10.