JP6645138B2 - Conductive polymer aqueous solution, conductive polymer film, and coated article - Google Patents

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 solution of a conductive composition, and further relates to a conductive polymer film obtained by drying them, and a coated article thereof.

  Conductive polymer materials in which a π-conjugated polymer represented by polyacetylene, polythiophene, polyaniline, polypyrrole, and the like are doped with an electron-accepting compound as a dopant have been developed. Applications to paints, electromagnetic wave shields, electrochromic devices, electrode materials, thermoelectric conversion materials, transparent conductive films, chemical sensors, actuators, and the like are being studied. Among these conductive polymer materials, a polythiophene-based conductive polymer material is practically useful from the viewpoint of chemical stability.

  Examples of the polythiophene-based conductive polymer material include a PEDOT / PSS aqueous dispersion solution obtained by polymerizing 3,4-ethylenedioxythiophene (EDOT) in an aqueous solution of polystyrenesulfonic acid (PSS) as a dopant. There is a so-called self-doping type conductive polymer having a substituent (sulfo group, sulfonate group, etc.) having both water solubility and doping action in a polymer main chain directly or via a spacer. Polyaniline, PEDOT-S and the like are known (for example, see Patent Documents 1 and 2).

  Conductive polymers have been studied for use not only in antistatic agents and solid electrolytes of solid electrolytic capacitors, but also in recent years as antistatic films and conductive films mounted on various electronic devices (for example, touch panels). , An organic EL display, etc.), and from the viewpoint of extending the life of the device, the conductive composition itself used is required to have durability (heat resistance in a solid or coated state, moisture resistance). . For this reason, a demand for a highly durable conductive polymer film with a small increase in surface resistance is increasing.

JP-A-2015-63652 JP-A-2015-147834

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

  The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the conductive polymer aqueous solution of the present invention, which contains a water-soluble polyurethane, solves the above problems. Was completed.

That is, the present invention relates to a conductive polymer aqueous solution composition, a conductive polymer film, and a coated article thereof as described below.
[1]
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): 0.01 to 10% by weight; A conductive polymer aqueous solution containing 0.001 to 10% by weight of 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 the above formula (3), 1 represents an integer of 6 to 12. ]

[In the above formula (4), m represents an integer of 1 to 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]
Further, the composition according to [1] or [2], further comprising 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. Conductive polymer aqueous solution.
[4]
The surfactant (C) is polyvinylpyrrolidone, a copolymer of polyvinylpyrrolidone, a polyethylene glycol surfactant, an acetylene glycol surfactant, a polyhydric alcohol surfactant, a betaine amphoteric surfactant, and a fluorine-based surfactant. The conductive polymer aqueous solution according to [3], which is at least one selected from the group consisting of a surfactant 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 alcohols and water-soluble resins.
[6]
The conductive polymer according to [5], wherein the alcohol is at least one alcohol selected from the group consisting of monohydric alcohol, dihydric alcohol, trihydric alcohol, and sugar alcohol. Aqueous solution.
[7]
The conductive polymer aqueous solution according to [5], wherein the water-soluble resin is at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, and a water-soluble polyester.
[8]
The conductive polymer aqueous solution according to any one of [1] to [7], further comprising an amine compound (E) and having a pH of 9 or less.
[9]
A method for producing a film, comprising drying the aqueous conductive polymer solution according to any one of [1] to [8].
[10]
A film containing 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 the above formula (3), 1 represents an integer of 6 to 12. ]

[In the above formula (4), m represents an integer of 1 to 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 made 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 round aluminum solid electrolytic capacitors.

  Hereinafter, the present invention will be described in detail. The present invention provides 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): The conductive polymer aqueous solution contains 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 the above formula (3), 1 represents an integer of 6 to 12. ]

[In the above formula (4), m represents an integer of 1 to 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 the alkali metal ion, for example, Li ion, Na ion and K ion are preferable.

The conjugate acid of the amine compound may be any amine compound which is formed by adding hydron (H ⁺ ) to the amine compound to form a cation species and reacts with a sulfonic acid group to form a conjugate acid. An amine compound represented by N (R ¹ ) ₃ having sp3 hybrid orbital [the conjugate acid is represented by [NH (R ¹ ) ₃ ] ⁺ . Or pyridine compounds and imidazole compounds having sp2 hybrid orbitals.

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, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Examples thereof include a butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, an n-hexyl group, a 2-ethylbutyl group, and a cyclohexyl group.

  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, and an alkyl group having 1 to 6 carbon atoms having a hydroxy group. Specifically, a trifluoromethyl group, a 2-hydroxyethyl group and the like are exemplified.

Among these, examples of the substituent R ^1, independently, a hydrogen atom, a methyl group, an ethyl group, 2-hydroxyethyl group is preferred.

The amine compound forming 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. .

Examples of the amine compound represented by N (R ¹ ) ₃ include, but are not particularly limited to, ammonia, methylamine, dimethylamine, ethylamine, triethylamine, normal-propylamine, isopropylamine, normal butylamine, and tertiary amine. L-butylamine, hexylamine, ethanolamine compounds (eg, 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.

Examples of the amine compound not represented by N (R ¹ ) ₃ include, but are not particularly limited to, imidazole compounds (eg, imidazole, N-methylimidazole, 1,2-dimethylimidazole), pyridinepicolin, Lutidine and the like. Of these, ethanolamine compounds and imidazole compounds are preferred.

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

  Examples of the quaternary ammonium cation include a tetramethylammonium cation, a tetraethylammonium cation, a tetranormal propyl ammonium cation, a tetranormal butylammonium cation, and a tetranormal hexylammonium cation. From the viewpoint of availability, a tetramethylammonium cation and a tetraethylammonium cation are preferred.

  In the above formula (3), l represents an integer of 6 to 12, preferably an integer of 6 to 8.

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

  Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include, but are not particularly limited to, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec group. -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 the above formula (4), m represents an integer of 1 to 6, preferably m is an integer of 1 to 4, and more preferably 2.

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

  Dopants that cause an insulator-metal transition by doping are divided into acceptors and donors. The former enters near the polymer chain of the conductive polymer by doping and removes π electrons from the conjugate system of the main chain. As a result, positive charges (holes, holes) are injected onto the main chain, and thus are also called p-type dopants. In the latter, on the other hand, electrons are given to the conjugate system of the main chain, and the electrons move in the conjugate system of the main chain.

  The dopant in the present invention is a sulfo group or a sulfonate group covalently bonded in a polymer molecule, and is a p-type dopant. Such a polymer exhibiting conductivity without adding a dopant from the outside is called a self-doping 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. ]
The metal ion represented by M in the formula (5) is not particularly limited, but may be a transition metal ion, a noble metal ion, a non-ferrous metal ion, or 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, if necessary, M can be converted to hydrogen ions by treating the obtained polymer with an acid, and by reacting this with an amine compound, M can be converted to an amine. The 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), which can be converted into a conjugate acid of the compound, specifically, , 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) Lithium hexane-1-sulfonate, 6- ( Potassium 2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1-sulfonate, 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 thereof include sodium sulfonate and potassium 8- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) octane-1-sulfonate.

In the above formula (1) or formula (2), as the thiophene monomer for obtaining the polythiophene of the present invention wherein L is represented by the above formula (4), 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 -Methyl-1-propanesulfonic acid sodium salt, 3-[(2,3-dihydrothieno [3,4-
b]-[1,4] dioxin-2-yl) methoxy] -1-ethyl-1-propanesulfonic acid sodium salt, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] Dioxin-2-yl) methoxy] -1-propyl-1-propanesulfonic acid sodium salt, 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-propanesulfonic acid sodium salt, 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- Sodium [(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-propanesulfonate, 3-[(2,3-di Potassium dorothieno [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-propanesulfonic acid 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- Potassium hydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-butanesulfonate, 4-[(2,3-dihydrothieno [3,4-b]-[1, 4] Dioxin-2-yl) methoxy] -1-methyl-1-butanesulfonic acid sodium salt, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) Potassium 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 and the like. Is exemplified.

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

  The water-soluble polyurethane in the present invention is not particularly limited, but is also referred to as an aqueous urethane resin, and is generally obtained by imparting hydrophilicity to an originally hydrophobic urethane resin by various methods and dispersing in water. There are forced emulsification type and self-emulsification type. In addition, depending on the raw materials used, they are classified into non-yellowing type / yellowing type, ester type, ether type, and ester ether type, and are classified into nonionic type (nonionic type), anionic type and cationic type 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, etc. when added to an aqueous conductive polymer solution, but is more preferably a nonionic (nonionic). Is preferred. When transparency of a coating film is required, a non-yellowing type is preferred.

  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 fluorine-based surfactant, or a silicone-based surfactant can be used. More preferably, it is at least one selected from the group consisting of nonionic surfactants and amphoteric surfactants.

  The nonionic surfactant is not particularly limited, and examples thereof include a polyethylene glycol type surfactant, an acetylene glycol type surfactant, a polyhydric alcohol type surfactant, and a polymer type nonionic surfactant. Can be

  Examples of the polyethylene glycol-type surfactant include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, Ethylene oxide adducts of fats and oils, and polypropylene glycol ethylene oxide adducts and the like can be mentioned.

  Examples of the acetylene glycol type surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, Surfynol (manufactured by Air Products), and Olfin (manufactured by Nissin Chemical Industry). And the like.

  Examples of the polyhydric alcohol surfactant include fatty acid esters of glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acid esters of sucrose, alkyl ethers of higher alcohols, fatty acid amides of alkanolamines, and the like. No.

  The high molecular weight nonionic surfactant is not particularly limited, and examples thereof include polyvinylpyrrolidone and a copolymer of polyvinylpyrrolidone. The average molecular weight of the polyvinylpyrrolidone used in the present invention is from 1,000 to 2,000,000, preferably from 10,000 to 1.5,000,000. The copolymer of polyvinylpyrrolidone is not particularly limited, but a copolymer having both a hydrophilic part and a hydrophobic part in a polymer chain is preferable. For example, a copolymer obtained by grafting polyvinylpyrrolidone on polyvinyl alcohol, -Vinyl acetate] block copolymer, [vinyl pyrrolidone-methyl methacrylate] copolymer, [vinyl pyrrolidone-normal butyl methacrylate] copolymer, [vinyl pyrrolidone-acrylamide] copolymer, and the like.

  The amphoteric surfactant is not particularly limited, and includes, for example, a betaine-type amphoteric surfactant. The betaine-type amphoteric surfactant is not particularly limited, and examples thereof include alkyl dimethyl betaine, lauryl dimethyl betaine, stearyl dimethyl betaine, lauryl dihydroxyethyl betaine and the like.

The fluorine-based surfactant is not particularly limited as long as it has a perfluoroalkyl group, and examples thereof include perfluoroalkanes, perfluoroalkylcarboxylic acids, perfluoroalkylsulfonic acids, and perfluoroalkylethylene oxide adducts. Can be

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

  Fluorine surfactants and silicone surfactants are effective as leveling agents to improve the flatness of the coating film.

  In the present invention, the surfactant (C) preferably has a solubility in water of not less than 0.01% by weight at 80 ° C, more preferably not less than 0.01% by weight at 30 ° C, and not more than 10 ° C. Is more preferably 0.01% by weight or more, and a surfactant having an HLB in the range of 7 to 20 is more preferable.

  The Griffin method HLB (Hydrophile-Lipophile Balance) is a numerical value indicating the hydrophilicity of the surfactant. The higher the value, the higher the hydrophilicity, which is represented by the following equation.

Griffin method HLB of nonionic surfactant
= (Molecular weight of hydrophilic group portion) / (molecular weight of surfactant) × 100/5
= (Weight of hydrophilic group) / (weight of hydrophobic group + weight of hydrophilic group) × 100/5
= (% By 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.

  Regarding the method of adding the surfactant (C) to the aqueous conductive polymer solution, it may be added as a solid or may be added as a solution prepared in advance as an aqueous solution. At that time, they may be added alone to the aqueous conductive polymer solution, or may be added as a mixture of two or more.

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

  The alcohol is not particularly limited, but includes, for example, at least one alcohol selected from the group consisting of monohydric alcohol, dihydric alcohol, trihydric alcohol, and sugar alcohol.

  The monohydric alcohol is not particularly limited, and includes, for example, methanol, ethanol, 1-propanol, isopropanol, butanol, etc., and ethanol is preferred from the viewpoint of operability. The dihydric alcohol is not particularly limited, but ethylene glycol is preferred from the viewpoint of availability. Although it does not specifically limit as a trihydric alcohol, For example, glycerol is preferable. Although the sugar alcohol is not particularly limited, for example, erythritol, sorbitol, arabitol and the like are preferable. More preferred is sorbitol.

  The water-soluble resin is not particularly limited, but is preferably, for example, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, poly (N-vinylacetamide), water-soluble polyester, or water-soluble polyurethane. From the viewpoint of reducing the amount of metal, it is preferable to use a granular or membrane-like cation exchange resin or a resin subjected to a metal removal filter treatment using zeta potential.

  The molecular weight of the water-soluble resin is not particularly limited as long as it has good water-solubility, but is preferably Mw = 1,000 to 2,000,000, more preferably 10,000 to 1.5,000,000, further preferably Mw = 1,000 to 250,000, and furthermore Preferably, it is in the range of 1,000 to 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 the surfactant (C) in an amount of 0.001 to 10% by weight, and the water-soluble compound (D) in an amount of 0.001 to 10% by weight.

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

  Here, the temperature at the time of mixing is not particularly limited. For example, the mixing can be performed at room temperature to under heating. The temperature is preferably from 0 ° C to 100 ° C.

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

  The pH of the aqueous conductive polymer solution of the present invention is preferably 10 or less, more preferably 9 or less. Further, 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, 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 mixing the polythiophene (A) and the water-soluble polyurethane (B) and then adding the amine compound (E). be able to. Further, the pH may be adjusted by adding an amine compound (E) to an aqueous solution of polythiophene (A) in advance. In addition, when used in an acidic region having a pH of 2 or less, it is not always necessary to add an amine.

  Examples of the amine compound (E) include, but are not particularly limited to, ammonia, methylamine, dimethylamine, ethylamine, triethylamine, normal-propylamine, isopropylamine, normal butylamine, tertiary butylamine, hexylamine, 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, ruti Emissions, and the like. When adding, neat or aqueous solution may be used.

  When mixing the conductive polymer aqueous solution of the present invention, in addition to a general mixing and dissolving operation using a stirrer chip, a stirring blade and the like, ultrasonic irradiation and homogenization treatment (for example, a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer) Etc.) may be performed. In the case of the homogenization treatment, it is preferable to perform the homogenization treatment at a low temperature in order to prevent thermal deterioration of the polymer.

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

  The concentration of the 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. . The conductive polymer aqueous solution containing the polythiophene (A) and the water-soluble polyurethane (B) of the present invention is dried and dehydrated after being applied, so that a good uniform film can be obtained in the above concentration range.

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

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

  Examples of the method for applying the conductive polymer aqueous solution include a casting method, a dipping method, a bar coating method, a dispenser method, a roll coating method, a gravure coating method, a flexographic printing method, a spray coating method, a spin coating method, and an inkjet method. No. Bar coating and spin coating 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 is obtained and the heat-resistant temperature of the substrate, but is in the range of room temperature to 300 ° C., preferably room temperature to 250 ° C. ° C, more preferably from room temperature to 200 ° C.

  The drying atmosphere may be in the air, in an inert gas, in a vacuum, or under reduced pressure. From the viewpoint of suppressing deterioration of the polymer film, it is preferable to use an inert gas such as nitrogen or argon.

Not particularly limited as the thickness of the conductive polymer film obtained is preferably in the range of 10 ^-3 ~10 ² μm. More preferably, it is 10 ⁻³ to 10 ⁻¹ μm. The conductivity of the conductive polymer film is not particularly limited, but is preferably higher. In addition, the conductivity of the conductive polymer film varies depending on the type and amount of the surfactant or the water-soluble resin to be added, and thus cannot be uniquely determined. However, as 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 still more preferably 1.0E + 7Ω / □ or less. The applied voltage when measuring the surface resistance is not particularly limited, but is measured at 10 V or 500 V.

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

  Examples of the present invention will be described below.

The analytical instruments and measuring methods used in this example are listed below.
[GC measurement]
Apparatus: GC-2014, manufactured by Shimadzu
[NMR measurement]
Apparatus: Gemini-200, manufactured by VARIAN
[Surface resistivity measurement]
Apparatus: Mitsubishi Chemical Corporation Loresta GP MCP-T600
Apparatus: Mitsubishi Chemical Corporation Hiresta UX MCP-HT8000
[Thickness measurement]
Equipment: DEKTAK XT manufactured by BRUKER
[Viscosity measurement]
Complete Viscometer / BROOKFIELD VISCOMETER DV-1 Prime
Conductivity [S / cm] = 10 ⁴ / (surface resistivity [Ω / □] × film thickness [μm])
[Particle size measurement]
Apparatus: Nikkiso Co., Ltd., Microtrac Nanotrac UPA-UT151
[Conductivity measurement of self-doping type conductive polymer]
0.5 ml of an aqueous solution containing a self-doping type conductive polymer is applied to a 25 mm square non-alkali glass plate, dried at room temperature overnight, and then placed on a hot plate at 120 ° C. for 20 minutes and further at 160 ° C. for 10 minutes. By heating, a conductive polymer film was obtained. It was calculated from the film thickness and the surface resistance value based on the following formula.
[Applicability & antistatic evaluation]
(1) Evaluation of applicability to polymer substrate (thermoplastic resin).
The conductive polymer aqueous solution was cast so as to spread over the entire PET film (2.5 cm square), and then spin-coated (Mixed by MIKASA: Spinner 1H-D2) to form a film (1200 rpm × 40 seconds, then 100 ° C. ×). Vacuum drying for 60 seconds). The surface resistance value of the obtained coating film was measured. When the surface resistance was stable, the applicability was judged to be good. When the surface resistance of the obtained conductive polymer film was 1.0E + 9Ω / □ or less, the antistatic ability was judged to be good.
[Evaluation of transparency of coating film (transmittance, haze ratio)]
-Equipment: Nippon Denshoku Co., Ltd. haze meter NDH4000
・ Condition: Substrate blank [Evaluation of durability of coating film]
・ Heat resistance evaluation device: ETTAS constant temperature dryer EOP-450B (natural convection method)
Conditions: 80 ° C., 300 hours Evaluation: A case where the rate of increase in the surface resistivity after the test compared to before the test was less than 10 times was regarded as good. Ten times or more were regarded as defective.
-Moisture resistance evaluation device: SH-241 manufactured by ESPEC
Conditions: 60 ° C., 95% RH, 300 hours Evaluation: The case where the rate of increase in the surface resistivity after the test before the test was less than 100 times was regarded as 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-shaped flask, and then (2,3-dihydrothieno [3,4-b] [1,4] dioxin- 1.52 g (8.84 ml) of 2-yl) methanol were added. Thereafter, the reaction solution was heated to the reflux temperature and stirred at the same temperature for 1 hour. Thereafter, a mixed solution consisting of 1.21 g (8.89 mmol) of 2,4-butanesultone and 10 ml of toluene was added dropwise, and the mixture was stirred at the same temperature for 2 hours. After cooling, the obtained reaction solution was dropped into 160 ml of acetone to perform reprecipitation. The obtained powder was filtered and dried under vacuum to obtain 1.82 g of a pale yellow powder in a yield of 62%. From NMR measurement, this was 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1 represented by the following formula (6). -It was 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) [a polymer containing a structural unit represented by the following formula (7) or (8)].
In a 500 ml separable flask, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1 synthesized according to Synthesis Example 1. -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 the mixture was 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 temperature of the reaction solution 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 dried under vacuum 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 the crude polymer to form a 2% by weight solution was passed through a column filled with 200 ml of a cation exchange resin Lewatit MonoPlus S100 (H type) (space velocity = 1.1). ) To obtain 738 g of an H-type polymer aqueous solution. Further, the polymer aqueous solution is purified by a cross-flow type ultrafiltration (filter: Vivaflow 200, molecular weight cut-off = 5,000, transmission magnification = 5), and is expressed by the following formula (7) or (8). 698 g of a deep blue aqueous solution of a polymer containing the structural unit was obtained. The amount of the polymer contained in the present polymer aqueous solution was 0.74% by weight. It also contained iron and sodium ions at 44 ppm and 12 ppm (based on polymer), respectively.

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

Embodiment 1 FIG.
Aqueous solution 1 containing 2.0% by weight of polythiophene (A) obtained in Synthesis Example 3 [polymer containing structural unit represented by formula (9) or formula (10)] [conductivity 119 S / cm] 1 0.564 g of an aqueous solution containing 2.5 wt% of a high-molecular-weight nonionic surfactant polyvinylpyrrolidone K90 (Sokalan K90, manufactured by BASF, molecular weight: 1.4 million) in 0.874 g, ethanol 0.741 g, water-soluble polyurethane Then, 0.274 g of a 5.0% aqueous solution of Superflex SFE2000 (manufactured by 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 Product Co., Ltd.) was 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 applying at a constant rate using a drying device, the film was dried 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 site. The transmittance of the laminated film produced in this example was 97.30%. Table 1 below shows the results of the durability test of the laminated film produced in this example.

Embodiment 2. FIG.
Example 1 was repeated except that the water-soluble polyurethane was changed to Superflex SF500M (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Table 1 below shows the results of the durability test of the laminated film produced in this example.

  As is clear from Examples 1 and 2, the surface resistivity of the coating film was not more than 1.30 times even after 300 hours at 60 ° C. and 95% RH in the moisture resistance test, indicating good moisture resistance. I understood. Also, there was no change in the transmittance of the coating film before and after the test, indicating good moisture resistance.

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

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

Claims (9)

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): 0.01 to 10% by weight; A conductive polymer aqueous solution containing 0.001 to 10% by weight of a water-soluble polyurethane (B).
[The formula (1) and formula (2), L represents lower following formula a (4), M represents a hydrogen ion, an alkali metal ion, the conjugate acid of the amine compound, or quaternary ammonium cation. ]
[In the above formula (4), m represents an integer of 1 to 6. R ² represents a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ] The conductive polymer aqueous solution according to claim 1, wherein the water-soluble polyurethane (B) is a nonionic water-soluble polyurethane. The composition according to claim 1, further comprising 0.001 to 10% by weight of at least one surfactant (C) selected from the group consisting of polyvinylpyrrolidone, a copolymer of polyvinylpyrrolidone, and an amphoteric surfactant. The conductive polymer aqueous solution according to claim 2. Further, a conductive polymer aqueous solution according to any one of claims 1 to 3, characterized in that it comprises an alcohol. The conductive polymer according to claim 4 , wherein the alcohol is at least one alcohol selected from the group consisting of monohydric alcohol, dihydric alcohol, trihydric alcohol, and sugar alcohol. Aqueous solution. The conductive polymer aqueous solution according to any one of claims 1 to 5, further comprising an amine compound (E) and having a pH of 10 or less. Film production method of which is characterized by drying the conductive polymer solution according to any one of claims 1 to 6. A film containing 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) .
[The formula (1) and formula (2), L represents lower following formula a (4), M represents a hydrogen ion, an alkali metal ion, the conjugate acid of the amine compound, or quaternary ammonium cation. ]
[In the above formula (4), m represents an integer of 1 to 6. R ² represents a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ] A coated article, wherein at least a part of the support is covered with the membrane according to claim 8 .