JP6969273B2 - Antistatic thin film and antistatic aqueous solution - Google Patents

Description

An object of the present invention is to provide a thin film having photodurability, a specific self-doped conductive polymer having high conductivity, a specific water-soluble resin, and a specific reducing polymorphism. It is a thin film characterized by containing a valent alcohol compound, and further relates to a production method for obtaining the thin film.

Conductive polymer materials have been developed in which π-conjugated polymers typified by polyacetylene, polythiophene, polyaniline, polypyrrole, etc. are doped with an electron-accepting compound as a dopant. Applications to paints, electromagnetic wave shields, electrochromic elements, electrode materials, thermoelectric conversion materials, transparent conductive polymers, chemical sensors, actuators, etc. are being studied. Among these, polythiophene-based conductive polymer materials are 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 polystyrene sulfonic acid (PSS) as a dopant. There is a so-called self-doped conductive polymer having a substituent (sulfo group, sulfonate group, etc.) having both water solubility and doping action in the polymer main chain directly or via a spacer, and examples thereof include the latter. , Sulfated polyaniline, PEDOT-S and the like are known (see, for example, Non-Patent Documents 1 and 2).

As applications of conductive polymers, the use of antistatic agents and solid electrolytic capacitors in solid electrolytes has been studied in many cases. For example, antistatic agents are used to coat a non-conductive substrate with a conductive polymer to impart conductivity. Generally, thermoplastic resins such as polyester films are widely used as base materials for adhesive films and carrier tapes for surface protection, but since these polymer base materials are insulating, they are used during molding, processing, and use. There is a problem that electronic devices such as electronic circuits and semiconductor parts are electrostatically destroyed due to dust and dirt adhering to the film due to static electricity, adhesion between the films, and charging during film cutting and unwinding of the roll-shaped film. As one of the measures for avoiding such a problem, there is a method in which the conductive polymer uses the polymer base material for the antistatic layer. Since the conductive polymer-based antistatic agent has an electron-conducting conductive mechanism, it has an advantage that the functional deterioration due to the humidity of the usage environment is small like the surfactant-type antistatic agent. For the use of such an antistatic material, a PEDOT / PSS aqueous solution showing high conductivity is used, and an antistatic coating composition (Patent Document 1), a conductive coating composition (Patent Document 2), and the like are used. Although it exists, it has been required to improve the antistatic light resistance and the moisture resistance of the antistatic film using the PEDOT / PSS.

As a technique for improving the light resistance and moisture resistance, a thin film using a self-doped conductive polymer and an antistatic film using the thin film have been proposed (Patent Document 3).

Japanese Unexamined Patent Publication No. 2010-90318 Japanese Unexamined Patent Publication No. 2014-148674 Japanese Unexamined Patent Publication No. 2017-105982

Journal of the American Chemical Society, 112, 2801-2803 (1990) Advanced Materials, Vol. 23 (38) 4403-4408 (2011)

With regard to antistatic films, the demand for light resistance has become stricter year by year with the extension of the life of display devices in recent years, and there is a demand for antistatic films that satisfy the stricter demands for light resistance.

It is an object of the present invention to provide a conductive thin film having higher light resistance than the conductive thin film reported in Patent Document 3 and an antistatic film using the same.

As a result of diligent studies to solve the above problems, the present inventors have made a conductive thin film having an unexpectedly excellent light resistance as compared with the prior art and charging using the conductive thin film due to the configuration of the present invention. We have found that a preventive film can be provided, and have completed the invention of the present application.

That is, the present invention relates to an antistatic thin film and an antistatic aqueous solution as shown below.
[1]
Polythiophene (A) containing at least one structural unit selected from the group consisting of the structural unit represented by the following general formula (1) and the structural unit represented by the following general formula (2) and at least one water-soluble resin ( An aqueous solution composition containing B) and the reducing polyhydric alcohol compound (C), wherein the content of (B) is 0.1 to 10 parts by weight with respect to 1 part by weight of (A), and the content of (C) is. (A) An aqueous solution composition having a pH of 0.5 to 10 parts by weight and a pH of 1.0 or more and 6.0 or less with respect to 1 part by weight.

[In the above formulas (1) and (2), L represents the following general formula (3) or formula (4), and M represents hydrogen ion or alkali metal ion. ]

[In the above equation (3), l represents an integer of 6 to 12. ]

[In the above equation (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 water-soluble resin (B) is the at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, a copolymer of polyvinylpyrrolidone, a water-soluble polyester, and a water-soluble polyurethane [2]. Aqueous solution composition.
[3]
The reducing polyhydric alcohol compound (C) is characterized by being an aldehyde group, _{a group represented by -CO-CH 2} OH, a polyhydric alcohol compound having a double bond, or an intramolecular dehydration condensation product thereof. The aqueous composition according to [1].
[4]
In addition to (A), (B), and (C), the surfactant (D) may be further contained, and the content of (D) is 0.01 to 100 per 1 part by weight of (A). The aqueous solution composition according to [1], which is characterized by a weight portion.
[5]
The surfactant (D) is from a polyethylene glycol-type surfactant, an acetylene glycol-type surfactant, a polyhydric alcohol-type surfactant, a betaine-type amphoteric surfactant, a fluorine-based surfactant, and a silicone-based surfactant. The aqueous composition according to [4], which is at least one selected from the group.
[6]
The aqueous solution composition according to [1], which comprises alcohol in addition to (A), (B), and (C).
[7]
A method for producing a thin film, which comprises applying the aqueous solution composition according to [1] or a composition containing the aqueous solution composition to a substrate and drying the substrate.
[8]
An antistatic film produced by using the water-soluble composition according to [1].

According to the present invention, it is possible to provide a conductive thin film having remarkably excellent light durability as compared with conventionally known techniques.

Further, according to the present invention, it is possible to provide a conductive thin film having both light durability and high conductivity. Since this thin film has an antistatic function, it can be expected to be used as an antistatic film.

Hereinafter, the present invention will be described in detail.

The antistatic thin film of the present invention contains polythiophene (A) containing at least one structural unit selected from the group consisting of the structural unit represented by the following general formula (1) and the structural unit represented by the following general formula (2). An aqueous solution composition containing at least one water-soluble resin (B) and a reducing polyhydric alcohol compound (C), wherein the content of (B) is 0.1 to 10 parts by weight based on 1 part by weight of (A). Aqueous solution composition characterized in that the content of (C) is 0.5 to 10 parts by weight with respect to 1 part by weight of (A), and the pH is 1.0 or more and 6.0 or less. ..

[In the above formulas (1) and (2), L represents the following general formula (3) or formula (4), and M represents hydrogen ion or alkali metal ion. ]

[In the above equation (3), l represents an integer of 6 to 12. ]

[In the above equation (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 (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.

The linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, and is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. , Se-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} of the formula (4) is preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom in terms of film forming property.

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 deprives the conjugated system of the main chain of π electrons. As a result, a positive charge (hole, hole) is injected onto the main chain, so it is also called a p-type dopant. The latter is also called an n-type dopant because, on the contrary, an electron is donated to the conjugated system of the main chain, and this electron moves in the conjugated 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 that exhibits conductivity without adding a dopant from the outside is called a self-doped polymer.

The polythiophene (A) containing at least one structural unit selected from the group consisting of the structural unit represented by the formula (1) and the structural unit represented by the following formula (2) has a film-forming property. , Polythiophene containing at least one structural unit selected from the group consisting of the structural units represented by the following formulas (1-3), formula (2-3), formula (1-4), and formula (2-4). A) is preferable.

[In the above formula,
M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation.
l represents an integer of 6 to 12.
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. ]
The polythiophene (A) of the present invention can be produced by polymerizing a thiophene monomer represented by the following formula (5) in a solvent such as water or alcohol in the presence of an oxidizing agent.

[In the above equation (5), L has the same definition as above. M represents a metal ion. ]
The metal ion represented by M in the general formula (5) is not particularly limited, and examples thereof include Li ion, Na ion, and K ion.

Since the polymer after polymerization is a metal salt, the metal ion represented by M can be converted into a hydrogen ion by acid-treating the obtained polymer, if necessary.

Specific examples of 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 the above formula (2), are 6- (2,3-dihydro). -Tieno [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) hexane-1-sodium 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) potassium 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- Examples thereof include sodium 1-sulfonate, 8- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) octane-1-potassium sulfonate, and the like.

Specifically, 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 the above formula (2), is specifically 3-[(2,3-). Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-sodium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1, 4] Dioxin-2-yl) methoxy] -1-potassium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1 -Sodium methyl-1-propanesulfonic acid, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-ethyl-1-propanesulfonic acid Sodium, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-propyl-1-sodium propanesulfonate, 3-[(2,2) 3-Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-butyl-1-sodium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-) b]-[1,4] dioxin-2-yl) methoxy] -1-pentyl-1-sodium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] Dioxin-2-yl) methoxy] -1-hexyl-1-sodium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-Isopropyl-1-propane Sulfonate Sodium, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isobutyl-1-propane Sodium Sulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isopentyl-1-propanesodium sulfonate, 3-[((2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] 2,3-Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-sodium propanesulfonate, 3-[(2,3-dihydrothieno [3,3] 4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-potassium propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1, 4] Dioxin-2-yl) methoxy] -1-methyl -1-Propane sulfonic 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-methyl-1-propanesulfonate triethylammonium, 4-[(2,3-) Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-sodium butane sulfonate, 4-[(2,3-dihydrothieno [3,4-b]-[1, 4] Dioxin-2-yl) methoxy] -1-potassium butane sulfonate, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1 -Sodium methyl-1-butanesulfonic acid, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-butanesulfonic acid Potassium, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-sodium butane sulfonate, and 4-[(2) , 3-Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-butane sulfonate potassium and the like are exemplified.

The water-soluble resin (B) of the present invention is not particularly limited, but for example, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyester, or water-soluble polyurethane (these water-soluble resins are homopolymers). May be a copolymer). The copolymer of polyvinylpyrrolidone 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 polyvinylpyrrolidone to polyvinyl alcohol, or [vinylpyrrolidone]. Examples thereof include a [vinyl acetate] block copolymer, a [vinylpyrrolidone-methylmethacrylate] copolymer, a [vinylpyrrolidone-normalbutylmethacrylate] copolymer, and a [vinylpyrrolidone-acrylamide] copolymer. Polyacrylamide, poly (N-vinylacetamide) and the like can also be used. Regarding these water-soluble resins, from the viewpoint of reducing the amount of metal in the water-soluble composition of the present invention, granule-like or film-like cation exchange resins and those subjected to metal removal filter treatment using zeta potential are used. It is preferable to use it.

The water-soluble resin (B) of the present invention is made of polyvinyl alcohol or polyvinylpyrrolidone (these water-soluble resins may be homopolymers or copolymers) in that they have excellent light resistance. It is preferably present, and more preferably polyvinylpyrrolidone (which may be a homopolymer or a copolymer).

The molecular weight of the water-soluble resin is not particularly limited as long as it has good water solubility, but is preferably in the range of Mw = 10 to 2 million, more preferably 10,000 to 1.5 million.

In the present invention, the content of the water-soluble resin (B) is in the range of 0.1 to 10 parts by weight with respect to 1 part by weight of (A), and is excellent in light resistance. On the other hand, it is preferably in the range of 0.5 to 8 parts by weight.

The reducing polyhydric alcohol compound (C) of the present invention is not particularly limited, but has an aldehyde group, _{a group represented by −CO—CH 2} OH, or a double bond in terms of excellent light resistance. It is preferably a polyhydric alcohol compound having, or an intramolecular dehydration condensate thereof, and preferred examples of such compounds include, but are not limited to, glucose, sucrose, fructose, galactose, maltose, lactose and the like. Examples thereof include monosaccharides and disaccharides, or compounds having a lactone ring such as L-ascorbic acid, erythorbic acid, glucuronic acid lactone, and glucaric acid lactone. Of these, glucose, sucrose, L-ascorbic acid, or erythorbic acid is preferable because of its excellent light resistance.

In the present invention, the content of the reducing polyhydric alcohol compound (C) is in the range of 0.5 to 10 parts by weight with respect to 1 part by weight of (A), and is excellent in light resistance. It is preferably 1.0 to 8 parts by weight with respect to the part by weight.

The aqueous solution composition of the present invention preferably further contains a surfactant (D) in addition to (A), (B), and (C). The content of the surfactant (D) is preferably 0.01 to 100 parts by weight, more preferably 0.05 to 80 parts by weight, still more preferably, with respect to 1 part by weight of (A). It is in the range of 0.1 to 50 parts by weight.

The surfactant (D) is not particularly limited, but is, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a fluorine-based surfactant, or a silicone-based surfactant. Surfactants and the like can be preferably used. Of these, at least one selected from the group consisting of nonionic surfactants and amphoteric surfactants is more preferable.

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

The polyethylene glycol type surfactant is not particularly limited, but for example, a higher alcohol ethylene oxide adduct, an alkylphenol ethylene oxide adduct, a fatty acid ethylene oxide adduct, a polyhydric alcohol fatty acid ester ethylene oxide adduct, and the like. Examples thereof include higher alkylamine ethylene oxide adducts, fats and oils ethylene oxide adducts, polypropylene glycol ethylene oxide adducts and the like.

The acetylene glycol-type surfactant is not particularly limited, but is, for example, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, surfinol (manufactured by Air Products & Chemicals). , Orphine (manufactured by Nisshin Kagaku Kogyo Co., Ltd.) and the like.

The polyhydric alcohol-type surfactant is not particularly limited, and is, for example, a glycerol fatty acid ester, a pentaerythritol fatty acid ester, a sorbitol and sorbitan fatty acid ester, a sucrose fatty acid ester, and a high alcohol alkyl. Examples thereof include fatty acid amides of ethers and alkanolamines.

The amphoteric tenside is not particularly limited, and examples thereof include betaine-type amphoteric tenside agents. The betaine-type amphoteric surfactant is not particularly limited, and examples thereof include alkyldimethylbetaine, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.

The fluorine-based surfactant is not particularly limited as long as it has a perfluoroalkyl group, such as perfluoroalkane, perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, or perfluoroalkylethyleneoxide adduct. Can be mentioned.

The silicone-based surfactant is not particularly limited, and is, for example, a polyether-modified polydimethylsiloxane, a polyether ester-modified polydimethylsiloxane, a hydroxyl group-containing polyether-modified polydimethylsiloxane, and an acrylic group-containing polyether-modified polydimethyl. Examples thereof include siloxane, acrylic group-containing polyester-modified polydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, and silicone-modified acrylic compound.

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

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

The method for preparing the aqueous solution composition of the present invention is not particularly limited, but for example, the aqueous solution or solid of the polythiophene (A) of the present invention, the water-soluble resin (B), and the reducing polyhydric alcohol compound. (C), a surfactant (D) as needed, and water as needed are used. By mixing these in any order, an aqueous solution for producing the thin film of the present invention can be prepared.

Here, the temperature at the time of mixing is not particularly limited, but for example, it can be carried out at room temperature to heating. It is preferably 0 ° C. or higher and 100 ° C. or lower.

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

The pH of this aqueous solution is in the range of 1.0 or more and 6.0 or less, and is preferably in the range of 1.0 or more and 5.0 or less in terms of excellent light resistance. When the pH is 6.0 or more, there is a tendency that the special effect of being remarkably excellent in the light resistance characteristic of the present invention cannot be obtained.

When mixing the aqueous solution for producing the aqueous solution composition of the present invention, in addition to the general mixing and dissolving operation using a stirrer chip, a stirring blade, etc., ultrasonic irradiation, homogenization treatment (for example, mechanical homogenizer, ultrasonic wave, etc.) (Use of homogenizer, high-pressure homogenizer, etc.) may be performed. When the homogenization treatment is performed, it is preferable to carry out the homogenization treatment while cooling the temperature in order to prevent thermal deterioration of the polymer.

The concentration of the aqueous solution for producing the aqueous solution composition of the present invention may be adjusted by a blending ratio or by concentration after blending. The method of concentration may be a method of distilling off the solvent under reduced pressure or a method of utilizing an ultrafiltration membrane.

The concentration of polythiophene (A) in the aqueous solution for producing the aqueous composition of the present invention is not particularly limited as long as it is 0.01% by weight or more, but is preferably 0.02% by weight to 0.2% by weight. It is in the range of% by weight.

The particle size of the solid content in the aqueous solution composition 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 conductive polymer aqueous solution prepared at room temperature or under heating is 10% by weight or less, and the particle size (D50) of the solid content is 0.02 μm or less, the water solubility is better. Become.

The viscosity (20 ° C.) of the aqueous solution composition 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, and more preferably 50 mPa · s or less.

The method for forming a thin film using the aqueous solution composition of the present invention is not particularly limited, and examples thereof include a method of applying the aqueous solution composition of the present invention to a support and drying the thin film. A thin film can be obtained on the support (hereinafter, the support and the thin film are collectively referred to as a "coated article").
The support is not particularly limited as long as the aqueous solution composition of the present invention can be applied, and examples thereof include a polymer base material and an inorganic base material. Examples of the polymer base material include thermoplastic resins, non-woven fabrics, papers, resist film substrates and the like. Examples of the thermoplastic resin include polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polycarbonate and the like. The non-woven fabric may be made of, for example, natural fiber, synthetic fiber, or glass fiber. The paper may be mainly composed of general cellulose. Examples of the inorganic base material include glass, ceramics, aluminum oxide, tantalum oxide and the like.

Examples of the coating method on the support 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, an inkjet method, and the like. .. The spin coating method and the bar coating method are preferable.

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

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

The film thickness of the obtained thin film is not particularly limited, but is preferably in the range of ^10-3 to ^{10 to 2 μm.} More preferably, it is 10 ^-3 to ^-1 μm. The conductivity of this thin film is not particularly limited, but is preferably high.

The surface resistance value of the obtained thin film is not particularly limited, but is preferably 1.0E + 4Ω / □ or more and 1.0E + 11Ω / □ or less, and more preferably 1.0E + 5Ω / □ or more and 1.0E + 10Ω / □ or less. be. The applied voltage when measuring the surface resistance value is not particularly limited, but is measured at 10 V or 500 V.

The coated article of the present invention is particularly used as an antistatic film.

The aqueous solution composition for producing the thin film of the present invention may further contain alcohol.

The alcohol is not particularly limited, and examples thereof include at least one alcohol selected from the group consisting of ethanol, divalent alcohol, and trihydric alcohol.

The divalent alcohol is not particularly limited, but ethylene glycol is preferable from the viewpoint of availability. The trihydric alcohol is not particularly limited, but for example, glycerol is preferable.

Examples of the present invention are shown below.

The analytical instruments and measurement methods used in this example are listed below.

[Measurement of surface resistivity]
Equipment: Mitsubishi Chemical Corporation Loresta GP MCP-T600.

Equipment: Mitsubishi Chemical Corporation High Resta UX MCP-HT8000.

[Film thickness measurement]
Equipment: DEKTAK XT manufactured by BRUKER.

[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 overnight at room temperature, and then placed on a hot plate at 120 ° C. for 20 minutes and then at 160 ° C. for 10 minutes. It was heated to obtain a conductive polymer film. It was calculated from the film thickness and surface resistance value based on the following formula.

Conductivity [S / cm] = 1.0E + 4 / (surface resistivity [Ω / □] x film thickness [μm]).

[Applicability & antistatic evaluation]
(1) Evaluation of coatability on polymer substrate (thermoplastic resin) A PET film (Toray Industries, Inc. Lumirror T60 / 38 μm) obtained by cutting a conductive aqueous solution into a 7 cm × 14 cm solution and an automatic bar coater (PK Print Coat Instruments K, Inc.) After applying at a constant speed using a control coater), the film was dried at 100 ° C. for 5 minutes with a hot air dryer to obtain a laminated film. If the surface resistance value of the obtained thin film is stable, the coatability is good, and if the surface resistance value is 1.0E + 5Ω / □ or more and 1.0E + 10Ω / □ or less, the antistatic ability is judged to be good.

[Light durability evaluation]
Equipment: UV fade meter U48 (manufactured by Suga Test Instruments Co., Ltd.)
Conditions: 60 ° C., 50% RH, 96 hours Evaluation: The rate of increase in surface resistivity after the test compared to before the test was calculated based on the following formula.

Increase rate = Surface resistivity before test [Ω / □] / Surface resistivity after test [Ω / □]
Light resistance in the present invention refers to resistance to ultraviolet rays (UV). Specifically, it means that the light resistance is excellent when the rate of increase in surface resistivity before and after irradiation with UV for 96 hours is small. The laminated film of the present invention preferably has such an increase rate of 20 or less, more preferably 10 or less, and particularly preferably 5 or less. If the rate of increase is too high, the light resistance will be inferior, and if the laminated film is used in a state of being exposed to ultraviolet rays, the conductive performance will deteriorate.

Synthesis example 1.
Synthesis of polythiophene (A) [polymer containing structural units represented by the following formula (6) or the following formula (7)].
3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl synthesized in a 500 ml separable flask according to a conventionally known production method. 10 g (30 mmol) of sodium -1-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. Then, while maintaining the reaction solution temperature of 30 ° C. or lower, a mixed solution consisting of 14.5 g (60.4 mmol) of sodium persulfate and 100 g of water was added dropwise. After the addition was completed, the mixture was stirred at room temperature for 3 hours, and then the reaction solution was added dropwise to 800 g of acetone to precipitate a black Na-type polymer. By filtering and vacuum drying the polymer, 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 a 2% by weight solution was passed through a column filled with 200 ml of a cation exchange resin Lewattit MonoPlus S100 (H type) (space velocity = 1.1). ) To obtain 738 g of an H-type polymer aqueous solution. Further, the present polymer aqueous solution is represented by the following formula (6) or formula (7) by purifying it by cross-flow type ultrafiltration (filter = Vivaflow 200, molecular weight cut-off = 5,000, permeation magnification = 5). 698 g of a dark blue aqueous solution of a polymer containing a structural unit was synthesized. The amount of the polymer contained in the aqueous solution of this polymer (polythiophene (A)) was 0.74% by weight. In addition, the present polymer aqueous solution contained iron ions and sodium ions at 44 ppm and 12 ppm (against the polymer), respectively.

Example 1.
An aqueous solution containing 2% by weight of polythiophene (A) [polymer containing the structural unit represented by the above formula (6) or the above formula (7)] [conductivity 119S / cm] obtained according to Synthesis Example 1. 4.80 g of an aqueous solution containing 2.5% by weight of polyvinylpyrrolidone K90 (Sokalan K90 molecular weight 1.4 million manufactured by BASF) as a water-soluble resin (B) and 10% by weight of glucose as a reducing polyhydric alcohol compound (C) in .60 g. % 3.60 g of an aqueous solution, 11.250 g of ethanol, and 126.75 g of water were added, and the mixture was thoroughly stirred and mixed. The composition of this compounding solution has (A) content of 0.048% by weight, (B) content of 1.67 parts by weight with respect to (A) 1 part by weight, and (C) content of (A). ) 5.0 parts by weight with respect to 1 part by weight. The pH of this compound was 4.0.

A bar coater (Select Roller OSP-22 manufactured by OSG System Products Co., Ltd.) was applied to a PET film (Lumirror T60 / 38 μm manufactured by Toray Industries, Inc.) obtained by cutting 0.3 g of the conductive polymer aqueous solution thus obtained into a size of 7 cm × 14 cm. After applying at a constant rate, the film was dried at 100 ° C. for 5 minutes in a dryer to obtain a laminated film. The obtained film showed a uniform state without spots, and the surface resistance value of the film stably showed 7.0E + 7Ω / □ regardless of the measurement location, so that it had good antistatic ability. I understood. The light resistance test of the laminated film produced in this example was carried out. The results are shown in Table 1.

Examples 2-3
A laminated film was obtained according to the method of Example 1 except that the amount of glucose added was changed in Example 1, and a light resistance test was carried out. The results are shown in Table 1.

All of these laminated films had an increase rate of 10 or less after the light durability test, and were excellent in light durability.

Comparative example 1.
In Example 1, a laminated film was obtained according to the method of Example 1 except that poly (3,4-ethylenedioxythiophene) polystyrene sulfonic acid was used instead of polythiophene (A), and a light resistance test was carried out. .. The results are shown in Table 1.

Since the antistatic thin film of the present invention provides a thin film having both light durability and high conductivity, it can be used as a conductive coating agent (antistatic agent) and a solid electrolyte (cathode material) of a solid electrolytic capacitor. Further, the coated article made of a polymer base material coated with this thin 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, it can be expected to be applied to electrochromic elements, transparent electrodes, transparent conductive films, thermoelectric conversion materials, chemical sensors, actuators, electromagnetic wave shielding materials, and the like.

Claims (3)

A water-soluble resin composed of polythiophene (A) and polyvinylpyrrolidone consisting of at least one structural unit selected from the group consisting of the structural unit represented by the following general formula (1) and the structural unit represented by the following general formula (2). An aqueous solution composition containing the reducing polyhydric alcohol compound (C) composed of (B) and glucose, wherein the content of (B) is 0.1 to 10 parts by weight with respect to 1 part by weight of (A), (C). ) The aqueous solution composition is characterized in that the content is 0.5 to 10 parts by weight with respect to 1 part by weight of (A) and the pH is 1.0 or more and 5.0 or less.

[The formula (1) and formula (2), L represents the general formula (3) or formula (4), M represents a hydrogen ion. ]

[In the above equation (3), l represents an integer of 6 to 12. ]

[In the above equation (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. ] The aqueous solution composition according to claim 1, wherein an alcohol is contained in addition to (A), (B), and (C). A method for producing a thin film, which comprises applying the aqueous solution composition according to claim 1 or a composition containing the aqueous solution composition to a substrate and drying the substrate.