Conductive polymer solution and conductive polymer film

Abstract

To provide a conductive polymer solution that can simplify a manufacturing process by forming a layer with both antistatic and UV absorption properties with only one layer of coating applied.SOLUTION: A conductive polymer solution contains a polythiophene (A) comprising at least one structural unit selected from the group consisting of structural units represented by the general formula (1) and structural units represented by the general formula (2), a UV absorber (B), and an organic solvent (C).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a conductive polymer solution and a conductive polymer membrane. [Background technology]

[0002] In image display devices, it is necessary to protect the surfaces of the device and the components that make it up, and / or to prevent ultraviolet degradation of the components that make up the device by absorbing ultraviolet light from external light or a light source.

[0003] Patent Document 1 describes an antistatic film for use in a touch panel, which includes a substrate film and an antistatic layer provided on the substrate film. Patent Document 2 describes a surface protection film having a substrate film and a surface protection layer. Patent Document 3 describes an antistatic film including a substrate film layer made of a thermoplastic resin containing a polymer containing an alicyclic structure, and an antistatic layer provided on the substrate film layer and containing conductive metal oxide particles. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 181070 [Patent Document 2] Patent Publication No. 2016-107498 [Patent Document 3] International Publication No. 2016 / 208716 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the above-mentioned conventional technology, since the UV absorber cannot be dissolved in water, when trying to obtain antistatic properties using a water-based conductive polymer, it is necessary to apply two layers: a water-based coating film (antistatic layer) and an organic coating film (UV absorbing layer). As a result, the manufacturing process increases compared to a single-layer coating, and the conventional technology has room for further improvement from the viewpoint of simplifying the manufacturing process.

[0006] An object of one aspect of the present invention is to provide a conductive polymer solution that can form a layer having both antistatic properties and ultraviolet absorbing properties by applying it in one layer, thereby simplifying the manufacturing process. [Means for solving the problem]

[0007] In order to solve the above problems, one aspect of the present invention relates to the following conductive polymer solution and conductive polymer membrane. <1> A polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), an ultraviolet absorber (B); and an organic solvent (C).

[0008] [ka]

[0009] [In the general formula (1), M + represents an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium ion. 1 represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom; m independently represents an integer of 1 to 10; and n independently represents 0 or 1. <2> The ultraviolet absorber (B) includes at least one selected from the group consisting of benzophenone-based compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, and triazine-based compounds. <1> The conductive polymer solution according to claim 1. <3> The organic solvent (C) is at least one selected from the group consisting of alcohol solvents, ether solvents, ketone solvents, and aromatic solvents. <1> or <2> The conductive polymer solution according to claim 1. <4> Said M + is a conjugate acid of an amine compound having a total carbon number of 8 to 30, or a quaternary ammonium ion having a total carbon number of 8 to 30, <1> ~ <3> 10. The conductive polymer solution according to claim 9, wherein the conductive polymer solution is a solution containing a conductive polymer. <5> Said M + is at least one selected from the group consisting of octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, decylammonium ion, dodecylammonium ion, tridecylammonium ion, pentadecylammonium ion, hexadecylammonium ion, octadecylammonium ion, oleylammonium ion, di-n-octylammonium ion, bis(2-ethylhexyl)ammonium ion, dimethyloctylammonium ion, dimethyldecylammonium ion, dimethyldodecylammonium ion, dimethylstearylammonium ion, trihexylammonium ion, trioctylammonium ion, tris(2-ethylhexyl)ammonium ion, phenylammonium ion, decyltrimethylammonium ion, dodecyltrimethylammonium ion, and tetrahexylammonium ion, <1> ~ <3> 10. The conductive polymer solution according to claim 9, wherein the conductive polymer solution is a solution containing a conductive polymer. <6> The content of the polythiophene (A) is 0.01 to 10% by mass. <1> ~ <5> 10. The conductive polymer solution according to claim 9, wherein the conductive polymer solution is a solution containing a conductive polymer. <7> The content of the ultraviolet absorber (B) is 0.01 to 10 mass %. <1> ~ <6> 10. The conductive polymer solution according to claim 9, wherein the conductive polymer solution is a solution containing a conductive polymer. <8> A polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), an ultraviolet absorber (B); A single-layer conductive polymer film.

[0010] [ka]

[0011] [In the general formula (1), M + represents an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium ion. 1 represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom; m independently represents an integer of 1 to 10; and n independently represents 0 or 1. [Effects of the Invention]

[0012] According to one aspect of the present invention, a conductive polymer solution can be provided that can form a layer having both antistatic properties and ultraviolet absorbing properties by simply applying one layer of the above-mentioned coating film, thereby simplifying the production process. DETAILED DESCRIPTION OF THE INVENTION

[0013] An embodiment of the present invention will be described in detail below. In this specification, the symbol "to" means a range of values ​​that is inclusive of both the upper and lower limits of the symbol.

[0014] [1. Conductive polymer solution] As a result of intensive research, the present inventors have found that by using a conductive polymer solution containing a polythiophene having a structural unit represented by a specific formula, an ultraviolet absorber, and an organic solvent, a layer having both antistatic properties and ultraviolet absorbing properties can be formed by simply applying a single layer of the conductive polymer solution, thereby simplifying the manufacturing process, and have completed the present invention. A conductive polymer solution according to one embodiment of the present invention contains polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), an ultraviolet absorber (B), and an organic solvent (C).

[0015] [ka]

[0016] [1-1. Polythiophene (A)] In general formula (1), M + represents an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium ion. 1 represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom; m independently represents an integer of 1 to 10; and n independently represents 0 or 1.

[0017] The structural unit represented by the general formula (2) represents the doped state of the structural unit represented by the general formula (1), and the doped state is realized when the sulfo group or sulfonate group in the structural unit represented by the general formula (1) acts as a p-type dopant.

[0018] R in the above general formulas (1) and (2) 1The linear or branched alkyl group having 3 to 6 carbon atoms, represented by the formula (I), is not particularly limited, and examples thereof include an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-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.

[0019] R 1 In terms of excellent film-forming properties, is preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom, more preferably a hydrogen atom, a methyl group, or a fluorine atom, and most preferably a methyl group.

[0020] In the above general formula (1), M + represents an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium ion.

[0021] The alkali metal ions are not particularly limited, but examples thereof include Li ions, Na ions, and K ions.

[0022] The conjugate acid of the amine compound is a cationic compound in which a proton is added to an amine compound. The amine compound is not particularly limited, but examples thereof include ammonia, a compound represented by the general formula NH2(R 2 ), NH(R 2 )(R 3 ), and N(R 2 )(R 3 )(R 4 ) as well as amine compounds, pyridine compounds, and imidazole compounds.

[0023] R 2 ~R 4 each independently represents an alkyl group having a total of 1 to 40 carbon atoms, which may have a substituent (among these, the alkyl group having 3 to 40 carbon atoms may be linear, branched, or cyclic). 2 ~R 4are more preferably each independently a hydrogen atom or an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent (among which, alkyl groups having 3 to 20 carbon atoms may be linear, branched, or cyclic), and even more preferably each independently a hydrogen atom or an alkyl group having a total of 1 to 6 carbon atoms which may have a substituent (among which, alkyl groups having 3 to 6 carbon atoms may be linear, branched, or cyclic).

[0024] Also, R 2 ~R 4 When is an alkyl group having a substituent, examples of the substituent include an alkoxy group having 1 to 6 carbon atoms, an aryl group having 1 to 20 carbon atoms, a hydroxy group, an amino group, an alkyl ether group, an aryl ether group, a thiol group, an alkyl sulfide group, or a carboxyl group, and more preferably, an alkyl group having a hydroxy group such as a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, or a 2,3-dihydroxypropyl group.

[0025] Here, the alkyl group having a total of 1 to 40 carbon atoms which may have a substituent, or the alkyl group having a total of 1 to 20 carbon atoms which may have a substituent, is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2,3-dihydroxypropyl group, a methoxymethyl group, an ethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxyethoxyethyl group, a benzyl group, a phenethyl group, and an aminoethyl group.

[0026] The alkyl group having a total of 1 to 6 carbon atoms which may have the above-mentioned substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2,3-dihydroxypropyl group, a methoxymethyl group, an ethoxymethyl group, a hydroxyethoxyethyl group, and a hydroxyethoxyethoxyethyl group.

[0027] Among these, the substituent R 2 ~R 4 More preferably, each independently represents a hydrogen atom, a methyl group, an ethyl group, or a hydroxyethyl group.

[0028] The pyridine compound is not particularly limited, but examples thereof include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, picoline, lutidine, etc. Among these, pyridine, picoline, lutidine, etc. are preferred.

[0029] The imidazole compound is not particularly limited, but examples thereof include imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, etc. Among these, imidazole, 1-methylimidazole, 1,2-dimethylimidazole, etc. are preferred.

[0030] The total number of carbon atoms in the conjugated acid of the amine compound is not particularly limited, but may be, for example, 1 to 30, and preferably 8 to 30 from the viewpoint of solubility.

[0031] More specifically, examples of the conjugate acid of the amine compound include methylammonium ion, dimethylammonium ion, trimethylammonium ion, ethylammonium ion, triethylammonium ion, normal-propylammonium ion, isopropylammonium ion, normal-butylammonium ion, hexylammonium ion, 2-hydroxyethylammonium ion, N,N-dimethyl-N-(2-hydroxyethyl)ammonium ion, N-methyl-N-(2-hydroxyethyl)ammonium ion, di(2-hydroxyethyl)ammonium ion, N-methyl-N,N-di(2-hydroxyethyl)ammonium ion, N,N,N-tri(2-hydroxyethyl)ammonium ion, 2,3-dihydroxypropylammonium ion, N-methyl-N-(2,3-dihydroxypropyl)ammonium ion, N,N-dimethyl-N-(2,3-dihydroxypropyl)ammonium ion, ammonium ion, 1,4-butanediammonium ion, triisobutylammonium ion, triisopentylammonium ion, triisooctylammonium ion, octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, decylammonium ion, dodecylammonium ion, tridecylammonium ion, pentadecylammonium ion, hexadecylammonium ion, octadecylammonium ion, oleylammonium ion, di-n-octylammonium ion, bis(2-ethylhexyl)ammonium ion, dimethyloctylammonium ion, dimethyldecylammonium ion, dimethyldodecylammonium ion, dimethylstearylammonium ion, trihexylammonium ion, trioctylammonium ion, tris(2-ethylhexyl)ammonium ion, and phenylammonium ion.Among these, at least one selected from the group consisting of octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, decylammonium ion, dodecylammonium ion, tridecylammonium ion, pentadecylammonium ion, hexadecylammonium ion, octadecylammonium ion, oleylammonium ion, di-n-octylammonium ion, bis(2-ethylhexyl)ammonium ion, dimethyloctylammonium ion, dimethyldecylammonium ion, dimethyldodecylammonium ion, dimethylstearylammonium ion, trihexylammonium ion, trioctylammonium ion, tris(2-ethylhexyl)ammonium ion, and phenylammonium ion is preferred.

[0032] The total number of carbon atoms in the conjugate acid of the pyridine compound is preferably 3 to 20. The conjugate acid of the pyridine compound is not particularly limited, but examples thereof include a pyridinium ion, a 2-methylpyridinium ion, a 3-methylpyridinium ion, a 4-methylpyridinium ion, a picolinium ion, and a lutidinium ion. Of these, a pyridinium ion, a picolinium ion, and a lutidinium ion are preferred.

[0033] The total number of carbon atoms in the conjugate acid of the imidazole compound is preferably 3 to 20. The conjugate acid of the imidazole compound is not particularly limited, but examples thereof include imidazolium ion, 2-methylimidazolium ion, 2-ethyl-4-methylimidazolium ion, 2-phenylimidazolium ion, 2-phenyl-4-methylimidazolium ion, 1-methylimidazolium ion, and 1,2-dimethylimidazolium ion. Of these, imidazolium ion, 1-methylimidazolium ion, and 1,2-dimethylimidazolium ion are preferred.

[0034] The total number of carbon atoms in the quaternary ammonium ion is not particularly limited, but may be, for example, 4 to 30, and more preferably 8 to 30.

[0035] The quaternary ammonium ion is not particularly limited, but examples thereof include tetramethylammonium ion, tetraethylammonium ion, tetra-normal-propylammonium ion, tetra-normal-butylammonium ion, tetra-normal-hexylammonium ion, decyltrimethylammonium ion, dodecyltrimethylammonium ion, tetrahexylammonium ion, etc. Among these, at least one selected from the group consisting of decyltrimethylammonium ion, dodecyltrimethylammonium ion, and tetrahexylammonium ion is preferred.

[0036] The quaternary ammonium ion may be obtained by adding a quaternary ammonium salt to the conductive polymer solution according to one embodiment of the present invention and allowing it to react with the polythiophene (A). Examples of the quaternary ammonium salt include, but are not limited to, chlorides, bromides, hydroxides, and hydrogen sulfates. Specific examples include tetramethylammonium chloride, tetraethylammonium chloride, tetra-n-propylammonium chloride, tetra-n-butylammonium chloride, tetra-n-hexylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrahexylammonium hydroxide, tetrahexylammonium hydrogen sulfate, and tetrahexylammonium bromide. Among these, at least one selected from the group consisting of decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrahexylammonium hydroxide, tetrahexylammonium hydrogen sulfate, and tetrahexylammonium bromide is preferred.

[0037] The above M +In terms of excellent coating film application properties, the cation is preferably at least one selected from the group consisting of octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, decylammonium ion, dodecylammonium ion, tridecylammonium ion, pentadecylammonium ion, hexadecylammonium ion, octadecylammonium ion, oleylammonium ion, di-n-octylammonium ion, bis(2-ethylhexyl)ammonium ion, dimethyloctylammonium ion, dimethyldecylammonium ion, dimethyldodecylammonium ion, dimethylstearylammonium ion, trihexylammonium ion, trioctylammonium ion, tris(2-ethylhexyl)ammonium ion, phenylammonium ion, pyridinium ion, picolinium ion, lutidinium ion, imidazolium ion, 1-methylimidazolium ion, 1,2-dimethylimidazolium ion, decyltrimethylammonium ion, dodecyltrimethylammonium ion, and tetrahexylammonium ion.

[0038] In the above general formulas (1) and (2), m independently represents an integer of 1 to 10, and n independently represents 0 or 1. From the viewpoint of solubility and coatability of the conductive polymer solution, m is preferably an integer of 2 to 6, more preferably 2, 3, 4, or 5, and even more preferably 2 or 3. Furthermore, from the viewpoint of solubility and coatability of the conductive polymer solution, n is preferably 1.

[0039] For polythiophenes containing at least two or more structural units selected from the group consisting of structural units represented by general formula (1) and structural units represented by general formula (2), the polystyrene sulfonic acid-equivalent number average molecular weight measured by gel permeation chromatography is preferably 3,500 or more, more preferably 4,000 or more, and even more preferably 5,000 or more, in order to obtain high electrical conductivity. Furthermore, in order to facilitate the operability of the conductive polymer solution, the polystyrene sulfonic acid-equivalent number average molecular weight of the polythiophene measured by gel permeation chromatography is preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. Therefore, the polystyrene sulfonic acid-equivalent number average molecular weight of the polythiophene is preferably 3,500 to 30,000, more preferably 4,000 to 20,000, and even more preferably 5,000 to 15,000.

[0040] The method and conditions for measuring the molecular weight of the polythiophene by gel permeation chromatography are in accordance with ISO 16014-3:2012 (JIS K 7252-3:2016).

[0041] In the conductive polymer solution according to one embodiment of the present invention, from the viewpoint of improving conductivity, the content of polythiophene (A) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. From the viewpoint of improving film-forming properties, the content of polythiophene (A) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. Therefore, the content of polythiophene (A) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and even more preferably 0.1 to 3% by mass.

[0042] 1-1-1. Polythiophene Production Method Polythiophenes containing at least two or more structural units selected from the group consisting of structural units represented by the general formula (1) and structural units represented by the general formula (2) can be produced by polymerizing a thiophene monomer represented by the following general formula (3) in water or an alcohol solvent in the presence of an oxidizing agent such as an iron salt and / or persulfuric acid. If necessary, other procedures such as solvent washing, reprecipitation, centrifugal sedimentation, ultrafiltration, dialysis, and ion exchange resin treatment can also be combined.

[0043] [ka]

[0044] In the above formula (3), R 1 , m, and n are R in the above general formulas (1) and (2). 1 , m, and n have the same definitions. + represents a hydrogen ion or an alkali metal ion.

[0045] The thiophene monomer represented by the general formula (3) is not particularly limited, but specific examples thereof include sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propanesulfonate, potassium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate, Sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-ethyl-1-propanesulfonate, Sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propyl-1-propanesulfonate, Sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butyl-1-propanesulfonate, Sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-pentyl-1-propane Sodium sulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-hexyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isopropyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isobutyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isobutyl-1-propanesulfonate ]dioxin-2-yl)methoxy]-1-isopentyl-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-propanesulfonate, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate, potassium 3-[(2,3-dihydrothieno[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,Ammonium 3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate, Triethylammonium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate, Sodium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butanesulfonate, Sodium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butanesulfonate potassium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonate, sodium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonate, potassium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonate, sodium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-butanesulfonate , 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-butanesulfonic acid potassium salt, 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)hexane-1-sulfonic acid sodium salt, 6-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonic acid lithium salt Examples include ammonium 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, sodium 8-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)octane-1-sulfonate, and potassium 8-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)octane-1-sulfonate.

[0046] The aforementioned M +The alkali metal ion represented by the formula (I) is not particularly limited, but examples thereof include a lithium ion, a sodium ion, a potassium ion, and a cesium ion.

[0047] The solvent used in the polymerization reaction of the thiophene monomer represented by the above formula (3) is preferably water, alcohol, or an aqueous alcohol solution. Examples of water include pure water, and distilled water or ion-exchanged water may also be used. Examples of alcohol solvents include alcohols such as methanol, ethanol, propanol, and butanol. These alcohol solvents may be used alone or in combination with water. Of these solvents, water or methanol is preferred, and water is more preferred. The solvent may also be degassed or substituted with an inert gas such as nitrogen.

[0048] The amount of the solvent used in the polymerization reaction of the thiophene monomer is, for example, an amount that dissolves the thiophene monomer, and is not particularly limited. The amount is preferably in the range of 0.1 to 100 times by weight, more preferably in the range of 1 to 20 times by weight, the amount of the thiophene monomer according to the embodiment of the present invention that is charged.

[0049] The oxidizing agent used in the polymerization reaction of the thiophene monomer promotes oxidative polymerization by oxidative dehydrogenation. The oxidizing agent is not particularly limited, but examples thereof include persulfates, iron salts (II or III), hydrogen peroxide, permanganates, dichromates, cerium (IV) sulfate, and oxygen, which may be used alone or in combination.

[0050] Specific examples of persulfates include persulfuric acid, ammonium persulfate, sodium persulfate, and potassium persulfate.

[0051] Specific examples of iron salts include trivalent iron salts such as FeCl3, FeBr3, Fe2(SO4)3, Fe(NO3)3·9H2O, iron perchlorate, and iron(III) para-toluenesulfonate, and divalent iron salts such as FeCl2, FeBr2, FeSO4·7H2O, and iron(II) acetate. These may be used in either anhydrous or hydrate form.

[0052] Specific examples of permanganates include sodium permanganate, potassium permanganate, and magnesium permanganate.

[0053] Specific examples of dichromates include ammonium dichromate and potassium dichromate.

[0054] Among these oxidizing agents, FeCl3, Fe2(SO4)3, Fe2(SO4)3, or a combination of persulfate and iron salt (II or III) is particularly preferred.

[0055] The amount of the oxidizing agent used in the polymerization reaction of the thiophene monomer is not particularly limited, but is preferably 0.5 to 50 times the number of moles of the charged thiophene monomer, more preferably 1 to 20 times, and even more preferably 1 to 10 times.

[0056] When the oxidizing agent used in the polymerization reaction of the thiophene monomer is, for example, an iron salt (III) alone, it is preferable to use an iron salt (III) in an amount equal to or greater than the number of moles of thiophene monomer charged as a raw material, and to use the iron salt so that the iron concentration in the solvent is 10% by weight or more. To achieve better conductivity, it is even more preferable that the iron concentration in the solvent is 20% by weight or more. The iron concentration here is a value expressed as iron salt / (iron salt + water) × 100 (wt%), and the iron salt is calculated as an anhydrous form.

[0057] When the oxidizing agent used in the polymerization reaction of the thiophene monomer is a combination of a persulfate and an iron salt (II or III), the amount of the persulfate is preferably in the range of 0.5 to 20 times by mole and the amount of the iron salt (II or III) is preferably in the range of 0.01 to 10 times by mole, and more preferably in the range of 1.5 to 10 times by mole and the amount of the iron salt (II or III) is preferably in the range of 0.05 to 5 times by mole, relative to the number of moles of the charged thiophene monomer.

[0058] The pressure for the polymerization reaction of the thiophene monomer may be any of atmospheric pressure, reduced pressure, and increased pressure.

[0059] The reaction atmosphere for the polymerization reaction of the thiophene monomer may be air or an inert gas such as nitrogen or argon, more preferably an inert gas.

[0060] The reaction temperature for the polymerization reaction of the thiophene monomer is not particularly limited, but is preferably in the range of -10 to 100°C, more preferably in the range of 0 to 50°C.

[0061] The reaction time for the polymerization reaction of the thiophene monomer is a time during which the oxidative polymerization proceeds sufficiently, and is not particularly limited, but is preferably in the range of 0.5 to 200 hours, more preferably in the range of 0.5 to 80 hours.

[0062] The polymerization reaction method is not particularly limited, but for example, the thiophene monomer represented by the formula (3) may be dissolved in water in advance, and the oxidizing agent may be added dropwise all at once or slowly, or conversely, an aqueous solution of the thiophene monomer represented by the formula (3) may be added dropwise all at once or slowly to a solid or aqueous solution of the oxidizing agent. When two or more oxidizing agents are used, the oxidizing agents may be added sequentially.

[0063] In the polymerization reaction described above, the viscosity of the liquid tends to increase with the addition of the oxidizing agent, so it is necessary to stir the entire liquid uniformly. Regarding the stirring blades, propeller blades, paddle blades, Maxblend® blades (manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd.), Fullzone® blades (manufactured by Kobelco Environmental Solutions Co., Ltd.), and disc turbines can be used. Large blades such as Maxblend blades and Fullzone blades are preferred for more uniform mixing within the reaction vessel. Homomixers and homogenizers used for emulsification and dispersion may also be used in combination. When using a stirring method using conventional stirring blades, it is preferable to increase the rotation speed of the stirring blades as much as possible within a range that does not result in a decrease in stirring efficiency due to the incorporation of a large amount of gas from the gas phase of the reaction vessel into the reaction liquid.

[0064] A typical method for isolating and purifying the above polythiophene is, for example, as follows.

[0065] First, the aqueous solution after the polymerization reaction is desalted and purified directly using membrane separation methods such as ultrafiltration and dialysis, and then passed through cation and anion exchange resins to obtain M + is a hydrogen ion, an acid-type polythiophene aqueous solution can be obtained.

[0066] Furthermore, if necessary, the resulting aqueous solution can be roughly concentrated and added to a poor solvent such as acetone to cause precipitation, thereby obtaining polythiophene as a powder.

[0067] Furthermore, when forming a salt-type polythiophene, for example, a stock solution of various amine compounds or ammonium salts, or an aqueous solution thereof, or a solution obtained by diluting these with other suitable solvents is added to the aqueous solution of the acid-type polythiophene. + is NH4 + If necessary, the resulting aqueous solution can be added to a poor solvent such as acetone to obtain various ammonium salt-type polythiophenes in powder form.

[0068] [1-2. Ultraviolet absorber (B)] As used herein, ultraviolet absorbers refer to materials that absorb at wavelengths of about 400 nm or less.

[0069] In one embodiment of the present invention, the ultraviolet absorber (B) can be at least one selected from the group consisting of benzophenone-based compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, and triazine-based compounds.

[0070] Examples of benzophenone compounds include 2-hydroxy-4-(octyloxy)benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2,2',4,4'-tetrahydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0071] Benzotriazole compounds include 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-propenyl)phenol, and 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole. )benzotriazole, 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol, 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol], 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and the like.

[0072] Examples of cyanoacrylate compounds include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and 2,2-bis{[(2-cyano-3,3-diphenylacryloyl)oxy]methyl}propane-1,3-diyl bis(2-cyano-3,3-diphenylacrylate).

[0073] Examples of triazine compounds include 2-ethylhexanoic acid = 2-[3-hydroxy-4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenoxy]ethyl, 2,2,2-(1,3,5-triazine-2,4,6-triyl)tris[5-(hexyloxy)-6-methylphenol], 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoate tris(2-ethylhexyl), 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, Examples thereof include 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, N,N',N''-tri(m-tolyl)-1,3,5-triazine-2,4,6-triamine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,2'-[6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diyl]bis[5-[(2-ethylhexyl)oxy]phenol], 2,4,6-tris(4-butoxy-2-hydroxyphenyl)-1,3,5-triazine, and 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.

[0074] As the ultraviolet absorber (B), from the viewpoint of ultraviolet absorption ability, a benzophenone-based compound or a benzotriazole-based compound is preferred, and 2-hydroxy-4-(octyloxy)benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, or 2-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol is more preferred.

[0075] In the conductive polymer solution according to one embodiment of the present invention, from the viewpoint of ultraviolet absorption ability, the content of the ultraviolet absorber (B) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. Furthermore, from the viewpoint of solubility in the solvent, the content of the ultraviolet absorber (B) is preferably 10% by mass or less, more preferably 7.5% by mass or less, and even more preferably 5% by mass or less. Therefore, the content of the ultraviolet absorber (B) is preferably 0.01 to 10% by mass, more preferably 0.05 to 7.5% by mass, and even more preferably 0.1 to 5% by mass.

[0076] [1-3. Organic Solvents (C)] In one embodiment of the present invention, the organic solvent (C) can be at least one selected from the group consisting of alcohol solvents, ether solvents, ketone solvents, and aromatic solvents.

[0077] The alcohol solvent is not particularly limited, but examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tertiary butanol, and ethylene glycol.

[0078] The ether solvent is not particularly limited, but examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), methyl cellosolve, ethyl cellosolve, butyl cellosolve, and 1,4-dioxane.

[0079] The ketone solvent is not particularly limited, but examples thereof include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetone, methyl propyl ketone, and diacetone alcohol.

[0080] The aromatic solvent is not particularly limited, but examples thereof include benzene, toluene, and xylene.

[0081] As the organic solvent (C), 1-butanol, propylene glycol monomethyl ether (PGME), methyl cellosolve, ethyl cellosolve, butyl cellosolve, or methyl isobutyl ketone (MIBK) is preferred in terms of excellent coating film coating properties.

[0082] In the conductive polymer solution according to one embodiment of the present invention, the content of the solvent (C) is preferably 80 to 99.9 mass %, more preferably 90 to 99.9 mass %, from the viewpoint of improving film-forming properties.

[0083] [1-5. Manufacturing method of conductive polymer solution] The method for producing the conductive polymer solution according to this embodiment is not particularly limited, but may be, for example, a method in which a solution or solid of the polythiophene (A) according to this embodiment, an ultraviolet absorber (B), and an organic solvent (C) are mixed and homogenized by stirring or the like.

[0084] The temperature during mixing is not particularly limited, but may be, for example, room temperature or heated, preferably 0° C. or higher and 100° C. or lower. The atmosphere during mixing is not particularly limited, but may be air or an inert gas.

[0085] Furthermore, the conductive polymer solution according to one embodiment of the present invention may contain a component (D) other than those described above. The component (D) other than those described above is not particularly limited, but examples thereof include a binder, a visible light absorber, and a surfactant.

[0086] The binder is not particularly limited, but examples thereof include cellulose resins, vinylpyrrolidone resins, acrylic resins, urethane resins, methyl methacrylate resins, styrene butadiene resins, vinyl acetate resins, polyamide resins, phenolic resins, epoxy resins, melamine resins, thermosetting polyimides, nitrocellulose or other cellulose resins, polyvinyl alcohol resins, etc. Curing methods include heat curing and UV curing.

[0087] The binder resin is preferably at least one selected from the group consisting of cellulose-based resins, vinylpyrrolidone resins, urethane resins, acrylic resins, and epoxy resins, in view of their excellent film-forming properties.

[0088] When the conductive polymer solution according to one embodiment of the present invention contains the above-mentioned binder, the content of the binder is preferably 0.01 to 20 mass %, and more preferably 0.1 to 10 mass %, based on 100 mass % of the conductive polymer solution.

[0089] The visible light absorber is not particularly limited, but examples of the visible light absorber that can be used include FDB-001, FDB-002, FDB-004, FDB-009, FDB-027, and FDB-036 manufactured by Yamada Chemical Co., Ltd. Adding a visible light absorber can broaden the absorption wavelength range.

[0090] When the conductive polymer solution according to one embodiment of the present invention contains the above-mentioned visible light absorber, the content of the visible light absorber is preferably 0.01 to 10 mass %, and more preferably 0.1 to 5 mass %, based on 100 mass % of the conductive polymer solution.

[0091] The surfactant is not particularly limited, but examples thereof include anionic surfactants (e.g., sodium lauryl alcohol sulfate and sodium dodecylbenzenesulfonate), cationic surfactants (e.g., dodecyltrimethylammonium chloride), nonionic surfactants, amphoteric surfactants, fluorine-based surfactants, and silicone-based surfactants, and more preferably at least one selected from the group consisting of nonionic surfactants and amphoteric surfactants.

[0092] When the conductive polymer solution according to one embodiment of the present invention contains the above-mentioned surfactant and other components, the content of each of these components is preferably 0.1 to 60 mass %, and more preferably 1 to 40 mass %, based on 100 mass % of the conductive polymer solution.

[0093] [2. Conductive polymer film] The conductive polymer film according to one embodiment of the present invention is not particularly limited, and can be produced, for example, by applying a conductive polymer solution according to one embodiment of the present invention to a substrate and then drying it. The conductive polymer film produced in this manner is a monolayer film containing polythiophene (A) containing at least one structural unit selected from the group consisting of structural units represented by the following general formula (1) and structural units represented by the following general formula (2), and ultraviolet absorber (B).

[0094] [ka]

[0095] The substrate is not particularly limited, but examples thereof include glass, plastic, polyester, polyacrylate, polycarbonate, resist substrate, etc. The coating method is not particularly limited, but examples thereof include screen printing, casting, dipping, bar coating, roll coating, gravure coating, flexographic printing, spray coating, inkjet printing, etc.

[0096] The drying temperature is not particularly limited as long as it is a temperature at which a uniformly dried conductive polymer film can be obtained and is equal to or lower than the heat resistance temperature of the substrate, but is preferably in the range of room temperature (15 to 25°C) to 300°C, more preferably in the range of room temperature to 250°C, and even more preferably in the range of 90 to 250°C.

[0097] The drying atmosphere may be air, an inert gas, a vacuum, or a reduced pressure, but from the viewpoint of preventing deterioration of the conductive polymer film, an inert gas such as nitrogen or argon is preferred.

[0098] The thickness of the conductive polymer film according to one embodiment of the present invention is not particularly limited, but is preferably 1×10 -2 ~1×10 2 The range of μm is preferred.

[0099] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention. [Example]

[0100] Examples relating to the conductive polymer solution and conductive polymer film of the present invention are shown below, but the present invention is not limited to these examples. Conductive polymer films were prepared according to the following methods using the conductive polymer solutions of the examples, comparative examples, and reference examples described below, and the surface resistivity, ultraviolet transmittance, and haze of the prepared conductive polymer films were measured.

[0101] [Preparation of Conductive Polymer Film] A conductive polymer film was produced using a desktop printing tester (Matsuo Sangyo K202 Control Coater) in the following manner: Using a wire bar that gave a film thickness (wet film thickness) of 12 μm immediately after coating, the conductive polymer solution was screen-printed onto a PET film substrate (Toyobo Cosmoshine A4100), and then heated in a thermostatic chamber set to 120°C in air for 2 minutes to obtain a conductive polymer film.

[0102] [Method for measuring the surface resistivity of a conductive polymer film] The surface resistivity of the conductive polymer film was measured by the following method. Using a surface resistance measuring instrument (Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation or Hiresta UX MCP-HT8000 manufactured by Mitsubishi Chemical Corporation) and an ASP as the measurement probe, the surface resistivity of the conductive polymer film was measured in an atmosphere of 25°C and 50% RH. Measurements were taken at nine points spaced 6.25 mm apart in the x direction and 6.25 mm apart in the y direction, and the average surface resistivity at the nine points was calculated. It can be said that the lower the surface resistivity, the higher the antistatic ability.

[0103] [Measurement of UV transmittance of conductive polymer film] The ultraviolet transmittance of the conductive polymer film was measured using a UV-visible spectrophotometer (Shimadzu UV-3100). The measurement was performed at wavelengths of 325 nm and 365 nm. The lower the ultraviolet transmittance, the higher the ultraviolet absorption ability.

[0104] [Method for measuring haze and total light transmittance of conductive polymer film] The haze and total light transmittance of the conductive polymer film were measured using a haze meter (NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd.) The lower the haze value, the less cloudy the film is, i.e., the higher the transparency.

[0105] Synthesis Example 1: Synthesis of polythiophene (PT) A 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid polymer (a polymer containing repeating units represented by the following formula (4) and formula (5), having a number average molecular weight of approximately 7000) was produced according to a conventionally known production method.

[0106] [ka]

[0107] 50.0 g of an aqueous solution containing 1 wt % of the 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid polymer was stirred with 7.4 g of a methanol solution containing 5 wt % of dioctylamine, and the resulting precipitate was filtered and dried to obtain 0.6 g of a solid dioctylamine salt of the polymer (hereinafter also referred to as "PT"). That is, the PT is a dioctylamine salt of the polymer represented by the general formula (1), + It contains the conjugate acid of dioctylamine (i.e., dioctylammonium ion) as the cation.

[0108] Example 1 (Preparation and Evaluation of Conductive Polymer Solution) To 95.3 g of 1-butanol, 0.2 g of PT, 2.5 g of ethyl cellulose (Tokyo Chemical Industry Co., Ltd., product code G0478), and 2 g of 2-hydroxy-4-(octyloxy)benzophenone (Fujifilm Wako Pure Chemical Industries, Ltd., product code 089-06911) were added and stirred to prepare a conductive polymer solution according to Example 1. From this conductive polymer solution, a conductive polymer film according to Example 1 was produced according to the above-mentioned [Method for producing a conductive polymer film]. The conductive polymer film had low transmittance of ultraviolet light at wavelengths of 325 nm and 365 nm, and was confirmed to have ultraviolet absorption ability. Furthermore, the conductive polymer film was 10 8 It was confirmed that the surface resistivity was Ω / □ and that the film had antistatic properties.

[0109] Example 2 (Preparation and Evaluation of Conductive Polymer Solution) To 95.3 g of PGME, 0.2 g of PT, 2.5 g of ethyl cellulose (Tokyo Chemical Industry Co., Ltd., product code G0478), and 2 g of 2-hydroxy-4-(octyloxy)benzophenone (Fujifilm Wako Pure Chemical Industries, Ltd., product code 089-06911) were added and stirred to prepare a conductive polymer solution according to Example 2. From this conductive polymer solution, a conductive polymer film according to Example 2 was produced according to the above-mentioned [Method for producing a conductive polymer film]. The conductive polymer film had low transmittance of ultraviolet light at wavelengths of 325 nm and 365 nm, and was confirmed to have ultraviolet absorption ability. Furthermore, the conductive polymer film was immersed in water for 10 minutes. 8 It was confirmed that the surface resistivity was Ω / □ and that the film had antistatic properties.

[0110] Example 3 (Preparation and Evaluation of Conductive Polymer Solution) To 95.3 g of MIBK, 0.2 g of PT, 2.5 g of ethyl cellulose (Tokyo Chemical Industry Co., Ltd., product code G0478), and 2 g of 2-hydroxy-4-(octyloxy)benzophenone (Fujifilm Wako Pure Chemical Industries, Ltd., product code 089-06911) were added and stirred to prepare a conductive polymer solution according to Example 3. From this conductive polymer solution, a conductive polymer film according to Example 3 was produced according to the above-mentioned [Method for producing a conductive polymer film]. The conductive polymer film had low transmittance of ultraviolet light at wavelengths of 325 nm and 365 nm, and was confirmed to have ultraviolet absorption ability. Furthermore, the conductive polymer film was measured at 10 8 It was confirmed that the surface resistivity was Ω / □ and that the film had antistatic properties.

[0111] Comparative Example 1 (Preparation and Evaluation of Conductive Polymer Solution) To 95.3 g of water were added 0.2 g of PT, 2.5 g of ethyl cellulose (Tokyo Chemical Industry Co., Ltd., product code G0478), and 2 g of 2-hydroxy-4-(octyloxy)benzophenone (Fujifilm Wako Pure Chemical Industries, Ltd., product code 089-06911). The mixture was then stirred, but the compound added to the water did not dissolve.

[0112] Example 4 (Preparation and Evaluation of Conductive Polymer Solution) To 94.6 g of 1-butanol, 0.2 g of PT, 2.5 g of ethyl cellulose (Tokyo Chemical Industry Co., Ltd., product code G0478), and 2.7 g of 2-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol (BASF, product name Tinuvin 928) were added and stirred to prepare a conductive polymer solution according to Example 4. A conductive polymer film according to Example 4 was produced from the conductive polymer solution according to the above-mentioned "Method for producing a conductive polymer film." The conductive polymer film had low transmittance of ultraviolet light at wavelengths of 325 nm and 365 nm, and was confirmed to have ultraviolet absorption capabilities. Furthermore, the conductive polymer film was measured at 10 8 It was confirmed that the surface resistivity was Ω / □ and that the film had antistatic properties.

[0113] Example 5 (Preparation and Evaluation of Conductive Polymer Solution) To 94.6 g of PGME, 0.2 g of PT, 2.5 g of ethyl cellulose (Tokyo Chemical Industry Co., Ltd., product code G0478), and 2.7 g of 2-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol (BASF, product name Tinuvin 928) were added and stirred to prepare a conductive polymer solution according to Example 5. A conductive polymer film according to Example 5 was produced from the conductive polymer solution according to the above-mentioned "Method for producing a conductive polymer film." The conductive polymer film had low transmittance of ultraviolet light at wavelengths of 325 nm and 365 nm, and was confirmed to have ultraviolet absorption capabilities. Furthermore, the conductive polymer film was measured at 10 8 It was confirmed that the surface resistivity was Ω / □ and that the film had antistatic properties.

[0114] Example 6 (Preparation and Evaluation of Conductive Polymer Solution) To 94.6 g of MIBK, 0.2 g of PT, 2.5 g of ethyl cellulose (Tokyo Chemical Industry Co., Ltd., product code G0478), and 2.7 g of 2-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol (BASF, product name Tinuvin 928) were added and stirred to prepare a conductive polymer solution according to Example 6. A conductive polymer film according to Example 6 was produced from the conductive polymer solution according to the above-mentioned "Method for producing a conductive polymer film." The conductive polymer film had low transmittance of ultraviolet light at wavelengths of 325 nm and 365 nm, and was confirmed to have ultraviolet absorption capabilities. Furthermore, the conductive polymer film was measured at 10 8 It was confirmed that the surface resistivity was Ω / □ and that the film had antistatic properties.

[0115] Comparative Example 2 (Preparation and Evaluation of Conductive Polymer Solution) To 94.6 g of water, 0.2 g of PT, 2.5 g of ethyl cellulose (Tokyo Chemical Industry Co., Ltd., product code G0478), and 2.7 g of 2-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol (BASF, product name Tinuvin928) were added. The mixture was then stirred, but the compound added to the water did not dissolve.

[0116] Reference Example 1 (Preparation and Evaluation of Conductive Polymer Solution) 0.2 g of PT and 2.5 g of ethyl cellulose were added to 97.3 g of PGME and stirred to prepare a conductive polymer solution according to Reference Example 1. From this conductive polymer solution, a conductive polymer film according to Reference Example 1 was produced according to the above-mentioned [Method for producing a conductive polymer film]. The conductive polymer film had high transmittance of ultraviolet light at wavelengths of 325 nm and 365 nm, and it was confirmed that it did not have ultraviolet absorption ability. On the other hand, the conductive polymer film was also confirmed to have high transmittance of ultraviolet light at wavelengths of 325 nm and 365 nm. 8 It showed a surface resistivity of Ω / □, and it was confirmed that it had antistatic properties.

[0117] Table 1 shows the measurement results of ultraviolet transmittance, surface resistivity, total light transmittance and haze for each of the Examples, Comparative Examples and Reference Examples.

[0118] [Table 1]

[0119] From a comparison between the Example and Comparative Examples 1 and 2, it was confirmed that by using an organic solvent as the solvent, the compounds (polythiophene, ultraviolet absorber, etc.) added to the solvent were dissolved.

[0120] Furthermore, by comparing the Examples and Comparative Examples with the Reference Example, it was confirmed that the conductive polymer solution containing an ultraviolet absorber has low ultraviolet transmittance at wavelengths of 325 nm and 365 nm and has ultraviolet absorption ability.

[0121] That is, it was confirmed that by using the conductive polymer solution according to the present invention, a layer having both antistatic properties and ultraviolet absorbing properties can be formed by simply applying one layer. [Industrial Applicability]

[0122] The present invention can be used in, for example, antistatic materials, LCDs, organic EL devices, transparent electrodes, and the like.

Claims

1. A polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), an ultraviolet absorber (B); an organic solvent (C); The ultraviolet absorber (B) comprises at least one selected from the group consisting of 2-hydroxy-4-(octyloxy)benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, and 2-(2H-benzo[d][1,2,3]triazol-2-yl)-6-(2-phenylpropan-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol; The conductive polymer solution, wherein the organic solvent (C) is at least one selected from the group consisting of 1-butanol and propylene glycol monomethyl ether. 【Chemistry 1】 [In general formula (1), M ＋ represents an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium ion. １ represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom; m independently represents an integer of 1 to 10; and n independently represents 0 or 1.

2. Said M ＋ is a conjugated acid of an amine compound having a total of 8 to 30 carbon atoms, or a quaternary ammonium ion having a total of 8 to 30 carbon atoms.

3. Said M ＋ is at least one selected from the group consisting of octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, decylammonium ion, dodecylammonium ion, tridecylammonium ion, pentadecylammonium ion, hexadecylammonium ion, octadecylammonium ion, oleylammonium ion, di-n-octylammonium ion, bis(2-ethylhexyl)ammonium ion, dimethyloctylammonium ion, dimethyldecylammonium ion, dimethyldodecylammonium ion, dimethylstearylammonium ion, trihexylammonium ion, trioctylammonium ion, tris(2-ethylhexyl)ammonium ion, phenylammonium ion, decyltrimethylammonium ion, dodecyltrimethylammonium ion, and tetrahexylammonium ion.

4. 4. The conductive polymer solution according to claim 1, wherein the content of the polythiophene (A) is 0.01 to 10 mass %.

5. 5. The conductive polymer solution according to claim 1, wherein the content of the ultraviolet absorber (B) is 0.01 to 10 mass %.

Images