JP2024115530A - Conductive polymer solutions and their applications - Google Patents

Abstract

[Problem] To provide a conductive polymer solution in which the conductive polymer has high dispersibility in the adhesive and is less likely to aggregate, and an adhesive composition containing the conductive polymer solution. [Solution] To use a conductive polymer solution that contains polythiophene (A) containing two or more structural units represented by the following general formula (7), modified polyamine compound (B) having a specific structure, and organic solvent (C). JPEG2024115530000033.jpg34140 [Selected Figure] None

Description

The present invention relates to a conductive polymer solution and its uses.

Generally speaking, static electricity refers to the phenomenon in which an object accumulates an electric charge and becomes charged, or to the electric charge itself. Static electricity can be generated by the accumulation of electric charge caused by friction between two types of dielectric material, as well as by contact with a charged object, and can accumulate on the surface of the object.

The static electricity can cause inhalation of foreign objects such as dust, electrostatic damage to devices, malfunction of measuring instruments, or fires. Modern electromagnetic devices are also highly prone to temporary or permanent damage from static electricity discharges, making static electricity a particular problem in the electronics industry. The accumulation of static electricity on insulating objects is very likely and problematic when humidity is low or when liquids or solids are moving in contact with each other (frictional charging).

For example, in liquid crystal panels, an adhesive layer formed from an adhesive composition is often used to adhere a polarizing plate or a retardation plate to the glass substrate of a liquid crystal cell. These optical components such as polarizing plates and retardation plates are usually made of plastic materials, and therefore have high electrical insulation properties, so static electricity is likely to be generated when the adhesive layer is peeled off. Therefore, if a polarizing plate or retardation plate is attached to a liquid crystal cell while static electricity remains, dust may be attracted or the alignment of liquid crystal molecules may be disturbed, resulting in a decrease in performance.

In addition, when polarizing plates are manufactured at high speeds, static electricity can destroy TFTs and IC elements when the polarizing plate protective film is peeled off, something that did not occur in existing processes, and this can lead to malfunctions in the LCD panel.

To suppress the generation of static electricity, it is necessary to impart an antistatic function to the adhesive layer. As a means for achieving this, for example, it has been proposed to blend an ionic compound or a conductive complex containing a π-conjugated conductive polymer and a polyanion in the adhesive composition that forms the adhesive layer (Patent Documents 1 to 3).

JP 2014-058679 A JP 2022-092880 A Special Publication No. 2020-529511

However, the adhesive compositions containing conductive materials disclosed in Patent Documents 1 to 3 and the like have a problem in that the conductive materials have low dispersibility. Furthermore, the conductive adhesive films obtained from such adhesive compositions sometimes have low moisture resistance.

As a result of intensive research, the inventors discovered that the invention described below can solve the above problems, and have completed the present invention.

[1]
A conductive polymer solution comprising: polythiophene (A) containing two or more structural units represented by the following general formula (7); modified polyamine compound (B) constituted by a repeating unit represented by the following general formula (3-1) and/or a repeating unit represented by the following general formula (3-2), and a repeating unit represented by the following general formula (3-3); and an organic solvent (C).

[In general formula (7), R represents an organic group having a total of 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of sulfonic acid groups and phosphonic acid groups.]

[In the general formula (3-1), R ² represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms. X represents a divalent polymer group formed by random polymerization or block polymerization in a random order of k propyleneoxy groups (-CH ₂ -CH(CH ₃ )-O-) and j ethyleneoxy groups (-CH ₂ -CH ₂ -O-), k represents an integer of 0 to 50, j represents an integer of 10 to 100, and k+j=10 to 150. p represents 1 or 2. h represents an integer of 2 to 6. In the general formula (3-2), R ³ represents a divalent aliphatic hydrocarbon group having 8 to 22 carbon atoms which may be branched. m represents an integer of 2 to 11, and n represents an integer of 0 to 1000.]
[2]
The conductive polymer solution according to [1], wherein the organic solvent (C) is at least one selected from the group consisting of ester-based solvents and aromatic solvents.

[3]
The conductive polymer solution according to [1] or [2], wherein the organic solvent (C) is at least one selected from the group consisting of methyl acetate, ethyl acetate, n-propyl acetate, butyl acetate, isobutyl acetate, methoxybutyl acetate, benzene, toluene, and xylene.

[4]
The conductive polymer solution according to any one of [1] to [3], wherein the content of the polythiophene (A) is 0.01 to 10 parts by weight per 100 parts by weight of the organic solvent (C).

[5]
The conductive polymer solution according to any one of [1] to [4], wherein the content of the modified polyamine compound (B) is 0.01 to 10 parts by weight based on 100 parts by weight of the organic solvent (C).

[6]
The conductive polymer solution according to any one of [1] to [5], wherein the polythiophene (A) contains two or more structural units of at least one kind 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):

[In general formula (1), M ⁺ represents a proton, a conjugate acid of an amine compound, or a quaternary ammonium ion. In general formulas (1) and (2), ^R1 independently 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.]
[7]
The conductive polymer solution according to [6], wherein the M ⁺ is a proton or a conjugated acid of an amine compound having a total of 15 to 24 carbon atoms.

[8]
The conductive polymer solution according to [6] or [7], wherein M ⁺ is at least one selected from the group consisting of a dioctylammonium ion, a tridecylammonium ion, a hexadecylammonium ion, an octadecylammonium ion, an oleylammonium ion, a di-n-octylammonium ion, a bis(2-ethylhexyl)ammonium ion, a dimethylstearylammonium ion, a trihexylammonium ion, a trioctylammonium ion, a tris(2-ethylhexyl)ammonium ion, a dodecyltrimethylammonium ion, and a tetrahexylammonium ion.

[9]
A pressure-sensitive adhesive composition comprising the conductive polymer solution according to any one of [1] to [8] and a pressure-sensitive adhesive (D).

[10]
The pressure-sensitive adhesive composition according to [9], wherein the pressure-sensitive adhesive (D) is an acrylic pressure-sensitive adhesive.

[11]
A conductive adhesive film comprising: polythiophene (A) containing two or more structural units represented by the following general formula (7); modified polyamine compound (B) constituted by a repeating unit represented by the following general formula (3-1) and/or a repeating unit represented by the following general formula (3-2), and a repeating unit represented by the following general formula (3-3); and an adhesive (D).

[In general formula (7), R represents an organic group having a total of 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of sulfonic acid groups and phosphonic acid groups.]

[In the general formula (3-1), R ² represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms. X represents a divalent polymer group formed by random polymerization or block polymerization in a random order of k propyleneoxy groups (-CH ₂ -CH(CH ₃ )-O-) and j ethyleneoxy groups (-CH ₂ -CH ₂ -O-), k represents an integer of 0 to 50, j represents an integer of 10 to 100, and k+j=10 to 150. p represents 1 or 2. h represents an integer of 2 to 6. In the general formula (3-2), R ³ represents a divalent aliphatic hydrocarbon group having 8 to 22 carbon atoms which may be branched. m represents an integer of 2 to 11, and n represents an integer of 0 to 1000.]
[12]
The conductive adhesive film according to [11], wherein the polythiophene (A) contains two or more structural units 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):

[In general formula (1), M ⁺ represents a proton, a conjugate acid of an amine compound, or a quaternary ammonium ion. In general formulas (1) and (2), ^R1 independently 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.]
[13]
The conductive adhesive film according to [11] or [12], wherein the pressure-sensitive adhesive (D) is an acrylic pressure-sensitive adhesive.

[14]
[9] A resin composition for ultraviolet-curable hard coat, comprising the conductive polymer solution according to any one of [1] to [8] and an ultraviolet-curable resin (E).

[15]
A method for producing a hard coat, comprising the steps of applying the ultraviolet-curable hard coat resin composition according to [14] to a substrate, drying the applied composition, and then irradiating the substrate with ultraviolet light.

[16]
A cured product obtained by curing the ultraviolet-curable hard coat resin composition according to [14].

[17]
A hard coat comprising a polythiophene (A) containing two or more structural units represented by the following general formula (7), and a modified polyamine compound (B) constituted by a repeating unit represented by the following general formula (3-1) and/or a repeating unit represented by the following general formula (3-2), and a repeating unit represented by the following general formula (3-3):

[In general formula (7), R represents an organic group having a total of 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of sulfonic acid groups and phosphonic acid groups.]

[In the general formula (3-1), R ² represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms. X represents a divalent polymer group formed by random polymerization or block polymerization in a random order of k propyleneoxy groups (-CH ₂ -CH(CH ₃ )-O-) and j ethyleneoxy groups (-CH ₂ -CH ₂ -O-), k represents an integer of 0 to 50, j represents an integer of 10 to 100, and k+j=10 to 150. p represents 1 or 2. h represents an integer of 2 to 6. In the general formula (3-2), R ³ represents a divalent aliphatic hydrocarbon group having 8 to 22 carbon atoms which may be branched. m represents an integer of 2 to 11, and n represents an integer of 0 to 1000.]

According to one aspect of the present invention, it is possible to provide a conductive polymer solution or the like in which the conductive polymer has high dispersibility in the adhesive and the conductive polymer is less likely to aggregate. In addition, according to one aspect of the present invention, it is possible to provide a conductive adhesive film with excellent moisture resistance.

One embodiment of the present invention will be described in detail below. In this specification, unless otherwise specified, "A to B" representing a numerical range means "A or more, B or less."

Currently, commonly used adhesives are manufactured using acetate-based solvents. When adding additives to an adhesive to impart functionality, the additives must be uniformly mixed in the adhesive, and therefore the additives must be highly compatible with acetate-based solvents. As described below, no self-doped conductive polymers or compositions thereof that are known in the art and characterized by structural units represented by general formulas (1) and (2) have been found to have high compatibility with acetate-based solvents. On the other hand, the conductive polymer solution according to one embodiment of the present invention has been found to have high compatibility with acetate-based solvents, making it possible to impart antistatic functionality to adhesives that are widely available on the market.

According to one embodiment of the present invention, it is possible to provide a new adhesive composition having antistatic properties based on a conductive polymer solution that has not been reported before. In addition, according to one embodiment of the present invention, it is possible to provide an adhesive composition that has high dispersibility of the conductive material and is less susceptible to deterioration in quality due to aggregation of the conductive material, compared to those that have been reported before. By using such an adhesive composition, it is also possible to provide a conductive adhesive film with excellent moisture resistance.

In addition, according to the above-mentioned configuration, for example, by applying the conductive adhesive film according to one embodiment of the present invention to a liquid crystal display panel or the like, the occurrence rate of product defects caused by static electricity can be reduced. Such an effect also contributes to the achievement of, for example, Goal 12 of the Sustainable Development Goals (SDGs) advocated by the United Nations, "Ensure sustainable consumption and production patterns."

[1. Conductive polymer solution]
The conductive polymer solution according to one embodiment of the present invention contains a polythiophene (A) containing two or more structural units represented by the following general formula (7), a modified polyamine compound (B) constituted by a repeating unit represented by the following general formula (3-1) and/or a repeating unit represented by the following general formula (3-2), and a repeating unit represented by the following general formula (3-3), and an organic solvent (C).

[In general formula (7), R represents an organic group having a total of 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of sulfonic acid groups and phosphonic acid groups.]

[In the general formula (3-1), R ² represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms. X represents a divalent polymer group formed by random polymerization or block polymerization in a random order of k propyleneoxy groups (-CH ₂ -CH(CH ₃ )-O-) and j ethyleneoxy groups (-CH ₂ -CH ₂ -O-), k represents an integer of 0 to 50, j represents an integer of 10 to 100, and k+j=10 to 150. p represents 1 or 2. h represents an integer of 2 to 6. In the general formula (3-2), R ³ represents a divalent aliphatic hydrocarbon group having 8 to 22 carbon atoms which may be branched. m represents an integer of 2 to 11, and n represents an integer of 0 to 1000.]
[1-1. Polythiophene (A)]
In the above general formula (7), R represents an organic group having a total of 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group. The organic group having a total of 1 to 18 carbon atoms in a state not having at least one substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, an isobutoxymethyl group, a tert-butoxymethyl group, a hexyloxymethyl group, an isohexyloxymethyl group, a heptyloxymethyl group, and an octyloxymethyl group.

In the above general formula (7), the organic group having a total of 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of sulfonic acid groups and phosphonic acid groups is not particularly limited, but examples thereof include methyl sulfonate group, methyl phosphonate group, 2-ethyl sulfonate group, 2-ethyl phosphonate group, 3-propyl sulfonate group, 3-propyl phosphonate group, 2-propyl sulfonate group, 2-propyl phosphonate group, 4-butyl sulfonate group, 4-butyl phosphonate group, 3-butyl sulfonate group, 3-butyl phosphonate group, 6-hexyl sulfonate group, 6-hexyl phosphonate group, 5-hexyl sulfonate group, 5-hexyl phosphonate ... Examples of the alkoxyl group include methoxymethyl sulfonate, methoxymethyl phosphonate, ethoxymethyl 2-sulfonate, ethoxymethyl 2-phosphonate, propoxymethyl 3-sulfonate, propoxymethyl 3-phosphonate, propoxymethyl 2-sulfonate, propoxymethyl 2-phosphonate, butoxymethyl 4-sulfonate, butoxymethyl 4-phosphonate, butoxymethyl 3-sulfonate, butoxymethyl 3-phosphonate, hexyloxymethyl 6-sulfonate, hexyloxymethyl 6-phosphonate, hexyloxymethyl 5-sulfonate, and hexyloxymethyl 5-phosphonate.

The conductive polymer solution containing polythiophene (A) containing two or more structural units represented by the above general formula (7) may contain a base or a quaternary ammonium salt compound. When the conductive polymer solution contains a base or a quaternary ammonium salt compound, the sulfonic acid group or phosphonic acid group of polythiophene (A) containing two or more structural units represented by the above general formula (7) reacts with the base or quaternary ammonium salt compound to form a salt.

The base may be an alkaline alkali metal salt compound, a monoamine compound, or a diamine compound.

Examples of the alkaline alkali metal salt compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.

Examples of the monoamine compounds include ammonia, trimethylamine, triethylamine, dioctylamine, tridecylamine, hexadecylamine, octadecylamine, oleylamine, di-n-octylamine, bis(2-ethylhexyl)amine, dimethylstearylamine, trihexylamine, trioctylamine, and tris(2-ethylhexyl)amine.

Examples of the diamine compound include ethylenediamine, hexamethylenediamine, norbornanediamine, dimethylaminopropylamine, metaxylenediamine, and 1,3-bisaminomethylcyclohexane.

From the viewpoint of film-forming properties, the polythiophene (A) is preferably a polythiophene (A) containing two or more structural units 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).

[In general formula (1), M ⁺ represents a proton, a conjugate acid of an amine compound, or a quaternary ammonium ion. In general formulas (1) and (2), ^R1 independently 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.]
The structural unit represented by the general formula (2) represents a doped state of the structural unit represented by the general formula (1), and the doped state is realized by the sulfo group or sulfonate group in the structural unit represented by the general formula (1) acting as a p-type dopant.

The linear or branched alkyl group having 3 to 6 carbon atoms represented by R ¹ in the above general formulas (1) and (2) 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.

From the viewpoint of excellent film-forming properties, R ¹ 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 even more preferably a methyl group.

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

The conjugate acid of the amine compound is a cationic compound in which a proton is added to an amine compound. Examples of the amine compound include, but are not limited to, ammonia, amine compounds represented by the general formulas _NH2 ( ^R4 ), NH( ^R5 )( ^R6 ), and N( ^R4 )( ^R5 )( ^R6 ), pyridine compounds, and imidazole compounds.

The above R ⁴ to R ⁶ each independently represent an alkyl group having a total of 1 to 40 carbon atoms which may have a substituent (among which, the alkyl group having 3 to 40 carbon atoms may be linear, branched, or cyclic). Of these, it is more preferable that R ⁴ to R ⁶ each independently represent an alkyl group having a total of 1 to 20 carbon atoms which may have a substituent (among which, the alkyl group having 3 to 20 carbon atoms may be linear, branched, or cyclic), and it is even more preferable that R 4 to R 6 each independently represent an alkyl group having a total of 1 to 6 carbon atoms which may have a substituent (among which, the alkyl group having 3 to 6 carbon atoms may be linear, branched, or cyclic).

Furthermore, when ^R to ^R are alkyl groups 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.

Here, examples of 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, include, but are not limited to, 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, an octyl group, a decyl group, a hexadecyl group, an octadecyl group, an oleyl group, a 2-ethylhexyl group, a dimethylstearyl 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.

The alkyl group having a total of 1 to 6 carbon atoms, which may have the above-mentioned substituent, is not particularly limited, but 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.

Of these, more preferred examples of R ⁴ to R ⁶ are each independently a methyl group, an ethyl group, an octyl group, a decyl group, a hexadecyl group, an octadecyl group, an oleyl group, a 2-ethylhexyl group, a dimethylstearyl group, or a hydroxyethyl group.

The pyridine compound is not particularly limited, but examples thereof include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, picoline, and lutidine. Of these, pyridine, picoline, and lutidine are preferred.

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, and 1,2-dimethylimidazole. Of these, imidazole, 1-methylimidazole, and 1,2-dimethylimidazole are preferred.

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 from the viewpoint of solubility, the total number of carbon atoms is preferably 5 to 30, more preferably 8 to 30, and even more preferably 15 to 24.

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, pentylammonium ion, hexylammonium ion, dimethylisopropylammonium ion, diethylmethylammonium ion, heptylammonium ion, diisopropylmethylammonium 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, and N-methyl-N-(2,3-dihydroxypropyl)ammonium ion. , N,N-dimethyl-N-(2,3-dihydroxypropyl)ammonium ion, 1,4-butanediammonium ion, triisobutylammonium ion, triisopentylammonium ion, triisooctylammonium ion, octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, diisopropylethylammonium 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, or phenylammonium ion. Among these, at least one selected from the group consisting of pentylammonium ion, dimethylisopropylammonium ion, diethylmethylammonium ion, hexylammonium ion, triethylammonium ion, heptylammonium ion, diisopropylmethylammonium ion, octylammonium ion, dioctylammonium ion, 2-ethylhexylammonium ion, diisopropylethylammonium 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.

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.

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.

The total number of carbon atoms in the quaternary ammonium ion is not particularly limited, but may be, for example, 4 to 30, more preferably 5 to 30, even more preferably 8 to 30, and even more preferably 15 to 24.

The above-mentioned 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, and tetrahexylammonium ion. Among these, at least one selected from the group consisting of decyltrimethylammonium ion, dodecyltrimethylammonium ion, and tetrahexylammonium ion is preferable.

Polythiophene (A) in which M ⁺ is a quaternary ammonium ion can be prepared by mixing a quaternary ammonium salt with polythiophene (A) in which M ⁺ is a proton. The above-mentioned quaternary ammonium salt is not particularly limited, but examples thereof include chlorides, bromides, hydroxides, and hydrogen sulfates. Specific examples include tetramethylammonium chloride, tetraethylammonium chloride, tetranormalpropylammonium chloride, tetranormalbutylammonium chloride, tetranormalhexylammonium 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.

The above M ⁺ is preferably a proton or a conjugate acid of an amine compound having a total carbon number of 15 to 24. From the viewpoint of excellent coating film coatability, the above M ⁺ is preferably at least one selected from the group consisting of a dioctylammonium ion, a tridecylammonium ion, a hexadecylammonium ion, an octadecylammonium ion, an oleylammonium ion, a di-n-octylammonium ion, a bis(2-ethylhexyl)ammonium ion, a dimethylstearylammonium ion, a trihexylammonium ion, a trioctylammonium ion, a tris(2-ethylhexyl)ammonium ion, a dodecyltrimethylammonium ion, and a tetrahexylammonium ion.

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 the solubility and coatability of the conductive polymer solution, m in the above general formulas (1) and (2) 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 the solubility and coatability of the conductive polymer solution, n in the above general formulas (1) and (2) is preferably 1.

If the conductive polymer solution has good coatability, the adhesive composition described below will also have good coatability.

For 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), the number average molecular weight in terms of polystyrene sulfonic acid 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 terms of obtaining high electrical conductivity. In addition, in terms of the operability of the conductive polymer solution, the number average molecular weight in terms of polystyrene sulfonic acid measured by gel permeation chromatography of the polythiophene (A) is preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. Therefore, the number average molecular weight in terms of polystyrene sulfonic acid of the polythiophene (A) is preferably 3,500 to 30,000, more preferably 4,000 to 20,000, and even more preferably 5,000 to 15,000.

The method and conditions for measuring the molecular weight of the above polythiophene (A) by gel permeation chromatography shall comply with ISO 16014-3:2012 (JIS K 7252-3:2016).

[1-1-1. Method for producing polythiophene (A)]
A polythiophene containing at least two or more structural units represented by the above general formula (7) can be produced by polymerizing a thiophene monomer represented by the following general formula (8) in a water or alcohol solvent in the presence of an oxidizing agent such as an iron salt and/or persulfuric acid. If necessary, operations such as solvent washing, reprecipitation, centrifugal sedimentation, ultrafiltration, dialysis, or ion exchange resin treatment can be combined.

[In the general formula (8), R represents an organic group having a total of 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group. The sulfonic acid group and/or the phosphonic acid group may be an alkali metal salt.]
In the general formula (8), R has the same definition as R in the above general formula (7).

Examples of the alkali metal salt in general formula (8) include lithium salt, sodium salt, potassium salt, rubidium salt, and cesium salt.

In addition, polythiophenes containing at least two or more structural units selected from the group consisting of structural units represented by the above 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 (4) in water or an alcohol solvent in the presence of an oxidizing agent such as an iron salt and/or persulfuric acid. If necessary, operations such as solvent washing, reprecipitation, centrifugal sedimentation, ultrafiltration, dialysis, or ion exchange resin treatment can also be combined.

In the above general formula (4), R ¹ , m, and n are defined the same as R ¹ , m, and n in the above general formulas (1) and (2). In the above general formula (4), M ⁺ represents a proton or an alkali metal ion.

The thiophene monomer represented by the above general formula (4) is not particularly limited, but specific examples 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-[( Sodium 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-butyl-1-propanesulfonate ) methoxy]-1-pentyl-1-propanesulfonic acid sodium salt, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl) methoxy]-1-hexyl-1-propanesulfonic acid sodium salt, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl) methoxy]-1-isopropyl-1-propanesulfonic acid sodium salt, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl) methoxy]-1-isobutyl-1-propanesulfonic acid sodium salt 3-[(2,3-dihydrothieno[3,4-b]-[1,4]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, potassium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate, oxin-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 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, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butanesulfonic acid potassium salt, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonic acid sodium salt, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonic acid potassium salt, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonic acid potassium salt, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1 -fluoro-1-butanesulfonic acid sodium salt, 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- Examples include lithium 1-sulfonate, potassium 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.

The alkali metal ion represented by M ⁺ is not particularly limited, but examples thereof include a lithium ion, a sodium ion, a potassium ion, and a cesium ion.

The solvent used in the polymerization reaction of the thiophene monomer represented by the above general formula (8) or (4) is preferably water, alcohol, or an aqueous alcohol solution. Examples of water include pure water, and may be distilled water or ion-exchanged water. 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 be degassed or replaced with an inert gas such as nitrogen.

The amount of 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 1 to 20 times by weight, relative to the amount of the thiophene monomer charged.

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 sulfate (IV), and oxygen, and these may be used alone or in combination of two or more.

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

Specific examples of iron salts include trivalent iron salts such as FeCl ₃ , FeBr ₃ , Fe ₂ (SO ₄ ) ₃ , Fe (NO ₃ ) _{3.9H 2} O, iron perchlorate, and iron (III) para-toluenesulfonate, and divalent iron salts such as FeCl ₂ , FeBr ₂ , FeSO _{4.7H 2} O, and iron (II) acetate. These may be used in the form of anhydride or hydrate.

Specific examples of permanganate salts include sodium permanganate, potassium permanganate, and magnesium permanganate.

Specific examples of dichromates include ammonium dichromate and potassium dichromate.

Among these oxidizing agents, FeCl ₃ , Fe ₂ (SO ₄ ) ₃ , Fe ₂ (SO ₄ ) ₃ , or a combination of a persulfate and an iron salt (II or III) is particularly preferred.

The amount of 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, it is 1 to 20 times the number of moles. Even more preferably, it is 1 to 10 times the number of moles.

When the oxidizing agent used in the polymerization reaction of the thiophene monomer is, for example, a system of iron salt (III) alone, it is preferable to use iron salt (III) in an amount equal to or greater than the number of moles of the thiophene monomer used as the raw material, and to polymerize the thiophene monomer so that the iron concentration in the solvent is 10% by weight or more. In order 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) x 100 (weight%), and the iron salt is calculated as anhydrous.

When the oxidizing agent used in the polymerization reaction of the thiophene monomer is a combination of persulfate and iron salt (II or III), it is preferable that the persulfate is in the range of 0.5 to 20 times the molar amount and the iron salt (II or III) is in the range of 0.01 to 10 times the molar amount of the charged thiophene monomer, and it is more preferable that the persulfate is in the range of 1.5 to 10 times the molar amount and the iron salt (II or III) is in the range of 0.05 to 5 times the molar amount of the charged thiophene monomer.

The pressure for the polymerization reaction of the thiophene monomer may be normal pressure, reduced pressure, or increased pressure.

The reaction atmosphere for the polymerization reaction of the thiophene monomer may be air or an inert gas such as nitrogen or argon. An inert gas is more preferable.

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, and more preferably in the range of 0 to 50°C.

The reaction time for the polymerization reaction of the thiophene monomer is not particularly limited as long as the oxidative polymerization proceeds sufficiently, but is preferably in the range of 0.5 to 200 hours, and more preferably in the range of 0.5 to 80 hours.

The reaction method for the polymerization reaction of the thiophene monomer is not particularly limited. For example, the thiophene monomer represented by the general formula (8) or (4) may be dissolved in water in advance, and the oxidizing agent may be added dropwise to the solution all at once or slowly. Conversely, an aqueous solution of the thiophene monomer represented by the general formula (8) or (4) may be added dropwise to a solid or aqueous solution of the oxidizing agent all at once or slowly. When two or more types of oxidizing agents are used, the oxidizing agents may be added sequentially, or may be added in a premixed state.

In addition, the above-mentioned polymerization reaction of thiophene monomers tends to increase the liquid viscosity with the addition of an oxidizing agent, so it is necessary to stir the entire liquid uniformly. As for the stirring blades, propeller blades, paddle blades, Maxblend (registered trademark) blades (manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd.), Fullzone (registered trademark) blades (manufactured by Kobelco Environmental Solutions Co., Ltd.), or disk turbines can be used, and large blades such as Maxblend blades or Fullzone blades are preferred to mix more uniformly inside the reaction vessel. In addition, a homomixer or homogenizer used for emulsification or dispersion may also be used in combination. When using a stirring method using general stirring blades, it is preferable to make the rotation speed of the stirring blades as fast as possible within the range in which a large amount of gas from the gas phase of the reaction vessel is not taken into the reaction liquid and the stirring efficiency is not reduced.

A typical method for isolating and purifying the above polythiophene (A) is, for example, as follows.

First, the solution after the polymerization reaction of the thiophene monomer is subjected to ultrafiltration as it is, and desalted and purified using a membrane separation method such as dialysis, and then passed through a cation and anion exchange resin to obtain a solution of an acid-type polythiophene (A) in which M ⁺ is a proton.

If necessary, the resulting solution can be roughly concentrated and added to a poor solvent such as acetone to cause precipitation, thereby obtaining polythiophene (A) as a powder.

In addition, when forming a salt-type polythiophene (A), for example, various amine compounds, their aqueous solutions, or solutions obtained by diluting them with other suitable solvents are added to the solution of the acid-type polythiophene (A). Although not particularly limited, for example, a solution of an ammonium salt-type polythiophene (A) in which M ⁺ is _NH4 ⁺ can be formed by adding ammonia to the solution of the acid-type polythiophene (A). If necessary, the obtained solution can be added to a poor solvent such as acetone to obtain various ammonium salt-type polythiophenes (A) in powder form.

[1-2. Modified polyamine compound (B)]
In the present specification, the modified polyamine compound (B) refers to a polymer constituted of a repeating unit represented by the following general formula (3-1) and/or a repeating unit represented by the following general formula (3-2), and a repeating unit represented by the following general formula (3-3):

[In the general formula (3-1), R ² represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms. X represents a divalent polymer group formed by random polymerization or block polymerization in a random order of k propyleneoxy groups (-CH ₂ -CH(CH ₃ )-O-) and j ethyleneoxy groups (-CH ₂ -CH ₂ -O-), k represents an integer of 0 to 50, j represents an integer of 10 to 100, and k+j=10 to 150. p represents 1 or 2. h represents an integer of 2 to 6. In the general formula (3-2), R ³ represents a divalent aliphatic hydrocarbon group having 8 to 22 carbon atoms which may be branched. m represents an integer of 2 to 11, and n represents an integer of 0 to 1000.]
The aliphatic hydrocarbon group having 1 to 22 carbon atoms in ^R2 may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group having 1 to 22 carbon atoms in ^R2 is not particularly limited, but examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a lauryl group, a hexadecyl group, a palmityl group, an octadecyl group, a stearyl group, an oleyl group, an eicosapentadienyl group, and a docosahexaenyl group.

The divalent aliphatic hydrocarbon group having 8 to 22 carbon atoms which may be branched for ^R3 may be a divalent aliphatic saturated hydrocarbon group having 8 to 22 carbon atoms which may be branched, or a divalent aliphatic unsaturated hydrocarbon group having 8 to 22 carbon atoms which may be branched.

The optionally branched divalent aliphatic hydrocarbon group having 8 to 22 carbon atoms for ^R3 is not particularly limited, and examples thereof include an octanediyl group, an isooctanediyl group, a 2-ethylhexanediyl group, a decanediyl group, a dodecanediyl group, a tetradecanediyl group, a pentadecanediyl group, a hexadecanediyl group, a heptadecanediyl group, an octadecanediyl group, a cis-9-octadecanediyl group, an eicosapentadienediyl group, and a docosahexaenediyl group.

^R3 is preferably a heptadecanediyl group, and more preferably a heptadecane-1,11-diyl group.

The modified polyamine compound (B) is preferably a polymer composed of a repeating unit represented by general formula (3-1) and a repeating unit represented by the following general formula (3-3), or a polymer composed of a repeating unit represented by general formula (3-2) and a repeating unit represented by the following general formula (3-3). The modified polyamine compound (B) may also be a polymer composed of a repeating unit represented by general formula (3-1), a repeating unit represented by general formula (3-2), and a repeating unit represented by general formula (3-3).

[1-3. Organic solvent (C)]
In one embodiment of the present invention, as the organic solvent (C), at least one selected from the group consisting of ester-based solvents and aromatic-based solvents can be used.

The ester solvent is not particularly limited, but may be at least one selected from the group consisting of methyl acetate, ethyl acetate, normal propyl acetate, butyl acetate, isobutyl acetate, methoxybutyl acetate, γ-butyrolactone, γ-valerolactone, γ-nonalactone, δ-valerolactone, ε-caprolactone, and α-acetyl-γ-butyrolactone.

Aromatic solvents include, but are not limited to, benzene, toluene, xylene, etc.

As the organic solvent (C), it is preferable to include ethyl acetate, butyl acetate, or toluene, in view of excellent coating film application properties.

In addition, by including a highly polar solvent such as gamma-butyrolactone as all or part of the organic solvent (C), compatibility with adhesives of various polarities may be improved.

In the conductive polymer solution according to one embodiment of the present invention, from the viewpoint of producing an adhesive composition by mixing with the adhesive (D) described below, the content of the organic solvent (C) is preferably 80 to 99.9% by weight, and more preferably 90 to 99.9% by weight, with the total of the polythiophene (A), the modified polyamine compound (B), and the organic solvent (C) being 100% by weight.

For 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 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.1 to 3 parts by weight, per 100 parts by weight of the organic solvent (C).

For the conductive polymer solution according to one embodiment of the present invention, from the viewpoint of producing an adhesive composition by mixing with the adhesive (D), the content of the modified polyamine compound (B) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 7.5 parts by weight, and even more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the organic solvent (C).

[1-4. Method for producing 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, a modified polyamine compound (B), and an organic solvent (C) are mixed and homogenized by stirring or the like.

The temperature during mixing is not particularly limited, but may be, for example, room temperature or heated. It may be 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. In this specification, room temperature refers to 15°C to 25°C.

Furthermore, the conductive polymer solution according to one embodiment of the present invention may contain components other than those described above. The components other than those described above are not particularly limited, but may include, for example, a binder and a surfactant.

The above-mentioned binder is not particularly limited, but examples thereof include cellulose-based 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, and polyvinyl alcohol resins.

As for the binder resin, at least one selected from the group consisting of cellulose-based resins, vinylpyrrolidone resins, urethane resins, acrylic resins, and epoxy resins is preferred because of its excellent film-forming properties.

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 parts by weight, and more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the polythiophene (A), the modified polyamine compound (B), and the organic solvent (C).

The above-mentioned 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.

When the conductive polymer solution according to one embodiment of the present invention contains the above-mentioned surfactant, the content of the surfactant is preferably 0.1 to 60 parts by weight, and more preferably 1 to 40 parts by weight, per 100 parts by weight of the total of the polythiophene (A), the modified polyamine compound (B), and the organic solvent (C).

[1-5. Pressure-sensitive adhesive composition]
The pressure-sensitive adhesive composition according to one embodiment of the present invention is characterized by containing the conductive polymer solution and a pressure-sensitive adhesive (D). As the pressure-sensitive adhesive (D), a generally known pressure-sensitive adhesive can be used.

The adhesive (D) is not particularly limited, but examples thereof include acrylic adhesives, silicone adhesives, urethane adhesives, and rubber adhesives.

Acrylic adhesives refer to adhesives whose main component is acrylic polymer. Silicone adhesives refer to adhesives whose main component is a polymer with a siloxane bond as the main skeleton. Urethane adhesives refer to adhesives whose main component is polyurethane obtained by condensing compounds with isocyanate groups and hydroxyl groups. Rubber adhesives refer to adhesives whose main component is natural rubber or synthetic rubber.

Among these adhesives (D), acrylic adhesives are preferred because of their excellent adhesive properties for optical components, and ARONTAC adhesive or Cyvinol adhesive is more preferred. ARONTAC and Cyvinol are registered trademarks.

Specific product names for ARONTAC adhesives include ARONTAC S-1601, ARONTAC S-1605, ARONTAC S-1511X, ARONTAC S-1511 modified, ARONTAC S-3403, and ARONTAC S-3452YKF. Examples of the Saibinol adhesive include Saibinol AT-245, Saibinol AT-191, Saibinol ATR-340, Saibinol AT-D37L, Saibinol AT-211, Saibinol AT-262, Saibinol AT-197, Saibinol AT-193, Saibinol ATR-1, Saibinol ATR-373, Saibinol ATR-347, Saibinol ATR-300, Saibinol AT-420NT, Saibinol AT-422NT, Saibinol AT-260NT, Saibinol AT-D54, Saibinol AT-352, Saibinol AT-D50, Saibinol AT-D40, Saibinol AT-D37, and Saibinol AT-D45. As the adhesive (D), these adhesives may be used alone or in a mixture of two or more types.

The adhesive (D) may also contain a solidifying agent or a crosslinking agent. The crosslinking agent is not particularly limited, but examples thereof include isocyanate compounds, epoxy compounds, melamine resins, aziridine derivatives, and metal chelate compounds. These crosslinking agents may be used alone or in combination of two or more.

In the pressure-sensitive adhesive composition according to one embodiment of the present invention, from the viewpoint of improving electrical conductivity, the content of polythiophene (A) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.1 to 3 parts by weight, per 100 parts by weight of the pressure-sensitive adhesive (D).

In the adhesive composition according to one embodiment of the present invention, since the modified polyamine compound (B) improves the compatibility between the polythiophene (A) and the adhesive (D) in the organic solvent (C), the content of the modified polyamine compound (B) is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 8 parts by weight, and even more preferably 0.1 to 6 parts by weight, relative to 100 parts by weight of the adhesive (D).

For the pressure-sensitive adhesive composition according to one embodiment of the present invention, from the viewpoint of operability such as coatability, the concentration of the organic solvent (C) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and even more preferably 40 to 60% by weight, with the entire pressure-sensitive adhesive composition being taken as 100% by weight.

2. Method for producing conductive adhesive film
The conductive adhesive film according to one embodiment of the present invention is not particularly limited, but can be produced, for example, by applying the adhesive composition according to one embodiment of the present invention to a substrate and then drying it. The conductive adhesive film produced in this manner is characterized by containing the above polythiophene (A), the above modified polyamine compound (B), and the above adhesive (D).

The above substrate is not particularly limited, but examples thereof include glass, plastic, polyester, polyacrylate, polycarbonate, or resist substrates. 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, and inkjet printing.

There are no particular limitations on the drying temperature, so long as it is a temperature at which a uniformly dried conductive adhesive film can be obtained and is equal to or lower than the heat resistance temperature of the substrate, but a temperature in the range of room temperature (15-25°C) to 300°C is preferred, a temperature in the range of room temperature to 250°C is more preferred, and a temperature in the range of 90-250°C is even more preferred.

The drying atmosphere may be air, an inert gas, a vacuum, or a reduced pressure. From the viewpoint of preventing deterioration of the conductive adhesive film, an inert gas such as nitrogen or argon is preferable.

The thickness of the conductive adhesive film according to one embodiment of the present invention is not particularly limited, but is preferably in the range of 1×10 ⁻² to 1×10 ² μm.

According to the above-mentioned manufacturing method, a conductive adhesive film having good antistatic properties can be obtained. The antistatic properties of the conductive adhesive film can be evaluated, for example, by the surface resistivity. In other words, the lower the surface resistivity of the conductive adhesive film, the higher the antistatic properties.

[3. UV-curable hard coat resin composition]
The conductive polymer solution according to one embodiment of the present invention can be mixed with an ultraviolet curable resin (E) to produce a hard coat exhibiting antistatic properties, and a resin composition for ultraviolet curable hard coat for obtaining such a hard coat exhibiting antistatic properties. That is, the resin composition for ultraviolet curable hard coat according to one embodiment of the present invention contains the conductive polymer solution and an ultraviolet curable resin (E) described above.

The ultraviolet-curable resin (E) may be any known resin. Although there are no particular limitations on the ultraviolet-curable resin (E), generally, resins containing an oligomer (e1), a monomer (e2), and a photopolymerization initiator (e3) are often used.

The oligomer (e1) is a polymer composed of multiple repeating units to which at least one polymerizable group, such as an acrylic group or a methacrylic group (hereinafter, both of which are referred to as "(meth)acrylic"). For example, the oligomer (e1) is a polymer selected from the group consisting of polyoxyethylene, polyurethane, polyester, polyacrylic acid, polymethacrylic acid, and poly(oxyperfluoroalkylene), to which at least one polymerizable group, such as (meth)acrylic, is bonded.

The number of polymerizable groups represented by (meth)acrylic groups or the like contained in the oligomer (e1) is not limited, and may be one, two, three, four, or five.

The oligomer (e1) is not particularly limited, but examples thereof include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyoxyethylene (meth)acrylate oligomers, polyoxypropylene (meth)acrylate oligomers, polyester (meth)acrylate oligomers, poly(meth)acrylic acid (meth)acrylate oligomers, poly(oxyperfluoroalkylene) (meth)acrylate oligomers, etc., and these oligomers (e1) may be used alone or in combination of two or more. Among these, from the viewpoint of improving the hardness of the hard coat, it is preferable to use at least one selected from the group consisting of urethane acrylate oligomers and epoxy acrylate oligomers. In addition, the oligomer (e1) preferably contains an acrylate oligomer having 15 or less functionalities (i.e., the number of acryloyl groups in the oligomer is 15 or less), and more preferably contains an acrylate oligomer having 10 or less functionalities.

Examples of the oligomer (e1) include trade names: UA-1100H (Shin-Nakamura Chemical Co., Ltd.), UN-904 (Negami Industries Co., Ltd.), RUA-071 (Asia Industries Co., Ltd.), RUA-076MG (Asia Industries Co., Ltd.), EBECRYL 600 (Daicel Allnex Co., Ltd.), X-40-2669 (Shin-Etsu Silicones), and KR-470 (Shin-Etsu Silicones). These may be used alone or in a mixture of two or more types.

Examples of the monomer (e2) include monomolecular compounds or low molecular compounds having at least one or more polymerizable groups (one, two, three, four, or five) such as acrylic or methacrylic groups. Examples of the monomer (e2) include, but are not limited to, acrylate monomers, methacrylate monomers, and acrylic silane monomers. More specifically, examples of the monomer (e2) include 2-hydroxyethyl acrylate, isobornyl acrylate, pentaerythritol tetraacrylate, 4-acryloylmorpholine, γ-butyrolactone acrylate ... Examples of the monomer (b2) include methacrylate, 5-oxotetrahydrofuran-3-yl methacrylate, glycol dimethacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate, diethylene glycol diacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monoacrylate, ethylene glycol diacrylate, ethylene glycol monomethacrylate, ethylene glycol dimethacrylate, 1,3-propanediol diacrylate, glycerol trimethacrylate, and 1,3-propanediol dimethacrylate. These monomers (b2) may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of acrylate monomers and methacrylate monomers is preferred, and from the viewpoint of increasing the compatibility of the composition, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol tetraacrylate, isobornyl acrylate, and 4-acryloylmorpholine are more preferred.

The photopolymerization initiator (e3) can be any photopolymerization initiator used in the art without any restrictions, and examples of such initiators include 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-1-[4-(morpholino)phenyl]-1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-dimethoxy-2-phenylacetophenone, and 2-hydroxy-2-methylpropiophenone.

The ultraviolet-curable resin (E) preferably contains at least an oligomer (e1), more preferably contains an oligomer (e1) and a monomer (e2), and even more preferably contains an oligomer (e1), a monomer (e2), and a photopolymerization initiator (e3).

The content of the ultraviolet-curable resin (E) in the ultraviolet-curable hard coat resin composition is not limited, but is preferably 10 to 80% by weight, and more preferably 10 to 60% by weight, with the entire ultraviolet-curable hard coat resin composition being 100% by weight.

The content of the oligomer (e1) in the ultraviolet-curable hard coat resin composition is not limited, but is preferably 5 to 80% by weight, more preferably 5 to 60% by weight, more preferably 5 to 40% by weight, and even more preferably 5 to 30% by weight, based on 100% by weight of the entire ultraviolet-curable hard coat resin composition.

The content of the monomer (e2) in the ultraviolet-curable hard coat resin composition is not limited, but is preferably 10 to 80% by weight, more preferably 10 to 60% by weight, and even more preferably 10 to 40% by weight, based on 100% by weight of the entire ultraviolet-curable hard coat resin composition.

The content of the photopolymerization initiator (e3) in the ultraviolet-curable hard coat resin composition is not limited, but is preferably 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, and even more preferably 0.5 to 5% by weight, based on 100% by weight of the entire ultraviolet-curable hard coat resin composition.

The content of the photopolymerization initiator (e3) is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and even more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total weight of the oligomer (e1) and monomer (e2).

The UV-curable hard coat resin composition may contain components other than those described above. The components other than those described above are not particularly limited, but examples thereof include solvents, water-repellent and antifouling agents (additives that impart water repellency and oil repellency), UV absorbers, antioxidants, colorants, inorganic fillers, defoamers, thickeners, precipitation inhibitors, antifogging agents, antibacterial agents, dispersants, and surface modifiers.

The solvent is not particularly limited, but any solvent that can dissolve or disperse each component contained in the composition and is known in the art as a solvent for compositions for forming a coating layer can be used without restriction. Examples of the solvent include alcohols (ethanol, isopropanol, trifluoroethanol, etc.), glycol ethers (1-methoxy-2-propanol, ethylene glycol n-butyl ether, etc.), and ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone, etc.). The solvents specifically exemplified here can be used alone or in combination of two or more.

As for the solvent, glycol ether solvents are preferred because of their excellent operability in film formation, and 1-methoxy-2-propanol (PGME) is more preferred.

The content of the solvent (C) in the ultraviolet-curable hard-coat resin composition is not limited, but is preferably 10 to 80% by weight, more preferably 20 to 70% by weight, and even more preferably 30 to 60% by weight, based on 100% by weight of the entire ultraviolet-curable hard-coat resin composition.

Inorganic fillers include single-walled carbon nanotubes, multi-walled carbon nanotubes, silver nanowires, carbon black, silica, alumina, boehmite, antimony oxide, chromium oxide, nickel oxide, copper oxide, tin oxide, titanium oxide, zirconium oxide, indium oxide, and zinc oxide.

The water-repellent and stain-resistant agents are not particularly limited, but examples thereof include fluorine compounds and silicone compounds. More specifically, examples of fluorine compounds include perfluoropolyether, product name: X-71-1203E (Shin-Etsu Chemical Co., Ltd.), product name: KY-1203 (Shin-Etsu Chemical Co., Ltd.), etc., and examples of silicone compounds include product name: KP-112 (Shin-Etsu Silicones), product name: KP-341 (Shin-Etsu Silicones), product name: KP-423 (Shin-Etsu Silicones), etc.

The dispersant is not particularly limited, but examples include those whose main chain is made of polyester, polyacrylic, polyurethane, polyamine, polycaprolactone, etc., and whose side chain has a polar group such as an amino group, a carboxyl group, a sulfone group, or a hydroxyl group.

Examples of polyester-based dispersants that can be used include Disparlon KS873N, Disparlon DA703-50, and Disparlon DA7400 (manufactured by Kusumoto Chemical Co., Ltd.).

Examples of polyacrylic dispersants include Disperbyk-2000, 2001, 2008, 2009, 2010, 2020, 2020N, 2022, 2025, 2050, 2070, 2095, 2150, 2151, 2155, 2163, 2164, BYKJET-9130, 9131, 9132, 9133, 9151 (manufactured by BYK-Chemie), Efka PX4310, PX4320, PX4330, PA4401, 4402, PA4403, 4570, 7411, 7477, PX4700, PX4701 (manufactured by BASF), and TREPLUS. D-1200, D-1410, D-1420, MD-1000 (manufactured by Otsuka Chemical Co., Ltd.), FLOWRENE DOPA-15BHFS, 17HF, 22, G-700, 900, NC-500, GW-1500 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. are used.

An example of a polyamine-based dispersant is Disparlon 1860 (Kusumoto Chemical Co., Ltd.).

Examples of polycaprolactone-based dispersants include Ajisper PB821, PB822, and PB881 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Hinoact KF-1000, KF-1500, KF-1700, T-6000, T-7000, T-8000, T-8000E, and T-9050 (manufactured by Kawaken Fine Chemical Co., Ltd.), Solsperse 20000, 24000, 32000, 32500, 32550, 32600, 33000, 33500, 34000, 35200, 36000, 37500, 39000, 71000, 76400, 76500, 86000, 88000, J180, J200 (manufactured by Lubrizol Corporation), TEGO Dispers 652, 655, 685, 688, 690 (manufactured by Evonik Japan), etc. are used.

Other commercially available dispersants include, for example, Esream AD-3172M, 374M, 508E, 221P, 221J, DP-2, DJ-2, Marialim AKM-0531, AFB-1521, AAB-0851, SC-0505K, SC-1015F, and SC-0708A (manufactured by NOF Corporation).

The content of the water repellent and antifouling agent in the UV-curable hard coat resin composition according to one embodiment of the present invention is not limited, but is preferably 0.1 to 5% by weight, and more preferably 0.1 to 2% by weight, based on 100% by weight of the entire UV-curable hard coat resin composition.

By curing the UV-curable hard coat resin composition, a cured product, a hard coat (hard coat film or hard coat film), or a laminate having the hard coat (hard coat film, hard coat film) is produced. The cured product, hard coat (hard coat film, hard coat film), or a laminate having the hard coat (hard coat film, hard coat film) contains the polythiophene (A) and the modified polyamine compound (B).

The cured product, hard coat, or laminate having a hard coat according to one embodiment of the present invention is not particularly limited, but can be produced, for example, by applying the ultraviolet-curable hard coat resin composition according to one embodiment of the present invention to a substrate and irradiating it with ultraviolet light. In order to increase the physical properties such as hardness of the cured product, hard coat, or laminate having a hard coat, it is preferable to dry the applied resin composition before irradiating it with ultraviolet light.

The above substrate is not particularly limited, but examples include glass, a resin film, a resin plate, and a resist substrate.

The resin film is not particularly limited, but examples thereof include cetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth)acrylonitrile film, cycloolefin polymer (COP) film, etc.

Examples of resin plates include acrylic plates, triacetyl cellulose plates, polyethylene terephthalate plates, diacetylene cellulose plates, acetate butyrate cellulose plates, polyethersulfone plates, polyurethane plates, polyester plates, polycarbonate plates, polysulfone plates, polyether plates, polymethylpentene plates, polyether ketone plates, and (meth)acrylonitrile plates.

All of these substrates have excellent transparency and are suitable for use in the display devices described below. The thickness of the substrate can be selected appropriately depending on the application, but generally, a thickness of about 25 to 1000 μm is used.

The method of applying the resin composition according to one embodiment of the present invention is not particularly limited, but examples thereof include screen printing, casting, dipping, bar coating, roll coating, gravure coating, flexographic printing, spray coating, air knife coating, curtain coating, spin coating, wire bar coating, extrusion coating, and inkjet printing.

The thickness of the hard coat film (hard coat layer) is not particularly limited, but it is usually preferable that it be 0.01 to 20 μm after coating and drying.

The coating film applied to the substrate and formed may be dried before being cured. When drying, heating may be applied as appropriate. The drying temperature is not particularly limited as long as it is a temperature at which a uniformly dried hard coat is obtained and is equal to or lower than the heat resistance temperature of the substrate, but is preferably in the range of room temperature (15-25°C) to 300°C, more preferably in the range of room temperature to 250°C, and even more preferably in the range of room temperature to 200°C.

The drying atmosphere may be air, an inert gas, a vacuum, or a reduced pressure. From the viewpoint of preventing deterioration of the hard coat, an inert gas such as nitrogen or argon is preferred.

After drying, the coating is cured by irradiating with ultraviolet light. The amount of UV light irradiation is about 100 to 21,000 mJ/cm ² , and preferably about 300 to 2,100 mJ/cm ^2. The irradiation atmosphere may be air, an inert gas, a vacuum, or a reduced pressure.

The thickness of the hard coat containing the polythiophene (A) (after drying and UV irradiation) is not particularly limited, but is preferably in the range of 1 to 100 μm, and more preferably in the range of 1 to 10 μm.

The hard coat produced from the resin composition according to one embodiment of the present invention has high hardness. For example, a hard coat formed with a film thickness of 3 μm using the resin composition according to one embodiment of the present invention preferably has a pencil hardness of H or more, and more preferably 2H or more, as measured according to JIS K-5600.

The cured product, hard coat, or laminate having a hard coat can be used together with a light source to be applied to a display device. In this case, the substrate on which the hard coat film is formed is preferably a light-transmitting substrate. As the light-transmitting substrate, the substrates described above for forming the hard coat film can be used. In addition, the light source is preferably disposed on the back surface of the substrate, i.e., the surface of the substrate opposite to the surface on which the hard coat layer is formed, and is preferably one that irradiates light toward the substrate from there.

There are no particular limitations on the light source that can be combined with the cured product, hard coat, or laminate having a hard coat, so long as it is capable of emitting light. Examples include light-emitting diodes, cold cathode fluorescent lamps, hot cathode fluorescent lamps, and EL elements, but liquid crystal modules, backlight units, and the like may also be used.

The liquid crystal module includes the above light source, and further includes a polarizing plate/liquid crystal cell/polarizing plate arranged in this order on top of the light source. There are no particular limitations on the liquid crystal cell, so long as it is one that is generally used in liquid crystal display devices. Examples include TN type liquid crystal cells, STN type liquid crystal cells, HAN type liquid crystal cells, IPS type liquid crystal cells, VA type liquid crystal cells, MVA type liquid crystal cells, and OCB type liquid crystal cells. Such display devices may further include a retardation plate, a brightness enhancement film, a light guide plate, a light diffusion plate, a light diffusion sheet, a light collecting sheet, a reflector, and the like.

Display devices equipped with the laminate include flat panel displays such as liquid crystal displays (liquid crystal displays), LEDs (light emitting diode displays), ELDs (electroluminescence displays), VFDs (fluorescent displays), and PDPs (plasma display panels). The resin composition according to one embodiment of the present invention used to manufacture the display devices has weather resistance in addition to anti-blocking properties, making it possible to use these display devices outdoors. For example, it can be installed outdoors or semi-outdoors as a panel display for the purpose of displaying information such as advertisements.

Another application of a display device equipped with this laminate is a touch panel, which has a mechanism for operating equipment by pressing the display on the screen, and is useful in, for example, bank ATMs, vending machines, personal digital assistants (PDAs), copiers, facsimiles, game machines, information display devices installed in facilities such as museums and department stores, car navigation systems, multimedia stations (multifunction terminals installed in convenience stores), mobile phones, and monitor devices for railway cars.

[Additional Notes]
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 the different embodiments are also included in the technical scope of the present invention.

The following examples are provided, but the present invention should not be construed as being limited to these examples. The analytical instruments and measurement methods used in the examples are listed below. In the following examples and comparative examples, the percentages indicating the content are by weight unless otherwise specified.

[Measurement of particle size of conductive polymer solution]
The particle size of the conductive polymer solution was measured using a particle size measuring device (UPA-UT151 manufactured by Nikkiso Co., Ltd.).

[Method for measuring surface resistance of conductive adhesive film]
A conductive adhesive composition containing a conductive polymer solution and an adhesive was applied to a poly film using a Select-Roller/A-Bar (manufactured by OSG System Products), and dried at 80° C. to prepare a conductive adhesive film having a thickness of 52 μm. The surface resistance of this conductive adhesive film was measured using a high resistivity meter Hiresta (registered trademark)-UX MCP-HT800 (manufactured by Nitto Seiko Analytech).

The lower the surface resistivity of the conductive adhesive film, the higher the antistatic ability. Specifically, if the surface resistivity of the conductive adhesive film is less than ¹⁰ Ω/□, it can be said to be a conductive adhesive film having antistatic ability, and it is preferably ¹⁰ Ω/□ or less, more preferably ¹⁰ Ω/□ or less, and even more preferably ¹⁰ Ω/□ or less.

[Method of producing hard coat]
A hard coat was prepared using a tabletop printing tester (K202 Control Coater, manufactured by Matsuo Sangyo Co., Ltd.) by the following method. Using a wire bar with a film thickness (wet film thickness) of 18 μm immediately after coating, the ultraviolet-curable hard coat resin composition according to one embodiment of the present invention was applied to a PET film (A4160, manufactured by Toyobo Co., Ltd.), and then heated in a thermostatic chamber set at 80° C. under air for 5 minutes. Thereafter, ultraviolet light was irradiated for 1 minute under air using a tabletop UV curing device (HC-96X, manufactured by Sen Special Light Sources Co., Ltd.) to obtain a hard coat.

[Method of measuring surface resistance of hard coat and evaluation criteria]
The measurement probe (USP) of a sheet resistance measuring device (Hiresta (registered trademark)-UX MCP-HT800, manufactured by Nitto Seiko Analytech) was pressed against the surface of the prepared hard coat, and the surface resistance value (Ω/□) was measured in air at room temperature. The evaluation results were rated as good when the surface resistance value was less than 1.0× ¹⁰ Ω/□, and poor when it was 1.0× ¹⁰ Ω/□ or more.

Synthesis Example 1 Synthesis of polythiophene (PT) According to a conventionally known production method, 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 (5) and formula (6), number average molecular weight: approximately 7000) was produced.

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

Production Example of Modified Polyamine Compound (B) According to the method described in JP-A-2004-89787 (Kawaken Fine Chemical Co., Ltd.), ether carboxylic acids (1), (2), (4), and (5) (all the same as those described in JP-A-2004-89787) were synthesized. Furthermore, according to the method described in the above-mentioned JP-A-2004-89787, the ether carboxylic acids were reacted with polyethyleneimine to synthesize modified polyamine compounds (1), (3), (7), and (9) (which correspond to the above-mentioned modified polyamine compound (B)).

A summary of the manufacturing examples of the above modified polyamine compounds (1), (3), (7), and (9) is shown in Table 1.

Polycarbonyl alkylene oxy acid (PCAO acid) 1, which is intermediate product 1 described in JP-A-11-197485, was synthesized according to the method described in JP-A-11-197485 (Kawaken Fine Chemical Co., Ltd.). Next, 578.9 g of the intermediate product 1 was added to 22.4 g of polyethyleneimine (trade name Epomin SP-018, manufactured by Nippon Shokubai Co., Ltd.) and stirred at 120°C for 7 hours in a nitrogen atmosphere. A wax-like modified polyamine compound (1') (corresponding to the above-mentioned modified polyamine compound (B)) was obtained at room temperature.

A summary of the above-mentioned production examples of modified polyamine compound (1') is shown in Table 2.

Example 1 (Preparation and Evaluation of Conductive Polymer Solution)
0.1 g of the PT and 0.2 g of the modified polyamine compound (1) were added to 9.7 g of ethyl acetate as an organic solvent (C) and stirred to prepare a conductive polymer solution. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution] and found to be 2.1 nm. It was found that the PT was uniformly dissolved or dispersed in the conductive polymer solution.

Example 2 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 0.2 g of the modified polyamine compound (3) was used instead of 0.2 g of the modified polyamine compound (1) in Example 1. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution], and was found to be 2.1 nm. It was found that PT was uniformly dissolved or dispersed in the conductive polymer solution.

Example 3 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 0.2 g of the modified polyamine compound (7) was used instead of 0.2 g of the modified polyamine compound (1) in Example 1. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution], and was found to be 2.1 nm. It was found that PT was uniformly dissolved or dispersed in the conductive polymer solution.

Example 4 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 0.2 g of the modified polyamine compound (9) was used instead of 0.2 g of the modified polyamine compound (1) in Example 1. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution], and was found to be 2.1 nm. It was found that PT was uniformly dissolved or dispersed in the conductive polymer solution.

Examples 5 to 12 (Preparation and Evaluation of Conductive Polymer Solutions)
Conductive polymer solutions were prepared in the same manner as in Examples 1 to 4, except that instead of using 9.7 g of ethyl acetate, 9.7 g of butyl acetate or 9.7 g of toluene was used as the organic solvent (C). The respective formulations are shown in Table 3. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 13 (Preparation and Evaluation of Conductive Polymer Solution)
0.1 g of the PT and 0.2 g of the modified polyamine compound (1') were added to 9.7 g of ethyl acetate as an organic solvent (C) and stirred to prepare a conductive polymer solution. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution] and found to be 2.1 nm. It was found that the PT was uniformly dissolved or dispersed in the conductive polymer solution. The results are shown in Table 3.

Examples 14 to 15 (Preparation and Evaluation of Conductive Polymer Solutions)
Conductive polymer solutions were prepared in the same manner as in Example 13, except that 9.7 g of butyl acetate or 9.7 g of toluene was used as the organic solvent (C) instead of 9.7 g of ethyl acetate. The respective formulations are shown in Table 3. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 16 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 0.97 g of γ-butyrolactone and 8.73 g of ethyl acetate were used as the organic solvent (C) instead of 9.7 g of ethyl acetate in Example 1. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 17 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 4.85 g of γ-butyrolactone and 4.85 g of ethyl acetate were used as the organic solvent (C) instead of 9.7 g of ethyl acetate in Example 1. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 18 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 8.73 g of γ-butyrolactone and 0.97 g of ethyl acetate were used as the organic solvent (C) instead of 9.7 g of ethyl acetate in Example 1. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 19 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 0.97 g of γ-butyrolactone and 8.73 g of 2-butanone were used instead of 9.7 g of ethyl acetate as the organic solvent (C) in Example 1. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 20 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 4.85 g of γ-butyrolactone and 4.85 g of 2-butanone were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 21 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 8.73 g of γ-butyrolactone and 0.97 g of 2-butanone were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 22 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 0.97 g of γ-butyrolactone and 8.73 g of toluene were used instead of 9.7 g of ethyl acetate as the organic solvent (C) in Example 1. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 23 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 4.85 g of γ-butyrolactone and 4.85 g of toluene were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 24 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 8.73 g of γ-butyrolactone and 0.97 g of toluene were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 25 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared by the same procedure as in Example 1, except that 0.01 g of modified polyamine compound (1) was used instead of 0.2 g of modified polyamine compound (1) in Example 1, and 4.94 g of γ-butyrolactone and 4.95 g of ethyl acetate were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 26 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared by the same procedure as in Example 1, except that 0.1 g of modified polyamine compound (1) was used instead of 0.2 g of modified polyamine compound (1) in Example 1, and 4.90 g of γ-butyrolactone and 4.90 g of ethyl acetate were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 27 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared by the same procedure as in Example 1, except that 0.5 g of the modified polyamine compound (1) was used instead of 0.2 g of the modified polyamine compound (1) in Example 1, and 4.70 g of γ-butyrolactone and 4.70 g of ethyl acetate were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 3.

Example 28 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared by the same procedure as in Example 1, except that 0.01 g of modified polyamine compound (1) was used instead of 0.2 g of modified polyamine compound (1) in Example 1, and 4.94 g of γ-butyrolactone and 4.95 g of 2-butanone were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Example 29 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared by the same procedure as in Example 1, except that 0.1 g of modified polyamine compound (1) was used instead of 0.2 g of modified polyamine compound (1) in Example 1, and 4.90 g of γ-butyrolactone and 4.90 g of 2-butanone were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Example 30 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared by the same procedure as in Example 1, except that 0.5 g of the modified polyamine compound (1) was used instead of 0.2 g of the modified polyamine compound (1) in Example 1, and 4.70 g of γ-butyrolactone and 4.70 g of 2-butanone were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Example 31 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared by the same procedure as in Example 1, except that 0.2 g of modified polyamine compound (3) was used instead of 0.2 g of modified polyamine compound (1) in Example 1, and 4.85 g of γ-butyrolactone and 4.85 g of ethyl acetate were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Example 32 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared by the same procedure as in Example 1, except that 0.2 g of modified polyamine compound (7) was used instead of 0.2 g of modified polyamine compound (1) in Example 1, and 4.85 g of γ-butyrolactone and 4.85 g of ethyl acetate were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Example 33 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared by the same procedure as in Example 1, except that 0.2 g of modified polyamine compound (9) was used instead of 0.2 g of modified polyamine compound (1) in Example 1, and 4.85 g of γ-butyrolactone and 4.85 g of ethyl acetate were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Example 34 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared by the same procedure as in Example 1, except that 0.2 g of modified polyamine compound (1') was used instead of 0.2 g of modified polyamine compound (1) in Example 1, and 4.85 g of γ-butyrolactone and 4.85 g of ethyl acetate were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Example 35 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 3.233 g of γ-butyrolactone, 3.234 g of ethyl acetate, and 3.233 g of 2-butanone were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Example 36 (Preparation and Evaluation of Conductive Polymer Solution)
A conductive polymer solution was prepared in the same manner as in Example 1, except that 3.233 g of γ-butyrolactone, 3.234 g of toluene, and 3.233 g of 2-butanone were used instead of 9.7 g of ethyl acetate as the organic solvent (C). The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Example 37 (Preparation and Evaluation of Conductive Polymer Solution)
0.05 g of the PT and 0.1 g of the modified polyamine compound (1) were added to 9.85 g of ethyl acetate as an organic solvent (C) and stirred to prepare a conductive polymer solution. The conductive polymer solution was measured for average particle size according to the above-mentioned [Measurement of particle size of conductive polymer solution]. The results are shown in Table 4.

Example 38 (Preparation and Evaluation of Conductive Polymer Solution)
0.2 g of the PT and 0.4 g of the modified polyamine compound (1) were added to 9.40 g of ethyl acetate as an organic solvent (C) and stirred to prepare a conductive polymer solution. The conductive polymer solution was measured for average particle size according to the above-mentioned [Measurement of particle size of conductive polymer solution]. The results are shown in Table 4.

Examples 39 to 44 (Preparation and Evaluation of Conductive Polymer Solutions)
Conductive polymer solutions were prepared in the same manner as in Example 37 or 38, except that the modified polyamine compound (3), the modified polyamine compound (7), or the modified polyamine compound (9) was used instead of the modified polyamine compound (1) as the modified polyamine compound (B). The respective formulations are shown in Table 4. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Examples 45 to 48 (Preparation and Evaluation of Conductive Polymer Solutions)
Conductive polymer solutions were prepared in the same manner as in Example 37 or 38, except that butyl acetate or toluene was used instead of ethyl acetate as the organic solvent (C). The respective formulations are shown in Table 4. The conductive polymer solutions were measured for average particle size according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Examples 49 and 50 (Preparation and Evaluation of Conductive Polymer Solutions)
Conductive polymer solutions were prepared in the same manner as in Example 37 or 38, except that the modified polyamine compound (1') was used as the modified polyamine compound (B) instead of the modified polyamine compound (1) in Example 37 or 38. The respective formulations are shown in Table 4. The average particle size of the conductive polymer solution was measured according to the above-mentioned [Particle size measurement of conductive polymer solution]. The results are shown in Table 4.

Comparative Example 1 (Preparation and Evaluation of Conductive Polymer Solution)
0.1 g of the above PT was added to 9.9 g of ethyl acetate and stirred to prepare a mixed solution, but the PT was not dissolved or dispersed in the mixed solution.

Comparative Example 2 (Preparation and Evaluation of Conductive Polymer Solution)
0.1 g of the above PT and 0.2 g of polyallylamine PAA-01 (manufactured by Nittobo Medical Co., Ltd.) were added to 9.7 g of ethyl acetate and stirred to prepare a mixed solution. However, PT was not dissolved or dispersed in the mixed solution.

Comparative Example 3 (Preparation and Evaluation of Conductive Polymer Solution)
0.1 g of PEDOT:PSS solid (Orbacon DRY, manufactured by ALDRICH) and 0.2 g of the modified polyamine compound (1) were added to 9.7 g of ethyl acetate and stirred to prepare a mixed solution. However, the PEDOT:PSS solid was not dissolved or dispersed in the mixed solution.

Comparative Example 4 (Preparation and Evaluation of Conductive Polymer Solution)
A mixed solution was prepared by adding 0.1 g of PEDOT:PSS solid (Orbacon DRY, manufactured by ALDRICH) to a mixed solution of 4.85 g of γ-butyrolactone and 4.85 g of ethyl acetate and stirring the mixture. However, the PEDOT:PSS solid was not dissolved or dispersed in the mixed solution.

For a summary of each Example and Comparative Example, the measurement results of the average particle size are shown in Tables 3 and 4. In Comparative Example 2, modified polyamine compound (B) was not added. In Comparative Examples 3 and 4, polythiophene (A) was not added. Therefore, in Comparative Examples 2 to 4, the compounds added as substitutes are shown in parentheses. The units of the numbers in square brackets in Tables 3 and 4 are the units in square brackets in the first row of the table, and this also applies to the following tables.

The results of the examples and comparative examples confirmed that by adding polythiophene (A) and modified polyamine compound (B), it is possible to produce a conductive polymer solution that is uniformly dissolved or dispersed in an organic solvent.

Example 51 (Preparation and Evaluation of Pressure-Sensitive Adhesive Composition)
An adhesive composition was prepared by mixing 2 g of the conductive polymer solution prepared in Example 1 above and 2 g of Saibinol AT-245 (manufactured by Saiden Chemical Industry Co., Ltd.) as adhesive (D) and stirring. A conductive adhesive film was produced according to the above [Method for measuring surface resistance of conductive adhesive film], and the surface resistance was measured, which was 10 ¹⁰ Ω/□.

To evaluate moisture resistance, the adhesive film was left to stand for 150 hours in an environment with a temperature of 85°C and a humidity of 85%, and the appearance was then checked, and no change was found in appearance. The results are shown in Table 5.

Examples 52 to 100 (Preparation and Evaluation of Pressure-Sensitive Adhesive Compositions)
In Example 51, instead of the 2 g of the conductive polymer solution prepared in Example 1, 2 g of the conductive polymer solution prepared in each of Examples 2 to 50 was used to prepare a pressure-sensitive adhesive composition. A conductive adhesive film was produced according to the above-mentioned [Method for measuring surface resistance of conductive adhesive film], and the surface resistance was measured. In addition, an appearance evaluation was performed in the same manner as in Example 51. The results are shown in Tables 5 and 6.

Comparative Examples 5 and 6 (Preparation and Evaluation of Mixed Solutions Containing Adhesive)
In Example 51, an attempt was made to prepare an adhesive composition by using 2 g of the conductive polymer solution prepared in Comparative Example 1 or 2 instead of 2 g of the conductive polymer solution prepared in Example 1. However, PT did not dissolve in the mixed solution, and a conductive adhesive film could not be produced.

Comparative Examples 7 and 8 (Preparation and Evaluation of Mixed Solutions Containing Adhesive)
In Example 51, an attempt was made to prepare an adhesive composition by using 2 g of the conductive polymer solution prepared in Comparative Example 3 or 4 instead of 2 g of the conductive polymer solution prepared in Example 1. However, PEDOT:PSS did not dissolve in the mixed solution, and a conductive adhesive film could not be produced.

Comparative Example 9 (Preparation and Evaluation of Mixed Solution Containing Adhesive)
In Example 51, instead of 2 g of the conductive polymer solution prepared in Example 1, 2 g of a composition consisting of 1 wt % tetrabutylammonium bromide (TBABr) and 99 wt % ethyl acetate was used to prepare a pressure-sensitive adhesive composition. A conductive adhesive film was produced according to the above-mentioned [Method for measuring the surface resistance of a conductive adhesive film], and the surface resistance was measured. In addition, when the appearance was evaluated in the same manner as in Example 51, dissolution of the adhesive film was observed. The results are shown in Table 6.

Comparative Example 10 (Preparation and Evaluation of Mixed Solution Containing Adhesive)
In Example 51, instead of 2 g of the conductive polymer solution prepared in Example 1, 2 g of a composition consisting of 1 wt % 1-ethyl-3-imidazolium tetrafluoroborate (EMIMBF4) and 99 wt % ethyl acetate was used to prepare an adhesive composition. A conductive adhesive film was produced according to the above [Method for measuring surface resistance of conductive adhesive film], and the surface resistance was measured. In addition, when the appearance was evaluated in the same manner as in Example 51, dissolution of the adhesive film was observed. The results are shown in Table 6.

Comparative Example 11 (Preparation and Evaluation of Mixed Solution Containing Adhesive)
In Example 51, instead of 2 g of the conductive polymer solution prepared in Example 1, 2 g of a composition consisting of 1 wt % tetrabutylammonium bromide (TBABr), 2 wt % of the modified polyamine compound (1), and 97 wt % ethyl acetate was used to prepare a pressure-sensitive adhesive composition. A conductive adhesive film was produced according to the above-mentioned [Method for measuring the surface resistance of a conductive adhesive film], and the surface resistance was measured. In addition, when the appearance was evaluated in the same manner as in Example 51, dissolution of the adhesive film was observed. The results are shown in Table 6.

Tables 5 and 6 show the results of measuring the surface resistance for each example and comparative example. Note that in comparative examples 9 to 11, the conductive polymer solution according to one embodiment of the present invention was not used. Therefore, in comparative examples 9 to 11, the composition used as a substitute for the conductive polymer solution according to one embodiment of the present invention is shown in parentheses.

From the results of the Examples and Comparative Examples, it was confirmed that by adding a conductive polymer solution according to one embodiment of the present invention, a conductive adhesive film having a relatively low surface resistance and exhibiting antistatic properties, and an adhesive composition for obtaining such a conductive adhesive film, can be obtained. In addition, it was confirmed that a conductive adhesive film containing polythiophene (A) and modified polyamine compound (B) according to one embodiment of the present invention has superior moisture resistance compared to a conductive adhesive film containing an ionic compound.

Example 101 (Preparation and Evaluation of Pressure-Sensitive Adhesive Composition)
2 g of the conductive polymer solution prepared in Example 16 above and 2 g of Saibinol AT-352 (manufactured by Saiden Chemical Industry Co., Ltd.) as adhesive (D) were mixed and stirred to prepare an adhesive composition. A conductive adhesive film was produced according to the above [Method for measuring surface resistance of conductive adhesive film], and the surface resistance was measured to be 10 ¹² Ω/□.

To evaluate moisture resistance, the adhesive film was left to stand for 150 hours in an environment with a temperature of 85°C and a humidity of 85%, and the appearance was then checked, with no change observed. The results are shown in Table 7.

Examples 102 to 121 (Preparation and Evaluation of Pressure-Sensitive Adhesive Compositions)
In Example 101, instead of the 2 g of the conductive polymer solution prepared in Example 16, 2 g of the conductive polymer solution prepared in each of Examples 17 to 36 was used to prepare a pressure-sensitive adhesive composition. A conductive adhesive film was produced according to the above-mentioned [Method for measuring the surface resistance of a conductive adhesive film], and the surface resistance was measured. In addition, an appearance evaluation was performed in the same manner as in Example 51. The results are shown in Table 7.

Comparative Example 12 (Preparation and Evaluation of Mixed Solution Containing Adhesive)
In Example 101, instead of the conductive polymer solution 2g prepared in Example 16, the conductive polymer solution 2g prepared in Comparative Example 4 was used to prepare an adhesive composition. However, PEDOT:PSS did not dissolve in the mixed solution, and a conductive adhesive film could not be produced. The results are shown in Table 7.

Comparative Example 13 (Preparation and Evaluation of Mixed Solution Containing Pressure-Sensitive Adhesive)
In Example 101, instead of 2 g of the conductive polymer solution prepared in Example 16, 2 g of a composition consisting of 1 wt % tetrabutylammonium bromide (TBABr) and 99 wt % ethyl acetate was used to prepare an adhesive composition. A conductive adhesive film was produced according to the above [Method for measuring surface resistance of conductive adhesive film], and the surface resistance was measured. In addition, when the appearance was evaluated in the same manner as in Example 101, dissolution of the adhesive layer was observed. The results are shown in Table 7.

Comparative Example 14 (Preparation and Evaluation of Mixed Solution Containing Pressure-Sensitive Adhesive)
In Example 101, instead of 2 g of the conductive polymer solution prepared in Example 16, 2 g of a composition consisting of 1 wt % 1-ethyl-3-imidazolium tetrafluoroborate (EMIMBF4) and 99 wt % ethyl acetate was used to prepare an adhesive composition. A conductive adhesive film was produced according to the above [Method for measuring surface resistance of conductive adhesive film], and the surface resistance was measured. In addition, when the appearance was evaluated in the same manner as in Example 101, dissolution of the adhesive film was observed. The results are shown in Table 7.

Comparative Example 15 (Preparation and Evaluation of Mixed Solution Containing Pressure-Sensitive Adhesive)
In Example 101, instead of 2 g of the conductive polymer solution prepared in Example 16, 2 g of a composition consisting of 1 wt% tetrabutylammonium bromide (TBABr), 2 wt% of the modified polyamine (1), and 97 wt% ethyl acetate was used to prepare a pressure-sensitive adhesive composition. A conductive adhesive film was produced according to the above-mentioned [Method for measuring the surface resistance of a conductive adhesive film], and the surface resistance was measured. In addition, when the appearance was evaluated in the same manner as in Example 101, dissolution of the adhesive film was observed. The results are shown in Table 7.

Table 7 shows the results of measuring the surface resistance for each example and comparative example. Note that in comparative examples 13 to 15, the conductive polymer solution according to one embodiment of the present invention was not used. Therefore, in comparative examples 13 to 15, the composition used as a substitute for the conductive polymer solution according to one embodiment of the present invention is shown in parentheses.

From the results of these examples and comparative examples, it was confirmed that by adding a conductive polymer solution according to one embodiment of the present invention, a conductive adhesive film having a relatively low surface resistance and exhibiting antistatic properties, and an adhesive composition for obtaining such a conductive adhesive film, can be obtained. In addition, it was confirmed that a conductive adhesive film containing polythiophene (A) and modified polyamine compound (B) according to one embodiment of the present invention has superior moisture resistance compared to a conductive adhesive film containing an ionic compound.

Example 122 (Preparation and Evaluation of Resin Composition for Hard Coating Using Conductive Polymer Solution)
0.9 g of the conductive polymer solution prepared in Example 1 above, 1.8 g of a urethane acrylate oligomer (Shin-Nakamura Chemical Co., Ltd., product name: UA-1100H, corresponding to the oligomer (e1) described above) as the ultraviolet curable resin (E), 1.8 g of 2-hydroxyethyl acrylate (corresponding to the monomer (e2) described above), 0.3 g of 1-hydroxycyclohexyl phenyl ketone (corresponding to the photopolymerization initiator (e3) described above), and 5.2 g of PGME (corresponding to the solvent described above) were mixed with the ultraviolet curable resin (E) and stirred until uniformly dissolved and dispersed to prepare an ultraviolet curable hard coat resin composition according to one embodiment of the present invention containing a conductive polymer. The composition of the ultraviolet curable hard coat resin composition is shown in Table 1. A hard coat was prepared from this prepared composition according to the above-mentioned [Hard coat preparation method], and evaluated according to [Method of measuring surface resistance of hard coat and evaluation criteria]. The obtained evaluation results are shown in Table 8.

Examples 123 to 171 (Preparation and Evaluation of Resin Compositions for Hard Coating Using Conductive Polymer Solutions)
In Example 122, 0.9 g of the conductive polymer solution prepared in Examples 2 to 50 was used instead of 2 g of the conductive polymer solution prepared in Example 1 to prepare UV-curable hard coat resin compositions. Hard coats were prepared according to the above [Hard coat preparation method] and evaluated according to [Method of measuring surface resistance of hard coat and evaluation criteria]. The obtained evaluation results are shown in Tables 8 and 9.

Comparative Examples 16 and 17 (Preparation and Evaluation of Resin Composition for Hard Coat Using Conductive Polymer Solution)
In Example 122, instead of 0.9 g of the conductive polymer solution prepared in Example 1, 0.9 g of the conductive polymer solution prepared in Comparative Example 1 or 2 was used to prepare a resin composition for ultraviolet-curable hard coat. A hard coat was prepared according to the above [Hard coat preparation method] and evaluated according to [Method of measuring surface resistance value of hard coat and evaluation criteria]. However, since PT was not sufficiently dissolved in the resin composition, the surface resistivity of the obtained hard coat film exceeded 10 ¹³ Ω/□ and it had no antistatic ability.

Comparative Examples 18 and 19 (Preparation and Evaluation of Resin Composition for Hard Coat Using Conductive Polymer Solution)
In Example 122, instead of 0.9 g of the conductive polymer solution prepared in Example 1, 0.9 g of the conductive polymer solution prepared in Comparative Example 3 or 4 was used to prepare an ultraviolet-curable hard coat resin composition. A hard coat was prepared according to the above [Hard coat preparation method] and evaluated according to [Method of measuring surface resistance value of hard coat and evaluation criteria]. However, since PEDOT:PSS was not sufficiently dissolved in the resin composition, the surface resistivity of the obtained hard coat film exceeded 10 ¹³ Ω/□ and it had no antistatic ability.

Comparative Example 20 (Preparation and Evaluation of Resin Composition for Hard Coating Using Conductive Polymer Solution)
In Example 122, instead of 0.9 g of the conductive polymer solution prepared in Example 1, 0.9 g of a composition consisting of 1 wt % tetrabutylammonium bromide (TBABr) and 99 wt % ethyl acetate was used to prepare an ultraviolet-curable hard coat resin composition. A hard coat was prepared according to the above [Hard coat preparation method] and evaluated according to [Method of measuring surface resistance value of hard coat and evaluation criteria]. The obtained evaluation results are shown in Table 9.

Tables 8 and 9 show the results of measuring the surface resistance for each example and comparative example. Note that in Comparative Example 20, the conductive polymer solution according to one embodiment of the present invention was not used. Therefore, in Comparative Example 20, the composition used as a substitute for the conductive polymer solution according to one embodiment of the present invention is shown in parentheses.

From the results of these examples and comparative examples, it was confirmed that by adding a conductive polymer solution according to one embodiment of the present invention, a conductive hard coat having a relatively low surface resistance and exhibiting antistatic properties, as well as a composition for obtaining such a conductive hard coat, can be obtained.

The present invention can be used, for example, in adhesives, antistatic materials, LCDs, organic electroluminescence, or transparent electrodes.

Claims (17)

A conductive polymer solution comprising: polythiophene (A) containing two or more structural units represented by the following general formula (7); modified polyamine compound (B) constituted by a repeating unit represented by the following general formula (3-1) and/or a repeating unit represented by the following general formula (3-2), and a repeating unit represented by the following general formula (3-3); and an organic solvent (C).
[In the general formula (7), R represents an organic group having a total of 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.]
[In the general formula (3-1), R ² represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms. X represents a divalent polymer group formed by random polymerization or block polymerization in a random order of k propyleneoxy groups (-CH ₂ -CH(CH ₃ )-O-) and j ethyleneoxy groups (-CH ₂ -CH ₂ -O-), k represents an integer of 0 to 50, j represents an integer of 10 to 100, and k+j=10 to 150. p represents 1 or 2. h represents an integer of 2 to 6. In the general formula (3-2), R ³ represents a divalent aliphatic hydrocarbon group having 8 to 22 carbon atoms which may be branched. m represents an integer of 2 to 11, and n represents an integer of 0 to 1000.] The conductive polymer solution according to claim 1, wherein the organic solvent (C) is at least one selected from the group consisting of ester solvents and aromatic solvents. The conductive polymer solution according to claim 1, wherein the organic solvent (C) is at least one selected from the group consisting of methyl acetate, ethyl acetate, normal propyl acetate, butyl acetate, isobutyl acetate, methoxybutyl acetate, benzene, toluene, and xylene. The conductive polymer solution according to claim 1, wherein the content of the polythiophene (A) is 0.01 to 10 parts by weight per 100 parts by weight of the organic solvent (C). The conductive polymer solution according to claim 1, wherein the content of the modified polyamine compound (B) is 0.01 to 10 parts by weight per 100 parts by weight of the organic solvent (C). 2. The conductive polymer solution according to claim 1, wherein the polythiophene (A) contains two or more structural units 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):
[In general formula (1), M ⁺ represents a proton, a conjugate acid of an amine compound, or a quaternary ammonium ion. In general formulas (1) and (2), ^R1 independently 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.] 7. The conductive polymer solution according to claim 6, wherein the M ⁺ is a proton or a conjugate acid of an amine compound having a total of 15 to 24 carbon atoms. 7. The conductive polymer solution according to claim 6, wherein M ⁺ is at least one selected from the group consisting of a dioctylammonium ion, a tridecylammonium ion, a hexadecylammonium ion, an octadecylammonium ion, an oleylammonium ion, a di-n-octylammonium ion, a bis(2-ethylhexyl)ammonium ion, a dimethylstearylammonium ion, a trihexylammonium ion, a trioctylammonium ion, a tris(2-ethylhexyl)ammonium ion, a dodecyltrimethylammonium ion, and a tetrahexylammonium ion. An adhesive composition comprising the conductive polymer solution according to any one of claims 1 to 8 and an adhesive (D). The adhesive composition according to claim 9, wherein the adhesive (D) is an acrylic adhesive. A conductive adhesive film comprising: polythiophene (A) containing two or more structural units represented by the following general formula (7); modified polyamine compound (B) constituted by a repeating unit represented by the following general formula (3-1) and/or a repeating unit represented by the following general formula (3-2), and a repeating unit represented by the following general formula (3-3); and an adhesive (D).
[In the general formula (7), R represents an organic group having a total of 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.]
[In the general formula (3-1), R ² represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms. X represents a divalent polymer group formed by random polymerization or block polymerization in a random order of k propyleneoxy groups (-CH ₂ -CH(CH ₃ )-O-) and j ethyleneoxy groups (-CH ₂ -CH ₂ -O-), k represents an integer of 0 to 50, j represents an integer of 10 to 100, and k+j=10 to 150. p represents 1 or 2. h represents an integer of 2 to 6. In the general formula (3-2), R ³ represents a divalent aliphatic hydrocarbon group having 8 to 22 carbon atoms which may be branched. m represents an integer of 2 to 11, and n represents an integer of 0 to 1000.] The conductive adhesive film according to claim 11, wherein the polythiophene (A) contains two or more structural units 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).
[In general formula (1), M ⁺ represents a proton, a conjugate acid of an amine compound, or a quaternary ammonium ion. In general formulas (1) and (2), ^R1 independently 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.] The conductive adhesive film according to claim 11, wherein the adhesive (D) is an acrylic adhesive. A resin composition for ultraviolet-curable hard coats, comprising the conductive polymer solution according to any one of claims 1 to 8 and an ultraviolet-curable resin (E). A method for producing a hard coat, comprising the steps of applying the ultraviolet-curable hard coat resin composition according to claim 14 to a substrate, drying the composition, and then irradiating the substrate with ultraviolet light. A cured product obtained by curing the UV-curable hard coat resin composition according to claim 14. A hard coat comprising a polythiophene (A) containing two or more structural units represented by the following general formula (7), and a modified polyamine compound (B) constituted by a repeating unit represented by the following general formula (3-1) and/or a repeating unit represented by the following general formula (3-2), and a repeating unit represented by the following general formula (3-3):
[In the general formula (7), R represents an organic group having a total of 1 to 18 carbon atoms and having at least one substituent selected from the group consisting of a sulfonic acid group and a phosphonic acid group.]
[In the general formula (3-1), R ² represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms. X represents a divalent polymer group formed by random polymerization or block polymerization in a random order of k propyleneoxy groups (-CH ₂ -CH(CH ₃ )-O-) and j ethyleneoxy groups (-CH ₂ -CH ₂ -O-), k represents an integer of 0 to 50, j represents an integer of 10 to 100, and k+j=10 to 150. p represents 1 or 2. h represents an integer of 2 to 6. In the general formula (3-2), R ³ represents a divalent aliphatic hydrocarbon group having 8 to 22 carbon atoms which may be branched. m represents an integer of 2 to 11, and n represents an integer of 0 to 1000.]