JP2016043496A - Conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive film excellent in conductivity, transparency, coating hardness, light resistance, and moisture and heat resistance.SOLUTION: A conductive film comprises a methylolated phenolic compound represented by formula (1) (R-Rrepresent a hydrogen atom, a halogen atom, an alkyl group or the like; Rand Rrepresent a hydrogen atom or an alkyl group; Xrepresents an amide group, an ether group or the like, or formula (2)).SELECTED DRAWING: None

Description

  The present invention relates to a conductive film.

  The conductive film has a conductive layer formed by applying a conductive compound on at least one of the surfaces of a plastic film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN). As this conductive compound, many organic and inorganic compounds are known.

  As a representative example of the inorganic conductive compound, an indium-tin composite oxide (ITO) is known. This ITO is widely used as a transparent electrode, an electromagnetic shielding material, and the like in electrical devices such as liquid crystal displays, touch panels, and solar cells. Such transparent electrodes, electromagnetic shielding materials, and the like are formed by depositing an ITO film on the surface of a base plastic film by a vacuum deposition method, a sputtering method, or the like.

  However, since the conductive film having the ITO film is inferior in flexibility, cracks due to bending tend to occur. In addition, the ITO film has a disadvantage of low productivity and high manufacturing cost because it uses indium which is a rare metal.

  On the other hand, π-conjugated polymers such as polypyrrole, polyaniline, and polythiophene are known as organic conductive compounds. These π-conjugated polymers form a coating film by applying or printing a coating solution in which the π-conjugated polymer is dissolved or dispersed in an appropriate solvent. By drying this coating film, a flexible organic conductive layer can be formed (see JP-A-6-273964).

  The organic conductive layer is excellent in flexibility and productivity as compared with the ITO film, but has a disadvantage of poor conductivity. Further, the organic conductive layer has a disadvantage that it is weak against ultraviolet rays and heat and inferior in stability to the ITO film. In order to improve the conductivity of the organic conductive layer, a method using a conductive polymer composition to which an organic compound containing two or more hydroxy groups in the molecule is added has been proposed. As this conductive polymer composition, for example, a dispersion of a conductive polymer in a glycol-containing compound such as ethylene glycol (see JP 2005-529474 A), a dispersion of the conductive polymer compound, Examples include those to which a small amount of ethylene glycol is added (see Non-Patent Document 1).

  However, since ethylene glycol has a relatively high boiling point, it is difficult to evaporate from the coating film. Therefore, in the conductive film in which the organic conductive layer containing ethylene glycol as a constituent component is laminated, the hardness of the obtained organic conductive layer is lowered, and as a result, there is a disadvantage that the conductivity is lowered.

  Therefore, it is desired to improve the conductivity and stability while enjoying the advantage of the organic conductive compound that a conductive film having flexibility can be formed at low cost.

JP-A-6-273964 JP 2005-529474 A

S. Ashizawa, R.A. Hirokawa, H .; Okuzaki, “Synthetic Metals”, 2005, Vol. 153, p. 5-p. 8

  This invention is made | formed based on the above situations, and it aims at providing the electroconductive film which is excellent in electroconductivity, transparency, coating-film hardness, light resistance, and heat-and-moisture resistance at low cost.

（式（１）中、Ｒ^１〜Ｒ^４は、それぞれ独立して、水素原子、ハロゲン原子、カルボキシ基、スルホ基、アルキル基、アルコキシ基、シクロアルキル基、アリル基又はフェニル基である。Ｒ^５及びＲ^６は、それぞれ独立して、水素原子又はアルキル基である。Ｘ^１は、アミド基、エーテル基、カルボニル基、キシレニル基、スルフィド基、スルホニル基、ジスルフィド基、シクロアルキレン基、フェニレン基又は下記式（２）で表される基である。ａ、ｂ及びｄは、それぞれ独立して、１又は２である。ｃは、０以上２以下の整数である。ｋは、０以上２以下の整数である。ただし、ｃ及びｋは同時に０となることはない。ｊは、０又は１である。また、ａ、ｂ、ｃ、ｄ及びｋは、下記式（Ｉ）及び（ＩＩ）を満たす。Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＸ^１がそれぞれ複数の場合、複数のＲ^３は同一でも異なっていてもよく、複数のＲ^４は同一でも異なっていてもよく、複数のＲ^５は同一でも異なっていてもよく、複数のＲ^６は同一でも異なっていてもよく、複数のＸ^１は同一でも異なっていてもよい。）
２≦ａ＋ｃ＋ｋ≦４ （Ｉ）
２≦ｂ＋ｄ≦３ （ＩＩ）

（式（２）中、Ｒ^７は、水素原子、アルキル基、フルオロアルキル基、シクロアルキル基又はフェニル基である。Ｙ^１は、水素原子、アルキル基、フルオロアルキル基、シクロアルキル基、フェニル基、アダマンチル基又は下記式（３）で表わされる基である。ただし、Ｙ^１とＲ^７とは互いに結合してシクロアルカン構造又はフルオレン構造を形成していてもよい。）

（式（３）中、Ｒ^８及びＲ^９は、それぞれ独立して、水素原子、ハロゲン原子、カルボキシ基、スルホ基、アルキル基、シクロアルキル基、アリル基又はフェニル基である。Ｒ^１０は、水素原子、アルキル基、シクロアルキル基、フェニル基又はベンジル基である。Ｒ^１１は、水素原子又はアルキル基である。ｅ及びｆは、それぞれ独立して０以上２以下の整数であり、下記式（ＩＩＩ）を満たす。ｅが２の場合、複数のＲ^１０は同一でも異なっていてもよい。ｆが２の場合、複数のＲ^１１は同一でも異なっていてもよい。）
０≦ｅ＋ｆ≦３ （ＩＩＩ） The invention made in order to solve the above-mentioned problem is that a conductive polymer compound (hereinafter also referred to as “conductive polymer compound (A)”) and the following formula (1) are formed on at least one surface of the base film. A conductive film in which a conductive layer containing a methylolated phenol compound (hereinafter also referred to as “methylolated phenol compound (B)”) is laminated.

(In formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group, an alkoxy group, a cycloalkyl group, an allyl group, or a phenyl group. ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group, and X ¹ is an amide group, an ether group, a carbonyl group, a xyenyl group, a sulfide group, a sulfonyl group, a disulfide group, a cycloalkylene group, or a phenylene group. Or a group represented by the following formula (2): a, b and d are each independently 1 or 2. c is an integer of 0 to 2, and k is 0 to 2. C and k are not simultaneously 0. j is 0 or 1. Further, a, b, c, d and k are represented by the following formulas (I) and (II). ) R ³ , R ⁴ , R ⁵ , when R ⁶ and X ¹ are plural, plural R ³ may be the same or different, plural R ⁴ may be the same or different, and plural R ⁵ may be the same or different. The plurality of R ⁶ may be the same or different, and the plurality of X ¹ may be the same or different.)
2 ≦ a + c + k ≦ 4 (I)
2 ≦ b + d ≦ 3 (II)

(In Formula (2), R ⁷ is a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, or a phenyl group. Y ¹ is a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, or a phenyl group. An adamantyl group or a group represented by the following formula (3), provided that Y ¹ and R ⁷ may be bonded to each other to form a cycloalkane structure or a fluorene structure.)

(In the formula (3), ^{R 8} and ^{R 9} are each independently hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group, a cycloalkyl group, ^{.R 10} an allyl group or a phenyl group, A hydrogen atom, an alkyl group, a cycloalkyl group, a phenyl group or a benzyl group, R ¹¹ is a hydrogen atom or an alkyl group, and e and f are each independently an integer of 0 or more and 2 or less. (III) is satisfied. When e is 2, the plurality of R ¹⁰ may be the same or different. When f is 2, the plurality of R ¹¹ may be the same or different.)
0 ≦ e + f ≦ 3 (III)

  In the conductive film, a conductive layer containing a methylolated phenol compound represented by the above formula (1) is laminated. The said conductive film is excellent in transparency, electroconductivity, coating-film hardness, light resistance, and heat-and-moisture resistance because the conductive layer of the said structure is laminated | stacked. The reason why the conductive film has the above-described effect by laminating the conductive layer having the above-described configuration is not necessarily clear, but can be estimated as follows, for example. The methylolated phenol compound contains two or more hydroxy groups in the molecule, like ethylene glycol, which is a known conductivity improving component. By this hydroxy group, the methylolated phenol compound and the conductive polymer compound form a hydrogen bond, the distance between the conductive polymer compounds is reduced, and the energy required for electrical conduction is reduced. This also increases the interaction between the methylolated phenol compound and the conductive polymer compound. As a result, it is considered that the electrical resistance of the conductive layer is reduced and the conductivity of the conductive film is increased. Moreover, the said conductive film can form the conductive film which is excellent in electroconductivity and coating-film hardness at low cost by laminating | stacking the conductive layer of the said structure at low cost.

  Further, the methylolated phenol compound has a radical scavenging ability by containing a phenolic hydroxy group, and acts as an antioxidant. Therefore, radicals generated by oxidative degradation of the conductive film can be deactivated, and progress of degradation can be suppressed. As a result, it is considered that the heat resistance and stability of the conductive layer are increased.

  Furthermore, the methylolated phenol compound has a methylol group. This methylol group causes a self-condensation of the methylolated phenol compound or a crosslinking reaction with the crosslinking agent and the binder resin. As a result, the hardness of the conductive layer is improved, and a conductive film excellent in conductivity and stability can be provided.

  In the above formula (1), it is preferable that k is 0 and c is 2, or k is 1 and c is 1 or 2. When c and k in the above formula (1) are such values, the solubility of the methylolated phenol compound in the solvent is increased, and the handleability and film formability are improved. Furthermore, the conductivity of the conductive layer is further improved.

R ^{1 to} R ⁴ in the above formula (1) are each independently a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and X ¹ is an ether group, a carbonyl group, a sulfide group, a sulfonyl group or the above formula ( 2), wherein R ⁷ in the above formula (2) is a hydrogen atom, an alkyl group or a fluoroalkyl group, and Y ¹ is a hydrogen atom, an alkyl group, a fluoroalkyl group or the above formula (3). It is preferable that R < ⁸ > -R < ¹¹ > in the said Formula (3) is a hydrogen atom or an alkyl group.

Thus, when the methylolated phenol compound satisfies the above-described conditions, the solubility in the above-described solvent becomes higher, and the handleability and the film-forming property are improved. Furthermore, the hue change of the conductive layer is reduced and the stability is improved.

Examples of the methylolated phenol compound include 2,6-dihydroxymethyl-4-methylphenol represented by the following formula (4), 4-fluoro-2,6-dihydroxymethylphenol represented by the following formula (5), and And 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane represented by the following formula (6) is preferable. By containing the said compound, stability and the solubility of a methylolation phenol compound improve more.

  The conductive layer may further contain a dopant that oxidizes or reduces the conductive polymer compound. By containing the dopant, the conductivity of the conductive layer can be further improved.

  The conductive polymer compound may be polythiophene or a derivative thereof, and the dopant may be an organic sulfonic acid, an organic sulfonic acid metal salt, or an organic sulfonic acid anion. When the conductive polymer compound and the dopant are the compounds, stability when the dopant is doped into the conductive polymer compound is improved. As a result, a conductive layer having higher conductivity can be formed.

  The conductive polymer compound is poly (3,4-ethylenedioxythiophene) (hereinafter also referred to as “PEDOT”), and the dopant is poly (4-styrenesulfonic acid) (hereinafter also referred to as “PSS”). .) When the conductive polymer compound and the dopant are the compounds, the dopant is doped into the conductive polymer compound to form a specific composite (hereinafter also referred to as “PEDOT / PSS”). Can do. Since this composite can be dispersed in water, the conductive layer can be easily formed by coating. Moreover, the transparency of a coating film and a conductive layer can also be improved.

（式（７）中、Ｒ^１２〜Ｒ^１５は、それぞれ独立して、水素原子、ハロゲン原子、カルボキシ基、スルホ基、アルキル基、アルコキシ基、シクロアルキル基、アリル基又はフェニル基である。Ｘ^２は、アミド基、エーテル基、カルボニル基、キシレニル基、スルフィド基、スルホニル基、ジスルフィド基、シクロアルキレン基、フェニレン基又は下記式（８）で表される基である。ｇ及びｈは、それぞれ独立して１以上３以下の整数である。ｎは、０以上３以下の整数である。ｍは１又は２の整数である。また、ｇ及びｎは、下記式（ＩＶ）を満たす。Ｒ^１４、Ｒ^１５及びＸ^２がそれぞれ複数の場合、複数のＲ^１４は同一でも異なっていてもよく、複数のＲ^１５は同一でも異なっていてもよく、複数のＸ^２は同一でも異なっていてもよい。）
２≦ｇ＋ｎ≦４ （ＩＶ）

（式（８）中、Ｒ^１６は、水素原子、アルキル基、フルオロアルキル基、シクロアルキル基、フェニル基である。Ｙ^２は、水素原子、アルキル基、フルオロアルキル基、シクロアルキル基、フェニル基、アダマンチル基又は下記式（９）で表わされる基である。但し、Ｙ^２とＲ^１６とは互いに結合してシクロアルカン構造又はフルオレン構造を形成していてもよい。）

（式（９）中、Ｒ^１７及びＲ^１８は、それぞれ独立して、水素原子、ハロゲン原子、カルボキシ基、スルホ基、アルキル基、シクロアルキル基、アリル基又はフェニル基である。Ｒ^１９は、水素原子、アルキル基、シクロアルキル基、フェニル基又はベンジル基である。ｉは、０以上３以下の整数である。ｉが２以上の場合、複数のＲ^１９は同一でも異なっていてもよい。） The conductive layer preferably contains a polyhydric phenol compound represented by the following formula (7) (hereinafter also referred to as “polyhydric phenol compound (C)”).

(In the formula ^{(7), R} 12 ~R ¹⁵ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group, an alkoxy group, a cycloalkyl group, an allyl group or a phenyl group .X ² is an amide group, an ether group, a carbonyl group, a xylenyl group, a sulfide group, a sulfonyl group, a disulfide group, a cycloalkylene group, a phenylene group, or a group represented by the following formula (8): g and h are respectively Independently, it is an integer of 1 to 3. n is an integer of 0 to 3. m is an integer of 1 or 2. Further, g and n satisfy the following formula (IV). ^14, when R ¹⁵ and X ² are a plurality of each of the plurality of R ¹⁴ may be the same or different, a plurality of R ¹⁵ may be the same or different, even if a plurality of X ² may be the same or different It has.)
2 ≦ g + n ≦ 4 (IV)

(In the formula (8), R ¹⁶ is a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, or a phenyl group. Y ² is a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, or a phenyl group. An adamantyl group or a group represented by the following formula (9), provided that Y ² and R ¹⁶ may be bonded to each other to form a cycloalkane structure or a fluorene structure.

(In the formula ^{(9), R 17} and ^{R 18} are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group, a cycloalkyl group, ^{.R 19} an allyl group or a phenyl group, A hydrogen atom, an alkyl group, a cycloalkyl group, a phenyl group, or a benzyl group, i is an integer of 0 or more and 3 or less, and when i is 2 or more, a plurality of R ¹⁹ may be the same or different. )

  Like the methylol compound, the polyhydric phenol compound acts as an antioxidant by containing a phenolic hydroxy group. Therefore, it is considered that the stability of the conductive layer is increased.

  Furthermore, since the polyphenol compound can be cured by heat with the methylolated phenol compound, it is considered that the strength of the conductive layer is further improved.

  In the above formula (7), g and h are preferably 1 or 2, and n is 1. When g, h, and n in the above formula (7) are such values, the solubility of the polyphenol compound in the solvent is increased, and the conductivity of the conductive layer is further improved.

R ^{12 to} R ¹⁵ in the above formula (7) are each independently represented by a hydrogen atom, an alkyl group or an alkoxy group, X ² is represented by an ether group, a carbonyl group, a sulfide group, a sulfonyl group or the above formula (7). R ¹⁶ in the above formula (8) is a hydrogen atom, an alkyl group or a fluoroalkyl group, Y ² is a hydrogen atom, an alkyl group, a fluoroalkyl group or a group represented by the above formula (8). In the above formula (9), R ^{17 to} R ¹⁹ are each independently a hydrogen atom or an alkyl group, and i is preferably 0 or more and 2 or less.

  Thus, when the polyhydric phenol compound satisfies the above conditions, the solubility in the above-mentioned solvent becomes higher, the compatibility with the methylolated phenol compound is further improved, and the handleability and film formability are further improved. To do. Further, the hue change is further reduced and the stability is further improved.

Examples of the polyhydric phenol compound include bis (4-hydroxyphenyl) sulfone represented by the following formula (10), bis (4-hydroxyphenyl) ether represented by the following formula (11), and the following formula (12). The bis (3,4-dihydroxy-6-methylphenyl) methane represented is preferred. By containing the said compound, stability and the solubility of a polyhydric phenol compound improve more. Furthermore, since these polyhydric phenol compounds have a structure that easily reacts with a methylolated phenol compound, they are easily cured by heat, and as a result, the hardness and the like of the resulting conductive layer are further improved.

  The conductive layer may further contain a solvent. As this solvent, water, an organic solvent, or a mixed solvent of water and an organic solvent is preferable. These solvents are excellent in solubility of methylolated phenol compounds and the like, and can further improve the uniformity of the conductive layer. Accordingly, the hardness of the conductive layer is further improved.

  The conductive layer may further contain a crosslinking agent. As the crosslinking agent, a compound having a group capable of reacting with active hydrogen is preferable. By containing such a crosslinking agent, sufficient hardness of the conductive layer can be obtained, so that a conductive film that can exhibit higher conductivity can be provided. Moreover, when forming a conductive layer on the surface etc. of a base film, adhesiveness with a base film can be improved more.

  The conductive layer may further contain a binder resin. By containing this binder resin, the hardness of the conductive layer and the adhesion to the substrate and the like are improved, so that the conductivity of the conductive film is further improved.

  The light transmittance of the conductive film at a wavelength of 550 nm is preferably 70% or more, and the surface resistance value measured in accordance with JIS-K7194 (1994) is preferably 1000Ω / □ or less. Such a conductive film can be suitably used for transparent electrodes, electromagnetic wave shielding materials, and the like in touch panels, solar cells, electronic paper, and the like.

  Here, the “methylolated phenol compound” includes a phenol compound having a methylol group and a compound in which the hydrogen atom of —OH in the methylol group is substituted with alkyl.

  The conductive film of the present invention is excellent in conductivity, transparency, coating film hardness, light resistance and wet heat resistance. Moreover, according to this invention, the electroconductive film excellent in electroconductivity and coating-film hardness can be formed at low cost. Therefore, the said electroconductive film can be used suitably for the transparent electrode, electromagnetic wave shielding material, etc. in a touch panel, a solar cell, electronic paper, a flexible light control material, etc., for example.

  Hereinafter, each component and characteristic of the conductive film of the present invention will be described.

[Conductive film]
The conductive film is formed by laminating a conductive layer described later on at least one surface of a substrate film described later. If the said electroconductive film is an aspect containing a base film and an electroconductive layer, it will not specifically limit about another layer.

[Conductive layer]
The conductive layer contains a conductive polymer compound (A) and a methylolated phenol compound (B) represented by the above formula (1). The conductive layer preferably further contains a dopant, a polyhydric phenol compound (C) represented by the above formula (7), a solvent (D), a crosslinking agent, and a binder resin. Moreover, unless the meaning of this invention is impaired, the other component may be contained. Hereinafter, each component will be described.

<Conductive polymer compound (A)>
The conductive polymer compound (A) is composed of a conjugated polymer having a conjugated double bond in the molecular chain.

(Conjugated polymer)
Examples of the conjugated polymer include polyacetylene, polydiacetylene, polyparaphenylene, polyfluorene, polyazulene, polyparaphenylene sulfide, polypyrrole, polythiophene, polyisothianaphthene, polyaniline, polyparaphenylene vinylene, poly (2,5-thieni). Lembinylene), double-chain conjugated polymers (such as polyacene and polyperinaphthalene), metal phthalocyanine-based polymers, other conjugated polymers (such as polyparaxylylene), and copolymers thereof.

  Although the conjugated polymer can be used without being substituted, it is preferable to introduce a functional group into the conjugated polymer in order to further improve conductivity and dispersibility or solubility in the binder resin. Examples of the functional group include an alkyl group, a carboxy group, a sulfo group, an alkoxyl group, a hydroxyl group, and a cyano group.

  Examples of the conjugated polymer into which the functional group is introduced include poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3- (Hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene) ), Poly (3-chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4- Dibutylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3-e Xylthiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly ( 3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3 , 4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxy) Thiophene), poly (3,4-didecyloxythiophene), poly (3,4-di Decyloxythiophene), poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butenedioxythiophene), poly (3-methyl-4-methoxy) Thiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly ( 3-methyl-4-carboxybutylthiophene), poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly (3-butyl Pyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly Li (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethyl) Pyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly ( 3-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), poly (3-methyl-4-hexyloxypyrrole), poly (2-methylaniline), poly (3-isobutylaniline), sulfone Polyaniline and the like.

  The conjugated polymer is preferably polythiophene, poly (3,4-ethylenedioxythiophene), polypyrrole, polyaniline or sulfonated polyaniline from the viewpoint of conductivity and reactivity, and poly (3,4-ethylenedioxy). Thiophene) and polypyrrole are more preferable, and poly (3,4-ethylenedioxythiophene) is particularly preferable. By using poly (3,4-ethylenedioxythiophene) or polypyrrole as the conjugated polymer, the conductivity of the conductive film is further improved and the heat resistance is also improved.

  As an upper limit of content with respect to 100 mass parts of solvent used in order to form the conductive layer of the conductive polymer compound (A) in the said conductive layer, 20 mass parts is preferable and 10 mass parts is more preferable. On the other hand, as a minimum of the above-mentioned content, 0.001 mass part is preferred and 0.005 mass part is more preferred. When the said content exceeds the said upper limit, there exists a possibility that the viscosity of the coating composition for forming a conductive layer may become high, and handling may become difficult. On the contrary, when the content is less than the lower limit, the conductivity of the conductive layer obtained may be reduced.

<Methylolated phenol compound (B)>
The methylolated phenol compound (B) is a compound represented by the following formula (1).

In the above formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group, an alkoxy group, a cycloalkyl group, an allyl group, or a phenyl group. R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group. X ¹ is an amide group, an ether group, a carbonyl group, a xylenyl group, a sulfide group, a sulfonyl group, a disulfide group, a cycloalkylene group, a phenylene group, or a group represented by the following formula (2). a, b and d are each independently 1 or 2; c is an integer of 0 or more and 2 or less. k is an integer of 0 or more and 2 or less. However, c and k are not 0 at the same time. j is 0 or 1. A, b, c, d and k satisfy the following formulas (I) and (II). When there are a plurality of R ³ , R ⁴ , R ⁵ , R ⁶ and X ¹ , a plurality of R ³ may be the same or different, a plurality of R ⁴ may be the same or different, and a plurality of R ⁵ May be the same or different, the plurality of R ⁶ may be the same or different, and the plurality of X ¹ may be the same or different.
2 ≦ a + c + k ≦ 4 (I)
2 ≦ b + d ≦ 3 (II)

In the formula (2), R ⁷ is a hydrogen atom, an alkyl group, fluoroalkyl group, a cycloalkyl group or a phenyl group. Y ¹ is a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, a phenyl group, an adamantyl group, or a group represented by the following formula (3). However, Y ¹ and R ⁷ may be bonded to each other to form a cycloalkane structure or a fluorene structure.

In the above formula (3), R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group, a cycloalkyl group, an allyl group, or a phenyl group. R ¹⁰ is a hydrogen atom, an alkyl group, a cycloalkyl group, a phenyl group or a benzyl group. R ¹¹ is a hydrogen atom or an alkyl group. e and f are each independently an integer of 0 or more and 2 or less and satisfy the following formula (III). When e is 2, the plurality of R ¹⁰ may be the same or different. When f is 2, the plurality of R ¹¹ may be the same or different.
0 ≦ e + f ≦ 3 (III)

Examples of the halogen atom represented by R ^{1 to} R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group represented by R ^{1 to} R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The C1-C6 alkyl group of these is mentioned.

Examples of the alkoxy group represented by R ^{1 to} R ⁴ include methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert- C1-C4 alkoxy groups, such as a butoxy group, are mentioned.

Examples of the cycloalkyl group represented by R ^{1 to} R ⁴ include a cyclohexyl group.

As R < ¹ > -R < ⁴ >, a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy group are preferable.

Examples of the alkyl group represented by R ⁵ and R ⁶ include the same groups as those exemplified for R ^{1 to} R ⁴ .

Examples of the cycloalkylene group represented by X ¹ include a cyclohexylene group.

X ¹ is preferably an ether group, a carbonyl group, a sulfide group, a sulfonyl group, or a group represented by the above formula (2).

  Preferably, k is 0 and c is 2, or k is 1 and c is 1 or 2.

Examples of the alkyl group, alkoxy group, and cycloalkyl group represented by R ⁷ include the same groups as those exemplified for R ^{1 to} R ⁴ .

Examples of the fluoroalkyl group represented by R ⁷ include a trifluoromethyl group.

R ⁷ is preferably a hydrogen atom, an alkyl group, or a fluoroalkyl group.

Examples of the alkyl group and cycloalkyl group represented by Y ¹ include the same groups as those exemplified above for R ^{1 to} R ⁴ .

Examples of the fluoroalkyl group represented by Y ¹ include the same groups as those exemplified for R ⁷ above.

Y ¹ is preferably a hydrogen atom, an alkyl group, a fluoroalkyl group, or a group represented by the above formula (3).

Examples of the halogen atom, alkyl group and cycloalkyl group represented by R ⁸ and R ⁹ include the same groups as those exemplified for R ^{1 to} R ⁴ above.

Examples of the alkyl group and cycloalkyl group represented by R ¹⁰ include the same groups as those exemplified in ^{1 to} R ⁴ above.

Examples of the alkyl group represented by R ¹¹ include the same groups as those exemplified in the above ^{1 to} R ⁴ .

As R < ⁸ > -R < ¹¹ >, a hydrogen atom and an alkyl group are preferable.

  Examples of the methylolated phenol compound (B) represented by the above formula (1) include a mononuclear methylolated phenol compound having one aromatic ring in the main skeleton and a dinuclear methylol having two aromatic rings in the main skeleton. And a trinuclear methylolated phenol compound having three aromatic rings in the main skeleton.

  Examples of the mononuclear methylolated phenol compound include 2,6-dihydroxymethyl-4-methylphenol, 4,6-dihydroxymethyl-2-methylphenol, 2,6-dihydroxymethyl-3,4-dimethylphenol, 4 , 6-Dihydroxymethyl-2,3-dimethylphenol, 4-ethyl-2,6-dihydroxymethylphenol, 2-ethyl-4,6-dihydroxymethylphenol, 4-tert-butyl-2,6-dihydroxymethyl Phenol, 2-tert-butyl-4,6-dihydroxymethylphenol, 4-cyclohexyl-2,6-dihydroxymethylphenol, 2-cyclohexyl-4,6-dihydroxymethylphenol, 2,6-dihydroxymethyl-4- Phenylphenol, 4,6-dihydroxy Methyl-2-phenylphenol, 2,6-dihydroxymethyl-4-methoxyphenol, 4,6-dihydroxymethyl-2-methoxyphenol, 4,6-dihydroxymethyl-2-methylresorcinol, 4-hydroxy-2,6 -Dihydroxymethylbenzoic acid, 4-hydroxymethyl-2,5-dimethylphenol, 4-hydroxymethyl-2,6-dimethylphenol, 4-fluoro-2,6-dihydroxymethylphenol, 2,6-dimethoxymethyl-4 -Methylphenol, 4,6-dimethoxymethyl-2-methylphenol, 4-ethyl-2,6-dimethoxymethylphenol, 2-ethyl-4,6-dimethoxymethylphenol and the like.

  Examples of the dinuclear methylolated phenol compound include 2,2 ′, 6,6′-tetrahydroxymethyl-4,4′-biphenol, bis (4-hydroxy-3,5-dihydroxymethylphenyl) methane, bis ( 2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, bis (4-hydroxy-3-hydroxymethyl-2,5-dimethyl) Phenyl) methane, bis (2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) methane, bis (3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) methane, bis (4-hydroxy-3- Hydroxymethyl-5-phenylphenyl) methane, bis (3-carboxy-6- Droxy-5-hydroxymethylphenyl) methane, bis (3-allyl-4-hydroxy-5-hydroxymethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dihydroxymethylphenyl) ethane, 1, 1-bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) ethane, 1,1-bis (2, 4-dihydroxy-5-hydroxymethyl-3-methylphenyl) ethane, 1,1-bis (3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) ethane, 1,1-bis (4-hydroxy-3-) Hydroxymethyl-5-phenylphenyl) ethane, 1,1-bis (3-chloro-4,6-dihydroxy-5- Loxymethylphenyl) ethane, 1,1-bis (4-hydroxy-3,5-dihydroxymethylphenyl) butane, 1,1-bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) butane, 1, 1-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) butane, 1,1-bis (2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) butane, 1,1-bis ( 3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) butane, 1,1-bis (4-hydroxy-3-hydroxymethyl-5-phenylphenyl) butane, 1,1-bis (3-chloro-4, 6-dihydroxy-5-hydroxymethylphenyl) butane, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenol) Nyl) propane, 2,2-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) propane, 2,2-bis (2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) propane, 2,2-bis (4-hydroxy-3-hydroxymethyl-5-phenylphenyl) propane, 2,2-bis ( 4-hydroxy-3,5-dihydroxymethylphenyl) -1,1,1,3,3,3-hexafluoropropane, [bis (4-hydroxy-3,5-dihydroxymethylphenyl) methyl] cyclohexane, [bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] cyclohexane, [bis (4-hydride) Xyl-3-hydroxymethyl-5-methylphenyl) methyl] cyclohexane, [bis (2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) methyl] cyclohexane, [bis (3-cyclohexyl-4-hydroxy-) 5-hydroxymethylphenyl) methyl] cyclohexane, [bis (4-hydroxy-3-hydroxymethyl-5-phenylphenyl) methyl] cyclohexane, [bis (3-chloro-4,6-dihydroxy-5-hydroxymethylphenyl) Methyl] cyclohexane, 1,1-bis (4-hydroxy-3,5-dihydroxymethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) cyclohexane, bis (4- Hydroxy-3,5-dihydroxy Methylphenyl) ketone, bis (4-hydroxy-3,5-dihydroxymethylphenyl) sulfone, (2-hydroxy-3,5-dihydroxymethylphenyl) (4-hydroxy-3,5-dihydroxymethylphenyl) sulfone, bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) sulfone, bis (4-hydroxy-3-hydroxymethyl-2,5-dimethylphenyl) sulfone, bis (3-allyl-4-hydroxy-5-hydroxy) Methylphenyl) sulfone, bis (3-chloro-4-hydroxy-5-hydroxymethylphenyl) sulfone, bis (4-hydroxy-3-hydroxymethyl-5-sulfophenyl) sulfone, bis (4-hydroxy-3,5 -Dihydroxymethylphenyl) sulfide, bis (4- Hydroxy-3-hydroxymethyl-5-methylphenyl) sulfide, bis (3-carboxy-4-hydroxy-5-hydroxymethylphenyl) sulfide, N- (4-hydroxy-3,5-dihydroxymethylphenyl) -4- Hydroxy-3,5-dihydroxymethylbenzamide, bis (4-hydroxy-3,5-dihydroxymethylphenyl) disulfide, bis (4-hydroxy-3,5-dihydroxymethylphenyl) ether, bis (4-hydroxy-3, 5-dimethoxymethylphenyl) methane, bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethoxymethylphenyl) ethane, 1,1- Bis (4-hydroxy-3-methoxymethyl-5-methyl) Phenyl) ethane, 1,1-bis (4-hydroxy-3,5-dimethoxymethylphenyl) butane, 1,1-bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) butane, 2,2- Bis (4-hydroxy-3,5-dimethoxymethylphenyl) propane, 2,2-bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) propane, [bis (4-hydroxy-3,5-dimethoxy Methylphenyl) methyl] cyclohexane, [bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) methyl] cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethoxymethylphenyl) cyclohexane, 1, 1-bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) cyclohexane, bis ( - hydroxy-3,5-dimethoxy-methylphenyl) sulfone, bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) sulfone, and the like.

  Examples of the trinuclear methylolated phenol compound include [bis (4-hydroxy-3,5-dihydroxymethylphenyl) methyl] benzene, [bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] benzene, [Bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] benzene, [Bis (2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) methyl] benzene, [Bis (3-cyclohexyl) -4-hydroxy-5-hydroxymethylphenyl) methyl] benzene, [bis (4-hydroxy-3-hydroxymethyl-5-phenylphenyl) methyl] benzene, [bis (3-chloro-4,6-dihydroxy-5) -Hydroxymethylphenyl) methyl] benzene, 1,1-bis (4 Hydroxy-3,5-dihydroxymethylphenyl) -1-phenylethane, 1,1-bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) -1-phenylethane, 1,1-bis (4- Hydroxy-3-hydroxymethyl-5-methylphenyl) -1-phenylethane, 1,1-bis (2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) -1-phenylethane, 1,1- Bis (3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-hydroxymethyl-5-phenylphenyl) -1-phenylethane, 1, 1-bis (3-chloro-4,6-dihydroxy-5-hydroxymethylphenyl) -1-phenylethane, 9,9- (4-hydroxy-3,5-dihydroxymethylphenyl) -9H-fluorene, 9,9-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) -9H-fluorene, 9,9-bis ( 2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) -9H-fluorene, 9,9-bis (3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) -9H-fluorene, 9,9- Bis (4-hydroxy-3-hydroxymethyl-5-phenylphenyl) -9H-fluorene, 9,9-bis (3-allyl-4-hydroxy-5-hydroxymethylphenyl) -9H-fluorene, 1,1- Bis (4-hydroxy-3,5-dihydroxymethylphenyl) -1-adamantylethane, tris (4-hydroxy -3,5-dihydroxymethylphenyl) methane, 4- [bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] -2,6-dihydroxymethylphenol, 4- [bis (4-hydroxy- 3-hydroxymethyl-5-methylphenyl) methyl] -2,6-dihydroxymethylphenol, 4- [bis (2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) methyl] -2,6-dihydroxy Methylphenol, 4- [bis (3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) methyl] -2,6-dihydroxymethylphenol, 4- [bis (4-hydroxy-3-hydroxymethyl-5-phenyl) Phenyl) methyl] -2,6-dihydroxymethylphenol, 4- [bis (3 Chloro-4,6-dihydroxy-5-hydroxymethylphenyl) methyl] -2,6-dihydroxymethylphenol, 1,1,1-tris (4-hydroxy-3,5-dihydroxymethylphenyl) ethane, 1,1 -Bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) -1- (4-hydroxy-3,5-dihydroxymethylphenyl) ethane, 1,1-bis (4-hydroxy-3-hydroxymethyl-) 5-methylphenyl) -1- (4-hydroxy-3,5-dihydroxymethylphenyl) ethane, 1,1-bis (2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) -1- (4 -Hydroxy-3,5-dihydroxymethylphenyl) ethane, 1,1-bis (3-cyclohexyl-4-hydroxy-) -Hydroxymethylphenyl) -1- (4-hydroxy-3,5-dihydroxymethylphenyl) ethane, 1,1-bis (4-hydroxy-3-hydroxymethyl-5-phenylphenyl) -1- (4-hydroxy -3,5-dihydroxymethylphenyl) ethane, 1,1-bis (3-chloro-4,6-dihydroxy-5-hydroxymethylphenyl) -1- (4-hydroxy-3,5-dihydroxymethylphenyl) ethane 2,6-bis [(4-hydroxy-3,5-dihydroxymethylphenyl) methyl] -4-methylphenol, 2,6-bis [(2-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl ] -4-methylphenol, 2,6-bis [(4-hydroxy-3-hydroxymethyl-5-methylphenyl) me Til] -4-methylphenol, 2,6-bis [(2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) methyl] -4-methylphenol, 2,6-bis [(3-cyclohexyl- 4-hydroxy-5-hydroxymethylphenyl) methyl] -4-methylphenol, 2,6-bis [(4-hydroxy-3-hydroxymethyl-5-phenylphenyl) methyl] -4-methylphenol, 2,6 -Bis [(4-hydroxy-3-hydroxymethyl-2,5-dimethylphenyl) methyl] -4-methylphenol, 4,6-bis [(4-hydroxy-3,5-dihydroxymethylphenyl) methyl]- 2-methylphenol, 4,6-bis [(2-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] -2-methyl Ruphenol, 4,6-bis [(4-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] -2-methylphenol, 4,6-bis [(2,4-dihydroxy-5-hydroxymethyl- 3-methylphenyl) methyl] -2-methylphenol, 4,6-bis [(3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) methyl] -2-methylphenol, 4,6-bis [(4 -Hydroxy-3-hydroxymethyl-5-phenylphenyl) methyl] -2-methylphenol, 4,6-bis [(4-hydroxy-3-hydroxymethyl-2,5-dimethylphenyl) methyl] -2-methyl Phenol, 4,6-bis [(3-allyl-4-hydroxy-5-hydroxymethylphenyl) methyl] -2-methylphenol 2,6-bis [(4-hydroxy-3,5-dihydroxymethylphenyl) methyl] -4-methoxyphenol, 2,6-bis [(2-hydroxy-3-hydroxymethyl-5-methylphenyl) ) Methyl] -4-methoxyphenol, 2,6-bis [(4-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] -4-methoxyphenol, 2,6-bis [(2,4-dihydroxy) -5-hydroxymethyl-3-methylphenyl) methyl] -4-methoxyphenol, 2,6-bis [(3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) methyl] -4-methoxyphenol, 2, 6-bis [(4-hydroxy-3-hydroxymethyl-5-phenylphenyl) methyl] -4-methoxyphenol, 2 , 6-Bis [(4-hydroxy-3-hydroxymethyl-2,5-dimethylphenyl) methyl] -4-methoxyphenol, 4,6-bis [(4-hydroxy-3,5-dihydroxymethylphenyl) methyl ] -2-methoxyphenol, 4,6-bis [(2-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] -2-methoxyphenol, 4,6-bis [(4-hydroxy-3-hydroxy) Methyl-5-methylphenyl) methyl] -2-methoxyphenol, 4,6-bis [(2,4-dihydroxy-5-hydroxymethyl-3-methylphenyl) methyl] -2-methoxyphenol, 4,6- Bis [(3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) methyl] -2-methoxyphenol, 4,6 Bis [(4-hydroxy-3-hydroxymethyl-5-phenylphenyl) methyl] -2-methoxyphenol, 4,6-bis [(4-hydroxy-3-hydroxymethyl-2,5-dimethylphenyl) methyl] 2-methoxyphenol, 1,4-bis [(4-hydroxy-3,5-dihydroxymethylphenyl) methyl] benzene, 1,4-bis [(2-hydroxy-3-hydroxymethyl-5-methylphenyl) Methyl] benzene, 1,4-bis [(4-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] benzene, 1,4-bis [(2,4-dihydroxy-5-hydroxymethyl-3-methyl) Phenyl) methyl] benzene, 1,4-bis [(3-cyclohexyl-4-hydroxy-5-hydroxymethylphenyl) Methyl] benzene, 1,4-bis [(4-hydroxy-3-hydroxymethyl-5-phenylphenyl) methyl] benzene, 1,4-bis [(4-hydroxy-3-hydroxymethyl-2,5-dimethyl) Phenyl) methyl] benzene, [bis (4-hydroxy-3,5-dimethoxymethylphenyl) methyl] benzene, [bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) methyl] benzene, 1,1- Bis (4-hydroxy-3,5-dimethoxymethylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) -1-phenylethane, 9,9- Bis (4-hydroxy-3,5-dimethoxymethylphenyl) -9H-fluorene, 9,9-bis (4-hydroxy-3-methyl) Toximethyl-5-methylphenyl) -9H-fluorene, tris (4-hydroxy-3,5-dimethoxymethylphenyl) methane, 4- [bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) methyl]- 2,6-dimethoxymethylphenol, 1,1,1-tris (4-hydroxy-3,5-dimethoxymethylphenyl) ethane, 1,1-bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) -1- (4-hydroxy-3,5-dimethoxymethylphenyl) ethane, 2,6-bis [(4-hydroxy-3,5-dimethoxymethylphenyl) methyl] -4-methylphenol, 2,6- Bis [(4-hydroxy-3-methoxymethyl-5-methylphenyl) methyl] -4-methylphenol, 4,6-bis [(4 Hydroxy-3,5-dimethoxymethylphenyl) methyl] -2-methylphenol, 4,6-bis [(4-hydroxy-3-methoxymethyl-5-methylphenyl) methyl] -2-methylphenol, 2,6 -Bis [(4-hydroxy-3,5-dimethoxymethylphenyl) methyl] -4-methoxyphenol, 2,6-bis [(4-hydroxy-3-methoxymethyl-5-methylphenyl) methyl] -4- Methoxyphenol, 4,6-bis [(4-hydroxy-3,5-dimethoxymethylphenyl) methyl] -2-methoxyphenol, 4,6-bis [(4-hydroxy-3-methoxymethyl-5-methylphenyl) ) Methyl] -2-methoxyphenol, 1,4-bis [(4-hydroxy-3,5-dimethymethylphenyl) methyl Benzene, 1,4-bis [(4-hydroxy-3-methoxymethyl-5-methylphenyl) methyl] benzene, and the like.

  As the methylolated phenol compound (B), 2,6-dihydroxymethyl-4-methylphenol, 4 from the viewpoint of reducing the coloring of the conductive layer and improving the solubility of the methylolated phenol compound (B) in the solvent. , 6-dihydroxymethyl-2-methylphenol, 4-ethyl-2,6-dihydroxymethylphenol, 2-ethyl-4,6-dihydroxymethylphenol, 4-fluoro-2,6-dihydroxymethylphenol, 2,6 -Dimethoxymethyl-4-methylphenol, 4,6-dimethoxymethyl-2-methylphenol, bis (4-hydroxy-3,5-dihydroxymethylphenyl) methane, bis (4-hydroxy-3-hydroxymethyl-5- Methylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dihy Loxymethylphenyl) ethane, 1,1-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) ethane, 1,1-bis (4-hydroxy-3,5-dihydroxymethylphenyl) butane, 1, 1-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) butane, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane, 2,2-bis (4-hydroxy- 3-hydroxymethyl-5-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) -1,1,1,3,3,3-hexafluoropropane, [bis ( 4-hydroxy-3,5-dihydroxymethylphenyl) methyl] cyclohexane, [bis (4-hydroxy-3-hydroxymethyl) -5-methylphenyl) methyl] cyclohexane, 1,1-bis (4-hydroxy-3,5-dihydroxymethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) Cyclohexane, bis (4-hydroxy-3,5-dihydroxymethylphenyl) sulfone, bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) sulfone, bis (4-hydroxy-3,5-dimethoxymethylphenyl) Methane, bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethoxymethylphenyl) ethane, 1,1-bis (4-hydroxy-) 3-methoxymethyl-5-methylphenyl) ethane, 2,2-bis (4-hydro Xy-3,5-dimethoxymethylphenyl) propane, 2,2-bis (4-hydroxy-3-methoxymethyl-5-methylphenyl) propane, [bis (4-hydroxy-3,5-dihydroxymethylphenyl) methyl Benzene, [bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] benzene, 1,1-bis (4-hydroxy-3,5-dihydroxymethylphenyl) -1-phenylethane, and 1 1,2-bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) -1-phenylethane is preferred.

  Moreover, as a methylolated phenol compound (B), a mononuclear methylolated phenol compound and a binuclear methylolated phenol compound are preferable, and a mononuclear methylolated phenol compound is more preferable.

  As mononuclear methylolated phenol compounds, 2,6-dihydroxymethyl-4-methylphenol represented by the following formula (4) and 4-fluoro-2,6-dihydroxymethyl represented by the following formula (5) Phenol is preferred. As the binuclear methylolated phenol compound, 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane represented by the following formula (6) is preferable. In addition to the above properties, these methylolated phenol compounds (B) have little change in hue in air and in solution, and have high stability.

  As an upper limit of content with respect to 1 mol of conductive polymer compounds (A) of the methylolation phenol compound (B) in the said conductive layer, 20 mol is preferable and 10 mol is more preferable. On the other hand, the lower limit of the content is preferably 0.001 mol, and more preferably 0.01 mol. When the said content exceeds the said upper limit, a methylolation phenol compound (B) may precipitate on the surface of an electroconductive layer, and there exists a possibility that transparency and electroconductivity may fall. On the other hand, when the content is less than the lower limit, the hardness and conductivity of the obtained conductive layer may be reduced.

(Method for producing methylolated phenol compound (B))
The methylolated phenol compound (B) can be produced by a reaction between phenols and formaldehyde. Such a reaction is known and is performed in the presence of a base catalyst. In addition, phenols here include a part of polyphenol compound (C) mentioned later.

  Examples of the method for producing the methylolated phenol compound (B) include the following methods. First, phenols and excess formaldehyde (for example, 1 mol to 20 mol of formaldehyde with respect to 1 mol of phenol) are dissolved in a solvent and reacted in the presence of a base catalyst. The end point of the reaction is determined by tracking the residual amount of phenols or formaldehyde by a known method such as gas chromatography, thin layer chromatography, liquid chromatography, gel filtration chromatography, IR analysis, and the peak area indicating this residual amount is The time when it no longer decreases.

  Examples of the phenols include phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, and 2-methoxyphenol. 4-methoxyphenol, 2-ethylphenol, 4-ethylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2-cyclohexylphenol, 4-cyclohexylphenol, 2-phenylphenol, 4-phenylphenol, 4- Fluorophenol, hydroquinone, catechol, 4-methylcatechol, 4-tert-butylcatechol, resorcinol, 2-methylresorcinol, 5-methylresorcinol, 4-chlororesorcinol 4-hydroxybenzoic acid, 4,4′-biphenol, bis (4-hydroxyphenyl) methane, bis (2-hydroxy-5-methylphenyl) methane, bis (4-hydroxy-3-methylphenyl) methane, bis ( 4-hydroxy-2,5-dimethylphenyl) methane, bis (2,4-dihydroxy-5-3-methylphenyl) methane, bis (3-cyclohexyl-4-hydroxyphenyl) methane, bis (4-hydroxy-3) -Phenylphenyl) methane, bis (3-carboxy-6-hydroxyphenyl) methane, bis (3-allyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (2-hydroxy-5-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenol) ) Ethane, 1,1-bis (2,4-dihydroxy-3-methylphenyl) ethane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-) 3-phenylphenyl) ethane, 1,1-bis (3-chloro-4,6-dihydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis (2-hydroxy-5) -Methylphenyl) butane, 1,1-bis (4-hydroxy-3-methylphenyl) butane, 1,1-bis (2,4-dihydroxy-3-methylphenyl) butane, 1,1-bis (3- Cyclohexyl-4-hydroxyphenyl) butane, 1,1-bis (4-hydroxy-3-phenylphenyl) butane, 1,1-bis (3-chloro-4,6-dihydroxyphenyl) Enyl) butane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (2,4-dihydroxy-3-methylphenyl) ) Propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -1 , 1,1,3,3,3-hexafluoropropane, [bis (4-hydroxyphenyl) methyl] cyclohexane, [bis (2-hydroxy-5-methylphenyl) methyl] cyclohexane, [bis (4-hydroxy- 3-methylphenyl) methyl] cyclohexane, [bis (2,4-dihydroxy-3-methylphenyl) methyl] cyclohexane Sun, [bis (3-cyclohexyl-4-hydroxyphenyl) methyl] cyclohexane, [bis (4-hydroxy-3-phenylphenyl) methyl] cyclohexane, [bis (3-chloro-4,6-dihydroxyphenyl) methyl] Cyclohexane, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfone, (2-hydroxyphenyl) (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4 -Hydroxy-2,5-dimethylphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-sulfophenyl) sulfone Bis (4-hydroxyphenyl) Fido, bis (4-hydroxy-3-methylphenyl) sulfide, bis (3-carboxy-4-hydroxyphenyl) sulfide, N- (4-hydroxyphenyl) -4-hydroxybenzamide, bis (4-hydroxyphenyl) disulfide , Bis (4-hydroxyphenyl) ether, [bis (4-hydroxyphenyl) methyl] benzene, [bis (2-hydroxy-5-methylphenyl) methyl] benzene, [bis (4-hydroxy-3-methylphenyl) Methyl] benzene, [bis (2,4-dihydroxy-3-methylphenyl) methyl] benzene, [bis (3-cyclohexyl-4-hydroxyphenyl) methyl] benzene, [bis (4-hydroxy-3-phenylphenyl) Methyl] benzene, [bis (3-chloro-4,6 -Dihydroxyphenyl) methyl] benzene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-phenyl) -1-phenylethane, 1,1-bis (2-hydroxy-5-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1, 1-bis (2,4-dihydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4- Hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis (3-chloro-4,6-dihydroxyphenyl) -1-phenyl Ruethane, 9,9-bis (4-hydroxyphenyl) -9H-fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) -9H-fluorene, 9,9-bis (2,4-dihydroxy- 3-methylphenyl) -9H-fluorene, 9,9-bis (3-cyclohexyl-4-hydroxyphenyl) -9H-fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) -9H-fluorene, 9,9-bis (3-allyl-4-hydroxyphenyl) -9H-fluorene, tris (4-hydroxyphenyl) methane, 4- [bis (2-hydroxy-5-methylphenyl) methyl] phenol, 4- [ Bis (4-hydroxy-3-methylphenyl) methyl] phenol, 4- [bis (2,4-dihydroxy-3-methylphenyl) Til] phenol, 4- [bis (3-cyclohexyl-4-hydroxyphenyl) methyl] phenol, 4- [bis (4-hydroxy-3-phenylphenyl) methyl] phenol, 4- [bis (3-chloro-4) , 6-dihydroxyphenyl) methyl] phenol, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1-bis (2-hydroxy-5-methylphenyl) -1- (4-hydroxyphenyl) ethane 1,1-bis (4-hydroxy-3-methylphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (2,4-dihydroxy-3-methylphenyl) -1- (4- Hydroxyphenyl) ethane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) ethane, , 1-bis (4-hydroxy-3-phenylphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (3-chloro-4,6-dihydroxyphenyl) -1- (4-hydroxyphenyl) ) Ethane, 2,6-bis [(4-hydroxyphenyl) methyl] -4-methylphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 2,6 -Bis [(4-hydroxy-3-methylphenyl) methyl] -4-methylphenol, 2,6-bis [(2,4-dihydroxy-3-methylphenyl) methyl] -4-methylphenol, 2,6 -Bis [(3-cyclohexyl-4-hydroxyphenyl) methyl] -4-methylphenol, 2,6-bis [(4-hydroxy-3-phenylphenyl) methyl ] -4-methylphenol, 2,6-bis [(4-hydroxy-2,5-dimethylphenyl) methyl] -4-methylphenol, 4,6-bis [(4-hydroxyphenyl) methyl] -2- Methylphenol, 4,6-bis [(2-hydroxy-5-methylphenyl) methyl] -2-methylphenol, 4,6-bis [(4-hydroxy-3-methylphenyl) methyl] -2-methylphenol 4,6-bis [(2,4-dihydroxy-3-methylphenyl) methyl] -2-methylphenol, 4,6-bis [(3-cyclohexyl-4-hydroxyphenyl) methyl] -2-methylphenol 4,6-bis [(4-hydroxy-3-phenylphenyl) methyl] -2-methylphenol, 4,6-bis [(4-hydroxy-2,5- Methylphenyl) methyl] -2-methylphenol, 4,6-bis [(3-allyl-4-hydroxyphenyl) methyl] -2-methylphenol, 2,6-bis [(4-hydroxymethylphenyl) methyl] -4-methoxyphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methoxyphenol, 2,6-bis [(4-hydroxy-3-methylphenyl) methyl] -4 -Methoxyphenol, 2,6-bis [(2,4-dihydroxy-3-methylphenyl) methyl] -4-methoxyphenol, 2,6-bis [(3-cyclohexyl-4-hydroxyphenyl) methyl] -4 -Methoxyphenol, 2,6-bis [(4-hydroxy-3-phenylphenyl) methyl] -4-methoxyphenol, 2,6- Bis [(4-hydroxy-2,5-dimethylphenyl) methyl] -4-methoxyphenol, 4,6-bis [(4-hydroxyphenyl) methyl] -2-methoxyphenol, 4,6-bis [(2 -Hydroxy-5-methylphenyl) methyl] -2-methoxyphenol, 4,6-bis [(4-hydroxy-3-methylphenyl) methyl] -2-methoxyphenol, 4,6-bis [(2,4 -Dihydroxy-3-methylphenyl) methyl] -2-methoxyphenol, 4,6-bis [(3-cyclohexyl-4-hydroxyphenyl) methyl] -2-methoxyphenol, 4,6-bis [(4-hydroxy -3-phenylphenyl) methyl] -2-methoxyphenol, 4,6-bis [(4-hydroxy-2,5-dimethylphenyl) methyl ] -2-methoxyphenol, 1,4-bis [(4-hydroxyphenyl) methyl] benzene, 1,4-bis [(2-hydroxy-5-methylphenyl) methyl] benzene, 1,4-bis [( 4-hydroxy-3-methylphenyl) methyl] benzene, 1,4-bis [(2,4-dihydroxy-3-methylphenyl) methyl] benzene, 1,4-bis [(3-cyclohexyl-4-hydroxyphenyl) ) Methyl] benzene, 1,4-bis [(4-hydroxy-3-phenylphenyl) methyl] benzene, 1,4-bis [(4-hydroxy-2,5-dimethylphenyl) methyl] benzene and the like. .

  Among them, from the viewpoint of obtaining a methylolated phenol compound (B) having high reactivity with formaldehyde and high solubility in a solvent, orthocresol, paracresol, 2-ethylphenol, 4-ethylphenol, 2-methoxyphenol, 4-methoxyphenol, 4-fluorophenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxy-3-methylphenyl) butane, 2,2-bis (4- Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, Bis (4-hydroxyphenyl) methyl] cyclohexane, [bis (4-hydroxy-3-methylphenyl) methyl] cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-) 3-phenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxyphenyl) ether, [bis (4-hydroxyphenyl) methyl] benzene, [ Bis (4-hydroxy-3-methylphenyl) methyl] benzene, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, and 1,1-bis (4-hydroxy-3-methylphenyl) -1 -Phenylethane is preferred. The above phenols may be used alone or in combination of two or more.

  Examples of the formaldehyde include formalin, paraformaldehyde, 1,3,5-trioxane and the like.

  Examples of the solvent include water, alcohol solvents, ether solvents and the like. Examples of the base catalyst include sodium hydroxide, potassium hydroxide, triethylamine and the like.

  As said reaction temperature, 20 to 100 degreeC is preferable, for example. As said reaction time, 30 minutes or more and 48 hours or less are preferable, for example.

  After completion of the reaction, the reaction solution is cooled to about room temperature, and the catalyst is neutralized using a neutralizing agent. Thereafter, an appropriate amount of a poor solvent such as water or an organic solvent (toluene, xylene, etc.) is added to precipitate the reaction product. A methylolated phenol compound (B) is obtained by separating the precipitate by filtration, purifying by washing with water, recrystallization, etc., if necessary, and drying.

  Furthermore, in order to improve the storage stability of the methylolated phenol compound (B), the reaction product of phenols and formaldehyde may be methoxylated. Such reactions are well known and are performed in the presence of a large excess of alcohol and acidic catalyst.

  The methoxylation of the reaction product is performed, for example, by the following method. First, a reaction product of phenols and formaldehyde is dissolved in an excessive amount of alcohol (for example, 1 mol to 40 mol of alcohol with respect to 1 mol of the product) and reacted in the presence of an acidic catalyst.

  Examples of the alcohol include methanol and ethanol. Examples of the acid catalyst include sulfuric acid and methanesulfonic acid.

  As said reaction temperature, 20 degreeC or more and 100 degrees C or less are preferable. The reaction time is preferably from 30 minutes to 48 hours.

  After completion of the reaction, the reaction solution is cooled to about room temperature, and the catalyst is neutralized using a neutralizing agent. Thereafter, the reaction solution is purified by distillation, or an appropriate amount of a poor solvent such as water or an organic solvent (toluene, xylene, etc.) is added to precipitate the reaction product. A methylolated phenol compound (B) is obtained by separating the precipitate by filtration, purifying by washing with water, recrystallization, etc., if necessary, and drying.

<Dopant>
The dopant improves or develops the conductivity of the conductive polymer compound (A). Since this dopant can oxidize or reduce the conjugated polymer constituting the conductive polymer compound (A), the dispersibility of the conjugated polymer in the solvent is improved. Since the conductive layer is often formed by coating, drying, or the like, the conductive layer having uniform conductivity can be formed by improving the dispersibility of the conjugated polymer in the solvent.

  The dopant is not particularly limited as long as it can oxidize or reduce a conjugated polymer, and either a donor dopant or an acceptor dopant may be used.

  Examples of the donor dopant include alkali metals (Li, Na, K, etc.), alkaline earth metals (Ca, Mg, etc.), quaternary amine compounds (tetramethylammonium, tetrabutylammonium, etc.) and the like.

  Examples of the acceptor dopant include halogen compounds, Lewis acids, proton acids, transition metal compounds, electrolyte anions, fullerenes, and organic cyano compounds.

Examples of the halogen compound include Cl ₂ , Br ₂ , I ₂ , ICl, IBr, IF, and the like.

Examples of the Lewis acid include PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , BBr ₃ , SO _{3 and the} like.

Examples of the protonic acid include HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, CISO ₃ H, CF ₃ SO ₃ H, organic carboxylic acid, organic sulfonic acid, organic sulfonic acid metal salt, Examples include phenols and amino acids.

Examples of the transition metal compound include FeCl ₃ , FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaCl ₅ , MoF ₅ , MoCl ₅ , WF ₆ , and WCl ₆ .

Examples of the electrolyte anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , inorganic sulfonate anion, and organic sulfonate anion.

  Examples of the fullerene include hydrogenated fullerene, hydroxylated fullerene, carboxylated fullerene, and sulfonated fullerene.

  Examples of the organic cyano compound include tetracyanoethylene, tetracyanoethylene oxide, and tetracyanobenzene.

  As a combination of the conductive polymer compound (A) and the dopant, the conductive polymer compound (A) is polythiophene and a derivative thereof, and the dopant is a sulfone such as an organic sulfonic acid, an organic sulfonic acid metal salt, or an organic sulfonic acid anion. A combination that is an acid compound is preferable, and a combination in which the conductive polymer compound (A) is poly (3,4-ethylenedithiophene) and the dopant is poly (4-styrenesulfonic acid) or poly (vinylsulfonic acid) is more preferable. A combination in which the dopant is poly (4-styrenesulfonic acid) is more preferable. Since the conductive polymer compound (A) and the dopant are in the above combination, the dopant is doped into the conductive polymer compound (A), and a specific composite (PEDOT / PSS) is formed. Since this PEDOT / PSS can be dispersed in water, the conductive layer can be easily formed by coating. Moreover, transparency after coating film formation is also high.

  Moreover, you may add a conductive polymer compound (A) and a dopant to the said coating composition as a compound which doped the dopant to the conductive polymer compound (A). As such a compound, a known compound such as a commercial product can be used. For example, an aqueous dispersion containing 1 to 2% by mass of PEDOT / PSS polymer (for example, product number “483095” manufactured by Aldrich, CLEVIOS (registered trademark) PH1000 manufactured by Heraeus Co., Ltd.), or “R-iCP (registered trademark) manufactured by Rigaku Corporation. ) ICP500 ") and the like.

  Although it does not specifically limit as content of the dopant in the said conductive layer, As an upper limit of content with respect to 100 mass parts of conductive polymer compounds (A), 1,000 mass parts is preferable and 500 mass parts is more preferable. On the other hand, as a minimum of the above-mentioned content, 0.00001 mass part is preferred and 0.001 mass part is more preferred. When the content exceeds the upper limit or when the content is less than the lower limit, the conductivity may be difficult to improve. Here, “with respect to 100 parts by mass of the conductive polymer compound (A)” means “with respect to 100 parts by mass of the solid content of the conductive polymer compound (A)”.

<Polyhydric phenol compound (C)>
The polyhydric phenol compound (C) is a compound represented by the following formula (7).

In said formula (7), R < ¹² > -R < ¹⁵ > is respectively independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group, an alkoxy group, a cycloalkyl group, an allyl group, or a phenyl group. X ² is an amide group, an ether group, a carbonyl group, a xylenyl group, a sulfide group, a sulfonyl group, a disulfide group, a cycloalkylene group, a phenylene group, or a group represented by the following formula (8). g and h are each independently an integer of 1 to 3. n is an integer of 0 or more and 3 or less. m is an integer of 1 or 2. G and n satisfy the following formula (IV). When there are a plurality of R ¹⁴ , R ¹⁵ and X ² , the plurality of R ¹⁴ may be the same or different, the plurality of R ¹⁵ may be the same or different, and the plurality of X ² are the same or different. Also good.
2 ≦ g + n ≦ 4 (IV)

In the formula (8), R ¹⁶ is a hydrogen atom, an alkyl group, fluoroalkyl group, a cycloalkyl group, a phenyl group. Y ² is a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, a phenyl group, an adamantyl group or a group represented by the following formula (9). However, Y ² and R ¹⁶ may be bonded to each other to form a cycloalkane structure or a fluorene structure.

In the above formula (9), R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group, a cycloalkyl group, an allyl group, or a phenyl group. R ¹⁹ is a hydrogen atom, an alkyl group, a cycloalkyl group, a phenyl group or a benzyl group. i is an integer of 0 or more and 3 or less. When i is 2 or more, the plurality of R ¹⁹ may be the same or different.

Examples of the halogen atom represented by R ^{12 to} R ¹⁵ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group represented by R ^{12 to} R ¹⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. And an alkyl group having 1 to 6 carbon atoms.

Examples of the alkoxy group represented by R ^{12 to} R ¹⁵ include methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert- C1-C4 alkoxy groups, such as a butoxy group, are mentioned.

Examples of the cycloalkyl group represented by R ^{12 to} R ¹⁵ include a cyclohexyl group.

As R < ¹² > -R < ¹⁵ >, a hydrogen atom, an alkyl group, and an alkoxy group are preferable.

Examples of the cycloalkylene group represented by X ² include a cyclohexylene group.

X ² is preferably an ether group, a carbonyl group, a sulfide group, a sulfonyl group, or a group represented by the above formula (8).

  g is preferably 1 or 2, and h is preferably 1 or 2. Further, n is preferably 1.

Examples of the alkyl group, alkoxy group and cycloalkyl group represented by R ¹⁶ include the same groups as those exemplified for R ^{12 to} R ¹⁵ above.

Examples of the fluoroalkyl group represented by R ¹⁶ include a trifluoromethyl group.

R ¹⁶ is preferably a hydrogen atom, an alkyl group or a fluoroalkyl group.

Examples of the alkyl group or cycloalkyl group represented by Y ² include the same groups as those exemplified for R ^{12 to} R ¹⁵ above.

Examples of the fluoroalkyl group represented by Y ² include the same groups as those exemplified for R ¹⁶ above.

Y ² is preferably a hydrogen atom, an alkyl group, a fluoroalkyl group, or a group represented by the above formula (9).

Examples of the halogen atom, alkyl group or cycloalkyl group represented by R ¹⁷ and R ¹⁸ include the same groups as those exemplified for R ^{12 to} R ¹⁵ above.

Examples of the alkyl group or cycloalkyl group represented by R ¹⁹ include the same groups as those exemplified above for R ^{12 to} R ¹⁵ .

As R < ¹⁷ > -R < ¹⁹ >, a hydrogen atom and an alkyl group are preferable.

  As said i, the integer of 0-2 is preferable.

Examples of the polyhydric phenol compound (C) represented by the above formula (7) include hydroquinone, catechol, 4-methylcatechol, 4-tert-butylcatechol, resorcinol, 2-methylresorcinol, 5-methylresorcinol, 4- Chlororesorcinol, 4-hexylresorcinol, 4-methoxyresorcinol, 4-chlororesorcinol, 5-methylresorcinol, 5-methoxyresorcinol, pyrogallol, 5-methylpyrogalol, phloroglicidol, 1,2,4-trihydroxybenzene, bis ( 4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) methane, bis (3-allyl-4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, bis (3,4- The Droxyphenyl) methane, bis (2,5-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (3,4-dihydroxy-6-methylphenyl) methane, bis (2, 4-dihydroxy-3-methylphenyl) methane, bis (2,4-dihydroxy-5-methylphenyl) methane, bis (3-hexyl-4,6-dihydroxyphenyl) methane, bis (3-chloro-4,6 -Dihydroxyphenyl) methane, bis (3-carboxy-2,4-dihydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane 1,1-bis (2,4-dihydroxyphenyl) ethane, 1,1-bis (3,4-dihydroxyphenyl) ethane 1,1-bis (2,5-dihydroxyphenyl) ethane, 1,1-bis (2,3,4-trihydroxyphenyl) ethane, 1,1-bis (3,4-dihydroxy-6-methylphenyl) ) Ethane, 1,1-bis (2,4-dihydroxy-3-methylphenyl) ethane, 1,1-bis (2,4-dihydroxy-5-methylphenyl) ethane, 1,1-bis (3-hexyl) -4,6-dihydroxyphenyl) ethane, 1,1-bis (3-chloro-4,6-dihydroxyphenyl) ethane, 1,1-bis (3-carboxy-2,4-dihydroxyphenyl) ethane, 1, 1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (2,4-dihydroxyphenyl) propane, , 1-bis (3,4-dihydroxyphenyl) propane, 1,1-bis (2,5-dihydroxyphenyl) propane, 1,1-bis (2,3,4-trihydroxyphenyl) propane, 1,1 -Bis (3,4-dihydroxy-6-methylphenyl) propane, 1,1-bis (2,4-dihydroxy-3-methylphenyl) propane, 1,1-bis (2,4-dihydroxy-5-methyl) Phenyl) propane, 1,1-bis (3-hexyl-4,6-dihydroxyphenyl) propane, 1,1-bis (3-chloro-4,6-dihydroxyphenyl) propane, 1,1-bis (3- Carboxy-2,4-dihydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxy-3-methylphenyl) butane 1,1-bis (2,4-dihydroxyphenyl) butane, 1,1-bis (3,4-dihydroxyphenyl) butane, 1,1-bis (2,5-dihydroxyphenyl) butane, 1,1 -Bis (2,3,4-trihydroxyphenyl) butane, 1,1-bis (3,4-dihydroxy-6-methylphenyl) butane, 1,1-bis (2,4-dihydroxy-3-methylphenyl) ) Butane, 1,1-bis (2,4-dihydroxy-5-methylphenyl) butane, 1,1-bis (3-hexyl-4,6-dihydroxyphenyl) butane, 1,1-bis (3-chloro) -4,6-dihydroxyphenyl) butane, 1,1-bis (3-carboxy-2,4-dihydroxyphenyl) butane, [bis (4-hydroxyphenyl) methyl] cyclohexane, Bis (4-hydroxy-3-methylphenyl) methyl] cyclohexane, [bis (2,4-dihydroxyphenyl) methyl] cyclohexane, [bis (3,4-dihydroxyphenyl) methyl] cyclohexane, [bis (2,5- Dihydroxyphenyl) methyl] cyclohexane, [bis (2,3,4-trihydroxyphenyl) methyl] cyclohexane, [bis (3,4-dihydroxy-6-methylphenyl) methyl] cyclohexane, [bis (2,4-dihydroxy) -3-methylphenyl) methyl] cyclohexane, [bis (2,4-dihydroxy-5-methylphenyl) methyl] cyclohexane, [bis (3-hexyl-4,6-dihydroxyphenyl) methyl] cyclohexane, [bis (3 -Chloro-4,6-dihydroxyphenyl) Methyl] cyclohexane, [bis (3-carboxy-2,4-dihydroxyphenyl) methyl] cyclohexane, [bis (4-hydroxyphenyl) methyl] benzene, [bis (4-hydroxy-3-methylphenyl) methyl] benzene, [Bis (2,4-dihydroxyphenyl) methyl] benzene, [Bis (3,4-dihydroxyphenyl) methyl] benzene, [Bis (2,5-dihydroxyphenyl) methyl] benzene, [Bis (2,3,4) -Trihydroxyphenyl) methyl] benzene, [bis (3,4-dihydroxy-6-methylphenyl) methyl] benzene, [bis (2,4-dihydroxy-3-methylphenyl) methyl] benzene, [bis (2, 4-dihydroxy-5-methylphenyl) methyl] benzene, [bis (3-hexyl -4,6-dihydroxyphenyl) methyl] benzene, [bis (3-chloro-4,6-dihydroxyphenyl) methyl] benzene, [bis (3-carboxy-2,4-dihydroxyphenyl) methyl] benzene, 2- [Bis (4-hydroxyphenyl) methyl] phenol, 2- [bis (4-hydroxy-3-methylphenyl) methyl] phenol, 2- [bis (2,4-dihydroxyphenyl) methyl] phenol, 2- [bis (3,4-dihydroxyphenyl) methyl] phenol, 2- [bis (2,5-dihydroxyphenyl) methyl] phenol, 2- [bis (2,3,4-trihydroxyphenyl) methyl] phenol, 2- [ Bis (3,4-dihydroxy-6-methylphenyl) methyl] phenol, 2- [bis (2,4-di Droxy-3-methylphenyl) methyl] phenol, 2- [bis (2,4-dihydroxy-5-methylphenyl) methyl] phenol, 2- [bis (3-hexyl-4,6-dihydroxyphenyl) methyl] phenol 2- [bis (3-chloro-4,6-dihydroxyphenyl) methyl] phenol, 2- [bis (3-carboxy-2,4-dihydroxyphenyl) methyl] phenol, 3- [bis (4-hydroxyphenyl) ) Methyl] phenol, 3- [bis (4-hydroxy-3-methylphenyl) methyl] phenol, 3- [bis (2,4-dihydroxyphenyl) methyl] phenol, 3- [bis (3,4-dihydroxyphenyl) ) Methyl] phenol, 3- [bis (2,5-dihydroxyphenyl) methyl] phenol, 3- [Bis (2,3,4-trihydroxyphenyl) methyl] phenol, 3- [bis (3,4-dihydroxy-6-methylphenyl) methyl] phenol, 3- [bis (2,4-dihydroxy-3-) Methylphenyl) methyl] phenol, 3- [bis (2,4-dihydroxy-5-methylphenyl) methyl] phenol, 3- [bis (3-hexyl-4,6-dihydroxyphenyl) methyl] phenol, 3- [ Bis (3-chloro-4,6-dihydroxyphenyl) methyl] phenol, 3- [bis (3-carboxy-2,4-dihydroxyphenyl) methyl] phenol, tris (4-hydroxyphenyl) methane, 4- [bis (4-Hydroxy-3-methylphenyl) methyl] phenol, 4- [bis (2,4-dihydroxyphenyl) methyl Ru] phenol, 4- [bis (3,4-dihydroxyphenyl) methyl] phenol, 4- [bis (2,5-dihydroxyphenyl) methyl] phenol, 4- [bis (2,3,4-trihydroxyphenyl) ) Methyl] phenol, 4- [bis (3,4-dihydroxy-6-methylphenyl) methyl] phenol, 4- [bis (2,4-dihydroxy-3-methylphenyl) methyl] phenol, 4- [bis ( 2,4-dihydroxy-5-methylphenyl) methyl] phenol, 4- [bis (3-hexyl-4,6-dihydroxyphenyl) methyl] phenol, 4- [bis (3-chloro-4,6-dihydroxyphenyl) ) Methyl] phenol, 4- [bis (3-carboxy-2,4-dihydroxyphenyl) methyl] phenol, 4- [ (4-hydroxyphenyl) methyl] resorcinol, 4- [bis (4-hydroxy-3-methylphenyl) methyl] resorcinol, tris (2,4-dihydroxyphenyl) methane, 4- [bis (3,4-dihydroxy) Phenyl) methyl] resorcinol, 4- [bis (2,5-dihydroxyphenyl) methyl] resorcinol, 4- [bis (2,3,4-trihydroxyphenyl) methyl] resorcinol, 4- [bis (3,4- Dihydroxy-6-methylphenyl) methyl] resorcinol, 4- [bis (2,4-dihydroxy-3-methylphenyl) methyl] resorcinol, 4- [bis (2,4-dihydroxy-5-methylphenyl) methyl] resorcinol 4- [Bis (3-hexyl-4,6-dihydroxyphenyl) Til] resorcinol, 4- [bis (3-chloro-4,6-dihydroxyphenyl) methyl] resorcinol, 4- [bis (3-carboxy-2,4-dihydroxyphenyl) methyl] resorcinol, 4- [bis (4 -Hydroxyphenyl) methyl] catechol, 4- [bis (4-hydroxy-3-methylphenyl) methyl] catechol 4- [bis (2,4-dihydroxyphenyl) methyl] catechol, tris (3,4-dihydroxyphenyl) Methane, 4- [bis (2,5-dihydroxyphenyl) methyl] catechol, 4- [bis (2,3,4-trihydroxyphenyl) methyl] catechol, 4- [bis (3,4-dihydroxy-6- Methylphenyl) methyl] catechol, 4- [bis (2,4-dihydroxy-3-methylpheny) ) Methyl] catechol, 4- [bis (2,4-dihydroxy-5-methylphenyl) methyl] catechol, 4- [bis (3-hexyl-4,6-dihydroxyphenyl) methyl] catechol, 4- [bis ( 3-chloro-4,6-dihydroxyphenyl) methyl] catechol, 4- [bis (3-carboxy-2,4-dihydroxyphenyl) methyl] catechol, 4- [bis (4-hydroxyphenyl) methyl] -2- Methoxyphenol, 4- [bis (4-hydroxy-3-methylphenyl) methyl] -2-methoxyphenol, 4- [bis (2,4-dihydroxyphenyl) methyl] -2-methoxyphenol, 4- [bis ( 3,4-dihydroxyphenyl) methyl] -2-methoxyphenol, 4- [bis (2,5-dihydroxyphene) L) Methyl] -2-methoxyphenol, 4- [bis (2,3,4-trihydroxyphenyl) methyl] -2-methoxyphenol, 4- [bis (3,4-dihydroxy-6-methylphenyl) methyl ] -2-methoxyphenol, 4- [bis (2,4-dihydroxy-3-methylphenyl) methyl] -2-methoxyphenol, 4- [bis (2,4-dihydroxy-5-methylphenyl) methyl]- 2-methoxyphenol, 4- [bis (3-hexyl-4,6-dihydroxyphenyl) methyl] -2-methoxyphenol, 4- [bis (3-chloro-4,6-dihydroxyphenyl) methyl] -2- Methoxyphenol, 4- [bis (3-carboxy-2,4-dihydroxyphenyl) methyl] -2-methoxyphenol, 2,4,6- Tris (4-hydroxybenzyl) phenol, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxy-3-methylphenyl) ethane, 1,1 , 2,2-Tetrakis (2,4-dihydroxyphenyl) ethane
2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (3,4-dihydroxy-6-methylphenyl) propane, 2,2-bis (2,4-dihydroxy-3-methylphenyl) propane, 2,2-bis (2,4-dihydroxy-5-methylphenyl) propane, 2,2-bis (3-hexyl-4, 6-dihydroxyphenyl) propane, 2,2-bis (3-chloro-4,6-dihydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3) -Phenyl) cyclohexane, 1,1-bis (3,4-dihydroxy-6-methylphenyl) cyclohexane, 9,9-bis (4-hydroxyphenyl) 9H-fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) -9H-fluorene, 9,9-bis (3-allyl-4-hydroxyphenyl) -9H-fluorene, 9,9-bis ( 3,4-dihydroxy-6-methylphenyl) -9H-fluorene, 1,1-bis (4-hydroxyphenyl) -1-adamantylethane, 1,1-bis (3,4-dihydroxy-6-methylphenyl) -1-adamantylethane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (2, 4-dihydroxyphenyl) -1-phenylethane, 1,1-bis (3,4-dihydroxyphenyl) -1-phenylethane, 1,1-bis (2,5-dihydride) Xylphenyl) -1-phenylethane, 1,1-bis (2,3,4-trihydroxyphenyl) -1-phenylethane, 1,1-bis (3,4-dihydroxy-6-methylphenyl) -1- Phenylethane, 1,1-bis (2,4-dihydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (2,4-dihydroxy-5-methylphenyl) -1-phenylethane, , 1-bis (3-hexyl-4,6-dihydroxyphenyl) -1-phenylethane, 1,1-bis (3-chloro-4,6-dihydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1- (4-hydroxyphenyl) ethane 1,1-bis (2,4-dihydroxyphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (3,4-dihydroxyphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (2,5-dihydroxyphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (2,3,4-trihydroxyphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (3,4-dihydroxy-6-methylphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (2,4-dihydroxy-3-methylphenyl) -1- (4 -Hydroxyphenyl) ethane, 1,1-bis (2,4-dihydroxy-5-methylphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (3-hexyl-4,6 Dihydroxyphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (3-chloro-4,6-dihydroxyphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (4- Hydroxyphenyl) -1- (2,4-dihydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1- (2,4-dihydroxyphenyl) ethane, 1,1,1- Tris (2,4-dihydroxyphenyl) ethane, 1,1-bis (3,4-dihydroxyphenyl) -1- (2,4-dihydroxyphenyl) ethane, 1,1-bis (2,5-dihydroxyphenyl) -1- (2,4-dihydroxyphenyl) ethane, 1,1-bis (2,3,4-trihydroxyphenyl) -1- (2,4-dihydroxyphenyl) 1,1-bis (3,4-dihydroxy-6-methylphenyl) -1- (2,4-dihydroxyphenyl) ethane, 1,1-bis (2,4-dihydroxy-3-methylphenyl)- 1- (2,4-dihydroxyphenyl) ethane, 1,1-bis (2,4-dihydroxy-5-methylphenyl) -1- (2,4-dihydroxyphenyl) ethane, 1,1-bis (3- Hexyl-4,6-dihydroxyphenyl) -1- (2,4-dihydroxyphenyl) ethane, 1,1-bis (3-chloro-4,6-dihydroxyphenyl) -1- (2,4-dihydroxyphenyl) Ethane, 1,4-bis [(4-hydroxyphenyl) methyl] benzene, 1,4-bis [(4-hydroxy-3-methylphenyl) methyl] benzene, 1,4-bis [(2, 4-dihydroxyphenyl) methyl] benzene, 1,4-bis [(3,4-dihydroxyphenyl) methyl] benzene, 1,4-bis [(2,5-dihydroxyphenyl) methyl] benzene, 1,4-bis [(2,3,4-trihydroxyphenyl) methyl] benzene, 1,4-bis [(3,4-dihydroxy-6-methylphenyl) methyl] benzene, 1,4-bis [(2,4-dihydroxy -3-methylphenyl) methyl] benzene, 1,4-bis [(2,4-dihydroxy-5-methylphenyl) methyl] benzene, 1,4-bis [(3-hexyl-4,6-dihydroxyphenyl) Methyl] benzene, 1,4-bis [(3-chloro-4,6-dihydroxyphenyl) methyl] benzene, bis (4-hydroxyphenyl) ketone, (2 Hydroxyphenyl) (4-hydroxyphenyl) ketone, (2,4-dihydroxyphenyl) (4-hydroxyphenyl) ketone, (2,3,4-trihydroxyphenyl) (4-hydroxyphenyl) ketone, bis (4- Hydroxyphenyl) sulfone, (2-hydroxyphenyl) (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxy-2,5-dimethylphenyl) sulfone, bis (3 -Allyl-4-hydroxyphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-sulfophenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy) -3-methylphenyl) sulfide, bis (3 Carboxy-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, N- (4-hydroxyphenyl) -4-hydroxybenzamide, bis (4-hydroxyphenyl) disulfide, 2,6-bis [(4- Hydroxyphenyl) methyl] -4-methylphenol, 2,6-bis [(4-hydroxy-3-methylphenyl) methyl] -4-methylphenol, 2,6-bis [(2,4-dihydroxyphenyl) methyl ] -4-methylphenol, 2,6-bis [(3,4-dihydroxyphenyl) methyl] -4-methylphenol, 2,6-bis [(2,5-dihydroxyphenyl) methyl] -4-methylphenol 2,6-bis [(2,3,4-trihydroxyphenyl) methyl] -4-methylphenol, 2,6-bis [(3,4-dihydroxy-6-methylphenyl) methyl] -4-methylphenol, 2,6-bis [(2,4-dihydroxy-3-methylphenyl) methyl] -4-methyl Phenol, 2,6-bis [(2,4-dihydroxy-5-methylphenyl) methyl] -4-methylphenol, 2,6-bis [(3-hexyl-4,6-dihydroxyphenyl) methyl] -4 -Methylphenol, 2,6-bis [(3-chloro-4,6-dihydroxyphenyl) methyl] -4-methylphenol, 4,6-bis [(4-hydroxyphenyl) methyl] -2-methylphenol, 4,6-bis [(4-hydroxy-3-methylphenyl) methyl] -2-methylphenol, 4,6-bis [(2,4-dihydroxyphenyl) methyl] -2 Methylphenol, 4,6-bis [(3,4-dihydroxyphenyl) methyl] -2-methylphenol, 4,6-bis [(2,5-dihydroxyphenyl) methyl] -2-methylphenol, 4,6 -Bis [(2,3,4-trihydroxyphenyl) methyl] -2-methylphenol, 4,6-bis [(3,4-dihydroxy-6-methylphenyl) methyl] -2-methylphenol, 4, 6-bis [(2,4-dihydroxy-3-methylphenyl) methyl] -2-methylphenol, 4,6-bis [(2,4-dihydroxy-5-methylphenyl) methyl] -2-methylphenol, 4,6-bis [(3-hexyl-4,6-dihydroxyphenyl) methyl] -2-methylphenol, 4,6-bis [(3-chloro-4,6-dihydro Cyphenyl) methyl] -2-methylphenol, 2,6-bis [(4-hydroxyphenyl) methyl] -4-tert-butylphenol, 2,6-bis [(4-hydroxy-3-methylphenyl) methyl]- 4-tert-butylphenol, 2,6-bis [(2,4-dihydroxyphenyl) methyl] -4-tert-butylphenol, 2,6-bis [(3,4-dihydroxyphenyl) methyl] -4-tert- Butylphenol, 2,6-bis [(2,5-dihydroxyphenyl) methyl] -4-tert-butylphenol, 2,6-bis [(2,3,4-trihydroxyphenyl) methyl] -4-tert-butylphenol 2,6-bis [(3,4-dihydroxy-6-methylphenyl) methyl] -4-tert-butyl Phenol, 2,6-bis [(2,4-dihydroxy-3-methylphenyl) methyl] -4-tert-butylphenol, 2,6-bis [(2,4-dihydroxy-5-methylphenyl) methyl]- 4-tert-butylphenol, 2,6-bis [(3-hexyl-4,6-dihydroxyphenyl) methyl] -4-tert-butylphenol, 2,6-bis [(3-chloro-4,6-dihydroxyphenyl) ) Methyl] -4-tert-butylphenol, 2,6-bis [(4-hydroxyphenyl) methyl] -4-cyclohexylphenol, 2,6-bis [(4-hydroxy-3-methylphenyl) methyl] -4 -Cyclohexylphenol, 2,6-bis [(2,4-dihydroxyphenyl) methyl] -4-cyclohexylpheno 2,6-bis [(3,4-dihydroxyphenyl) methyl] -4-cyclohexylphenol, 2,6-bis [(2,5-dihydroxyphenyl) methyl] -4-cyclohexylphenol, 2,6- Bis [(2,3,4-trihydroxyphenyl) methyl] -4-cyclohexylphenol, 2,6-bis [(3,4-dihydroxy-6-methylphenyl) methyl] -4-cyclohexylphenol, 2,6 -Bis [(2,4-dihydroxy-3-methylphenyl) methyl] -4-cyclohexylphenol, 2,6-bis [(2,4-dihydroxy-5-methylphenyl) methyl] -4-cyclohexylphenol, 2 , 6-Bis [(3-hexyl-4,6-dihydroxyphenyl) methyl] -4-cyclohexylphenol, 2 6-bis [(3-chloro-4,6-dihydroxyphenyl) methyl] -4-cyclohexylphenol, 4,6-bis [(4-hydroxyphenyl) methyl] -2-cyclohexylphenol, 4,6-bis [ (4-Hydroxy-3-methylphenyl) methyl] -2-cyclohexylphenol, 4,6-bis [(2,4-dihydroxyphenyl) methyl] -2-cyclohexylphenol, 4,6-bis [(3,4 -Dihydroxyphenyl) methyl] -2-cyclohexylphenol, 4,6-bis [(2,5-dihydroxyphenyl) methyl] -2-cyclohexylphenol, 4,6-bis [(2,3,4-trihydroxyphenyl) ) Methyl] -2-cyclohexylphenol, 4,6-bis [(3,4-dihydroxy-6-methylphenol) Phenyl) methyl] -2-cyclohexylphenol, 4,6-bis [(2,4-dihydroxy-3-methylphenyl) methyl] -2-cyclohexylphenol, 4,6-bis [(2,4-dihydroxy-5) -Methylphenyl) methyl] -2-cyclohexylphenol
4,6-bis [(3-hexyl-4,6-dihydroxyphenyl) methyl] -2-cyclohexylphenol, 4,6-bis [(3-chloro-4,6-dihydroxyphenyl) methyl] -2- Examples include cyclohexylphenol.

  The polyhydric phenol compound (C) includes hydroquinone, catechol, resorcinol, pyrogallol, bis (4-hydroxyphenyl) methane from the viewpoint of reducing coloring of the conductive layer and solubility of the polyhydric phenol compound (C) in the solvent. Bis (4-hydroxy-3-methylphenyl) methane, bis (3,4-dihydroxy-6-methylphenyl) methane, bis (2,4-dihydroxy-3-methylphenyl) methane, [bis (3,4 -Dihydroxy-6-methylphenyl) methyl] benzene, [bis (2,4-dihydroxy-3-methylphenyl) methyl] benzene, 4- [bis (3,4-dihydroxy-6-methylphenyl) methyl] catechol, 4- [bis (2,4-dihydroxy-3-methylphenyl) methyl] catechol, 2,2-bis ( -Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (3,4-dihydroxy-6-methylphenyl) propane, 2,2-bis (2, 4-dihydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1 , 1-bis (3,4-dihydroxy-6-methylphenyl) -1-phenylethane, 1,1-bis (2,4-dihydroxy-3-methylphenyl) -1-phenylethane, 1,1,1 -Tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bi (3,4-dihydroxy-6-methylphenyl) -1- (4-hydroxyphenyl) ethane, 1,1-bis (2,4-dihydroxy-3-methylphenyl) -1- (4-hydroxyphenyl) ethane Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, and bis (4-hydroxyphenyl) ether are preferred.

  Further, as the polyhydric phenol compound (C), bis (4-hydroxyphenyl) sulfone represented by the following formula (10), bis (4-hydroxyphenyl) ether represented by the following formula (11), and the following formula Bis (3,4-dihydroxy-6-methylphenyl) methane represented by (12) is more preferred. In addition to the above properties, these polyhydric phenol compounds (C) have little change in hue in air and in solution, and have high stability. Furthermore, since these polyhydric phenol compounds (C) have a structure that easily reacts with the methylolated phenol compound (B), the coating film is easily cured by heat, and as a result, the hardness of the obtained conductive layer is more improves.

  As an upper limit of content with respect to 1 mol of conductive polymer compounds (A) of the polyhydric phenol compound (C) in the said conductive layer, 20 mol is preferable and 1 mol is more preferable. On the other hand, the lower limit of the content is preferably 0.001 mol, and more preferably 0.01 mol. When the said content exceeds the said upper limit, a polyhydric phenol compound (C) may precipitate on the surface of an electroconductive layer, and there exists a possibility that transparency and electroconductivity may fall. On the other hand, when the content is less than the lower limit, the hardness and conductivity of the obtained conductive layer may be reduced.

(Method for producing polyphenol compound (C))
The polyhydric phenol compound (C) can be produced, for example, by a reaction between phenols and formaldehyde. Such a reaction is known and is carried out in the presence of an acid catalyst or a base catalyst.

  As a manufacturing method of a polyhydric phenol compound (C), the following method is mentioned, for example. First, aldehydes and an excessive amount of phenols (for example, 1 mol to 30 mol of phenol with respect to 1 mol of aldehydes) are dissolved in a solvent and reacted in the presence of an acid catalyst or a base catalyst. The end point of the reaction is determined by tracking the residual amount of phenols or formaldehyde by a known method such as gas chromatography, thin layer chromatography, liquid chromatography, gel filtration chromatography, IR analysis, and the peak area indicating this residual amount is The time when it no longer decreases.

  Examples of the phenols include phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, and 2-methoxyphenol. 4-methoxyphenol, 4-aminophenol, 2-ethylphenol, 4-ethylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2-cyclohexylphenol, 4-cyclohexylphenol, 2-phenylphenol, 4- Phenylphenol, hydroquinone, catechol, 4-methylcatechol, 4-tert-butylcatechol, resorcinol, 2-methylresorcinol, 5-methylresorcinol, 4-chlororesorcinol, - hexylresorcinol, 4-methoxy resorcinol, 4-chloro resorcinol, 5-methyl resorcinol, 5-methoxy resorcinol, pyrogallol, 5-methyl pyrogallol, fluoro glycidol, 1,2,4-trihydroxybenzene, and the like.

  As the above-mentioned phenols, a polyhydric phenol compound (C) having high reactivity with aldehydes and high solubility in a solvent can be obtained. Therefore, phenol, hydroquinone, catechol, 4-methylcatechol, resorcinol, 2 -Methylresorcinol and pyrogallol are preferred. The said phenols may be used independently and may be used in combination of 2 or more type.

  Further, aromatic carboxylic acids or aromatic sulfonic acids may be used in place of the phenols. Examples of the aromatic carboxylic acids include 4-hydroxybenzoic acid, salicylic acid, 3-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5 -Dihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, etc. are mentioned. Examples of the aromatic sulfonic acids include 4-phenolsulfonic acid.

  Examples of the aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, n-hexylaldehyde, cyclohexanecarbaldehyde, glyoxal, benzaldehyde, salicylaldehyde, Examples thereof include aromatic aldehydes such as 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, and vanillin.

  As the aldehydes, formaldehyde, benzaldehyde and 3,4-dihydroxyaldehyde are preferable from the viewpoint of obtaining a polyphenol compound (C) with little coloring.

  In place of the aldehydes, ketones or methylolated phenol compounds (B) may be used.

  Examples of the ketones include aliphatic ketones such as acetone, cyclohexanone, and 1-acetyladamantane, and aromatic aldehydes such as acetophenone, 4-hydroxyacetophenone, 2,4-dihydroxyacetophenone, and fluorenone. Among these, acetone, cyclohexanone, acetophenone, and 4-hydroxyacetophenone are preferable from the viewpoint of obtaining a polyhydric phenol compound (C) having high solubility in a solvent.

  Examples of the methylolated phenol compound (B) include 2,6-dihydroxymethyl-4-methylphenol, 4,6-dihydroxymethyl-2-methylphenol, 2,6-dihydroxymethyl-4-methoxyphenol, 4,6 -Dihydroxymethyl-2-methoxyphenol, 4-tert-butyl-2,6-dihydroxymethylphenol, 4-cyclohexyl-2,6-dihydroxymethylphenol, 2-cyclohexyl-4,6-dihydroxymethylphenol, etc. . Among these, from the viewpoint of obtaining a polyhydric phenol compound (C) that is less colored and highly soluble in a solvent, 2,6-dihydroxymethyl-4-methylphenol and 4,6-dihydroxymethyl-2- Methylphenol is preferred.

  Furthermore, in addition to the aldehydes, the ketones or the methylolated phenol compounds, aromatic methanol such as paraxylene glycol may be used.

  Examples of the solvent include water, alcohol solvents, ether solvents and the like. Examples of the acid catalyst include hydrochloric acid and sulfuric acid. Examples of the base catalyst include sodium hydroxide, potassium hydroxide, potassium carbonate, triethylamine and the like.

  As said reaction temperature, 20 to 150 degreeC is preferable, for example. As said reaction time, 30 minutes or more and 48 hours or less are preferable, for example.

  Moreover, as a manufacturing method of a polyhydric phenol compound (C), the manufacturing method by the condensation reaction of the said phenols and the said aromatic carboxylic acids or aromatic sulfonic acids other than the above-mentioned method, the condensation by the said phenols, for example Examples include a production method by reaction, a production method by reaction of the above phenols with a sulfur compound (sulfur dichloride, etc.), and the like.

  After completion of the reaction, the reaction solution is cooled to about room temperature, and the catalyst is neutralized using a neutralizing agent. Thereafter, an appropriate amount of a poor solvent such as water or an organic solvent (toluene, xylene, etc.) is added to precipitate the reaction product. The polyphenol compound (C) is obtained by separating the precipitate by filtration, purifying by washing with water, recrystallization, etc., if necessary, and drying.

<Solvent (D)>
The solvent (D) dissolves or disperses the conductive polymer compound (A) in the coating composition and dissolves the methylolated phenol compound (B) and the polyhydric phenol compound (C).

  As said solvent (D), the mixed solvent of water, an organic solvent, and water and an organic solvent is preferable, and the mixed solvent of water and an organic solvent is more preferable. According to the mixed solvent, it is possible to obtain a conductive layer that is excellent in solubility of the methylolated phenol compound (B) and the polyhydric phenol compound (C), and excellent in uniformity and the like.

  The organic solvent is preferably soluble in water. Such an organic solvent is not particularly limited as long as it becomes a uniform solution when mixed with water, and examples thereof include alcohols, ketones, ethylene glycols, propylene glycols, amides, and pyrrolidones. These organic solvents may use only 1 type and may use 2 or more types together.

  Examples of the alcohols include methanol, ethanol, isopropyl alcohol, propyl alcohol, and butanol. Examples of the ketones include acetone. Examples of the ethylene glycols include ethylene glycol methyl ether. Examples of the propylene glycols include propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, and propylene glycol propyl ether. Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide. Examples of the pyrrolidones include N-methylpyrrolidone and N-ethylpyrrolidone.

  As said organic solvent, alcohol is preferable from a viewpoint of the ease of drying of the conductive layer formed with the coating composition, and safety | security, and isopropyl alcohol is more preferable.

  The upper limit of the amount of alcohol mixed with 100 parts by mass of water in the solvent (D) is preferably 500 parts by mass, and more preferably 200 parts by mass. On the other hand, as a minimum of the said mixing amount, 5 mass parts is preferable and 10 mass parts is more preferable. When the mixing amount exceeds the upper limit, the solvent remains in the conductive layer after drying, and the strength of the conductive layer may be reduced. On the contrary, when the mixing amount is less than the lower limit, the uniformity of the conductive layer is lowered and the conductivity may be lowered.

<Crosslinking agent>
A crosslinking agent can bridge | crosslink a conductive polymer compound (A) etc., As a result, the damage resistance of the said conductive layer obtained, hardness, and the adhesiveness with respect to a base film can be improved. Moreover, the electroconductivity of a conductive layer may improve by forming the conductive layer excellent in stability by bridge | crosslinking.

  The crosslinking agent is preferably a compound having a group capable of reacting with active hydrogen from the viewpoint of improving the hardness of the conductive layer and the adhesion to the substrate film, for example, an isocyanate compound, a carbodiimide compound, an epoxy compound, an oxetane compound, A (meth) acryloyl compound etc. are mentioned.

  Examples of the isocyanate compound include hexamethylene diisocyanate, methylene diphenylene diisocyanate, xylene diisocyanate, 1,4-naphthalene diisocyanate, and phenylene diisocyanate.

  Moreover, the isocyanate compound may be protected with a blocking agent having an isocyanate group having thermal dissociation properties. Examples of the blocking agent include methanol, phenol, aliphatic mercaptan, aromatic mercaptan, N-methylaniline, methyl ethyl ketoxime, acetylacetone, and ε-caprolactam.

Examples of the carbodiimide compound include dicyclohexylmethane carbodiimide, dicyclohexyl carbodiimide, tetramethylxylylene carbodiimide, and urea-modified carbodiimide .

  Examples of the epoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl. Ether, polypropylene glycol diglycidyl ether, fatty acid-modified epoxy, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol polyglycidyl ether, ethylene oxide lauryl alcohol glycidyl Ether, ethyleneoxy Phenol glycidyl ether, adipic acid glycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanate. Among these, those having two or more epoxy groups are preferable.

  Examples of the oxetane compound include xylylene bisoxetane, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, 4,4 ′-(3-ethyloxetane-3-ylmethyl). Oxymethyl) biphenyl, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di {1-ethyl (3-oxetanyl)} methyl ether, 3-ethyl-3- (hydroxymethyl) ) Oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-phenoxymethyloxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane Etc. Among these, those having two or more oxetane rings are preferable.

  Examples of the (meth) acryloyl compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, and di Cyclopentanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-propanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified di (meth) acrylate of bisphenol A, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate, glycidyl (meth) acrylate, N, N- ( Examples include meth) acrylamide, dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, (meth) acryloylmorpholine, (meth) acryloylpiperidine and the like. Among these, those having two or more (meth) acryloyl groups are preferable. Here, “(meth) acryloyl” represents at least one selected from the group consisting of acryloyl and methacryloyl. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  As an upper limit of content of a crosslinking agent with respect to 100 mass parts of conductive polymer compounds (A) in the said conductive layer, 200 mass parts is preferable and 100 mass parts is more preferable. On the other hand, as a minimum of the above-mentioned content, 1 mass part is preferred and 5 mass parts is more preferred. When the said content exceeds the said upper limit, the viscosity of the coating composition for forming the said conductive layer will become high, and there exists a possibility that handling may become difficult. On the other hand, when the content is less than the lower limit, it is difficult to improve the hardness or the like of the conductive layer. Here, “with respect to 100 parts by mass of the conductive polymer compound (A)” means “with respect to 100 parts by mass of the solid content of the conductive polymer compound (A)”.

  When the said conductive layer contains the said crosslinking agent, from a viewpoint of promoting bridge | crosslinking of the conductive polymer compound (A) etc. by a crosslinking agent, and improving the water resistance and hardness of the obtained conductive layer, it contains a curing catalyst. It is preferable.

  The curing catalyst is not particularly limited as long as it can promote cross-linking by the cross-linking agent contained in the conductive layer. A radical polymerization initiator, a thermal radical polymerization initiator, etc. are mentioned.

  Examples of the thermopolymerizable curing catalyst include 2-methylimidazole, amine, triphenylphosphine, and the like.

  Examples of the photocationically polymerizable curing catalyst include diazonium salts, iodonium salts, sulfonium salts and the like.

  Examples of the thermal cationic polymerizable curing catalyst include aromatic onium salts and triflate salts.

  Examples of the photo radical polymerization initiator include acetophenone, benzophenone, 1-hydroxycyclohexyl phenyl ketone, and the like.

  Examples of the thermal radical polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl peroxide, azobisisobutyronitrile and the like.

  As an upper limit of content of the said curing catalyst with respect to 100 mass parts of said crosslinking agents, 150 mass parts is preferable and 100 mass parts is more preferable. On the other hand, as a minimum of the above-mentioned content, 0.1 mass part is preferred and 1 mass part is more preferred. When the said content exceeds the said upper limit, there exists a possibility that the electroconductivity of the said conductive layer may fall with an excess curing catalyst. On the other hand, when the content is less than the lower limit, the hardness or the like of the conductive layer may be difficult to improve.

<Binder resin>
The binder resin can improve the scratch resistance and surface hardness of the conductive layer and improve the adhesion between the conductive layer and the base film. Furthermore, the film formability can be improved and the uniformity of the conductive layer can be improved.

  The binder resin may be either a thermosetting resin or a thermoplastic resin. Examples of the binder resin include polyvinyl resins such as polyvinyl alcohol, polyvinyl acetal, polyvinyl ether, polyvinyl pyrrolidone, polyvinyl acetate, and polyvinyl chloride, polyacetal, polyester, acrylic resin, polyacrylamide, polyimide, polyamide, alkyd resin, xylene resin, Aramid resin, polyimide silicone, melamine resin, urea resin, phenol resin, epoxy resin, urethane resin, acrylic / styrene resin, vinyl acetate / acrylic copolymer resin, styrene / maleic acid copolymer resin, fluororesin and copolymers thereof Etc.

  As the binder resin, polyester, acrylic resin, polyimide, polyamide, epoxy resin, and urethane resin are preferable. These resins can be easily mixed with the conductive polymer compound (A) and the like. Moreover, since these resin can be hardened | cured with a methylolation phenol compound (B) and a heat | fever, the intensity | strength of a conductive layer further improves.

  Examples of the mode of addition of the binder resin to the coating composition forming the conductive layer include solid or liquid resins, those obtained by dissolving these resins in a solvent, and functional groups such as sulfonic acid groups and carboxylic acid groups. And those obtained by dissolving these resins in water, and emulsions obtained by dispersing these resins in water.

  When the said conductive layer contains binder resin and a solvent (D), as an upper limit of binder resin content with respect to 100 mass parts of solvent (D), 50 mass parts is preferable, and 30 mass parts is more preferable. On the other hand, the lower limit of the content is preferably 1 part by mass. When the said content exceeds the said upper limit, the viscosity of the coating composition for forming the said conductive layer will increase, and there exists a possibility that it may become difficult to handle. Conversely, when the content is less than the lower limit, the hardness of the conductive layer may be difficult to improve.

<Other ingredients>
Examples of other components that the conductive layer may have include, for example, a conductivity improving component, a surfactant, a silane coupling agent, a thickener, a dye, a curing catalyst, a rheology control agent, resin fine particles, inorganic fine particles, Examples include foaming agents, surface conditioners, ultraviolet absorbers, antioxidants, antiseptics, fungicides, and plasticizers.

  As said electroconductivity improvement component, well-known compounds, such as a compound containing 2 or more of hydroxyl groups in a molecule | numerator, can be used, for example. Examples of such a conductivity improving component include ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, sugar (fructose, etc.) and the like.

  As content of the said electroconductivity improvement component in the said conductive layer, 10 to 1000 mass parts is preferable with respect to 100 mass parts of conductive polymer compounds (A). Here, “with respect to 100 parts by mass of the conductive polymer compound (A)” means “with respect to 100 parts by mass of the solid content of the conductive polymer compound (A)”.

  As said surfactant, a nonionic surfactant, a fluorochemical surfactant, etc. can be used from a viewpoint of improving the wettability of the conductive layer with respect to a base film. Examples of the nonionic activator include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester and the like. Examples of the fluorosurfactant include fluoroalkyl carboxylates, perfluoroalkylbenzene sulfonates, perfluoroalkyl quaternary ammonium salts, and perfluoroalkyl polyoxyethylene ethanol.

  As content of the said surfactant in the said conductive layer, 0.5 to 20 mass parts is preferable with respect to 100 mass parts of conductive polymer compounds (A). Here, “with respect to 100 parts by mass of the conductive polymer compound (A)” means “with respect to 100 parts by mass of the solid content of the conductive polymer compound (A)”.

  The silane coupling agent is preferably a silane compound having an epoxycyclohydrocarbon group from the viewpoint of improving the hardness of the conductive layer and the adhesion to the substrate film. Examples of the silane compound having an epoxycyclohydrocarbon group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

  The content of the silane coupling agent in the conductive layer is preferably 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the conductive polymer compound (A). Here, “with respect to 100 parts by mass of the conductive polymer compound (A)” means “with respect to 100 parts by mass of the solid content of the conductive polymer compound (A)”.

<Coating composition>
The said conductive layer is formed by apply | coating the coating composition for forming a conductive layer on the layer which wants to form a conductive layer, and drying. The coating composition contains a conductive polymer compound (A) and a methylolated phenol compound (B) represented by the formula (1). Furthermore, it is preferable to contain a dopant, the polyhydric phenol compound (C) represented by the above formula (7), a solvent, a crosslinking agent or a binder resin. Moreover, you may contain the other arbitrary component for improving the performance of a conductive layer.

  The coating composition includes the conductive polymer compound (A), the methylolated phenol compound (B), the dopant, the polyhydric phenol compound (C), the cross-linking agent, the binder resin, and the like in any order as described above. Can be produced by mixing with a solvent (D). A known stirrer can be used for mixing each component.

<Method for producing conductive layer>
Examples of the method for forming the conductive layer include a method mainly comprising a step of applying the coating composition to the surface of the base film and a step of drying the coating film.

  As a method for applying the coating composition to the substrate film, a method used in general coating can be used. Examples of the coating method include a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a fountain coater, a rod coater, an air doctor coater, a knife coater, a blade coater, a cast coater, and a screen. Application of a coater or the like, spraying such as spray coating, dipping or the like.

As an upper limit of the coating amount of the coating composition on the base film, 5,000 μL / cm ² is preferable, and 1,000 μL / cm ² is more preferable. On the other hand, the lower limit of the coating amount is preferably from ^{0.02μL / cm 2, 0.1μL / cm} 2 is more preferable. When the coating amount exceeds the above upper limit, the conductive layer may be insufficiently dried and the strength may be reduced. On the contrary, when the coating amount is less than the lower limit, the resistance of the conductive layer may increase. Moreover, there exists a possibility that it may become difficult to apply | coat uniformly.

  The coating film may be dried by allowing it to stand at room temperature or by performing a heat treatment, but it is more preferable to perform the heat treatment. As this heat treatment, for example, a normal method such as hot air heating or infrared heating is used. As temperature in the case of performing heat processing, 70 to 250 degreeC is preferable. When the heating temperature is less than the above lower limit, when the conductive layer contains a solvent, a large amount of the solvent may remain and the conductivity may not be sufficiently exhibited. On the other hand, when the heating temperature exceeds the above upper limit, the conductive polymer compound (A) may be deteriorated and the conductivity of the conductive layer may be lowered.

  Furthermore, ultraviolet rays may be irradiated after drying to cure the coating film. As the ultraviolet irradiation treatment, for example, a method of irradiating ultraviolet rays from a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp is used.

  The upper limit of the average thickness of the conductive layer formed on the base film is preferably 50 μm and more preferably 10 μm. On the other hand, the lower limit of the average thickness is preferably 0.01 μm, more preferably 0.05 μm. When the average thickness exceeds the upper limit, the conductive layer may not be sufficiently dried, and the strength may be reduced. Conversely, if the average thickness is less than the lower limit, the resistance of the conductive layer may increase.

<Base film>
The base film is not particularly limited as long as the conductive layer can be laminated, but is preferably transparent. Examples of the base film include polyethylene terephthalate (PET), polyethylene naphthalate, cycloolefin polymer, polycarbonate, polymethyl methacrylate, polystyrene, polyimide, polyamide, polysulfone, polyvinyl chloride, polyethylene, polypropylene, and blends thereof. And a sheet made of a phenol resin, an epoxy resin, ABS, a film, a nonwoven fabric, and the like.

  Among these, the PET film that has been widely used conventionally is more preferable because it is inexpensive, excellent in strength, heat resistance, and dimensional stability, and has both transparency and flexibility.

  The average thickness of the base film is not particularly limited, but the upper limit of the average thickness of the base film is preferably 500 μm, and more preferably 350 μm. On the other hand, as a minimum of average thickness of the above-mentioned substrate film, 10 micrometers is preferred and 40 micrometers is more preferred. When the average thickness of the base film exceeds the above upper limit, the rigidity becomes too strong, so that the handleability may be lowered when the obtained conductive film is attached to a display or the like. When the average thickness of the base film is less than the lower limit, sufficient rigidity may not be obtained.

  The base film may be subjected to surface treatment such as corona discharge treatment or plasma discharge treatment on the surface on which the conductive layer is laminated for the purpose of improving the adhesion of the conductive layer to be laminated.

  The base film is a resin such as a polyester resin, an epoxy resin, or a polyurethane acrylate between the base film and the conductive layer for the purpose of improving the adhesion and transparency of the conductive layer to be laminated or optical properties such as antireflection. An anchor layer may be provided.

<Characteristics of conductive film>
(550 nm light transmittance)
The conductive film is excellent in transparency. For example, from the viewpoint of improving the visibility when used for a touch panel or the like, the light transmittance at 550 nm is preferably 70% or more, and more preferably 80% or more.

(Surface resistance value)
The said conductive film is excellent in electroconductivity. For example, from the viewpoint of improving the operability when used for a touch panel or the like, the upper limit of the surface resistance value is preferably 1,000 Ω / □, more preferably 400 Ω / □.

(Moisture and heat resistance)
The conductive film is excellent in heat and moisture resistance. For example, from the viewpoint of improving environmental stability when used for a touch panel or the like, the rate of change of the surface resistance value before and after the treatment for 240 hours under the conditions of 60 ° C. and 95% humidity is preferably ± 50% or less. An increase / decrease of ± 20% or less is more preferable.

(Light resistance)
The conductive film is excellent in light resistance. For example, from the viewpoint of improving environmental stability when used for a touch panel or the like, the rate of change of the surface resistance value before and after irradiation with ultraviolet light having an irradiation intensity of 10 mW / cm ² for 24 hours with a high-pressure mercury lamp is ± 50% or less. An increase / decrease of ± 20% or less is more preferable.

(Scratch resistance)
The conductive film is excellent in scratch resistance. The scratch resistance can be used as an index of adhesion between the base film and the conductive layer. For example, from the viewpoint of improving the durability when used for a touch panel or the like, the state of the conductive layer when using a paper towel and rubbing 20 reciprocations at a load of 100 gf / cm ² and a speed of 1 reciprocation / second is counted as several tens. Even if there is a scratch that can be removed, a state in which the conductive layer remains is preferable, and a state in which there is no scratch is more preferable.

(Pencil hardness)
The conductive film is excellent in coating film hardness. For example, from the viewpoint of improving durability when used for a touch panel or the like, the pencil hardness is preferably H or higher, and more preferably 2H or higher.

  The conductive film of the present invention is excellent in conductivity, transparency, coating film hardness, light resistance and moisture and heat resistance, and therefore suitable for transparent electrodes, electromagnetic wave shielding materials, etc. in touch panels, solar cells, electronic paper, flexible light control materials, etc. Can be used for

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Preparation of coating composition>
<Example 1>
0.220 g of methylolated phenol compound (component (B)), 0.055 g of diethylene glycol diglycidyl ether, 0.055 g of trimethylolpropane triglycidyl ether, 0.110 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 0.006 g of 2-methylimidazole was added to 24.304 g of solvent (6.076 g of water and 18.228 g of isopropyl alcohol), and dissolved at 25 ° C. Thereafter, 20.000 g of an aqueous dispersion of the conductive polymer compound (component (A)) (content of component (A) 0.220 g) was added and mixed at 25 ° C. to prepare a coating composition. As the component (B), (B-1) described later was used.

<Examples 2 to 17 and Comparative Examples 1 to 7>
As the component (B), the component (C), the crosslinking agent, the silane coupling agent, the curing catalyst, the additive, the binder resin, and the solvent (D), the components shown in Table 1 are used, and the amount of each component used is shown in Table 1. A coating composition was prepared in the same manner as in Example 1 except that. The compounds used in Examples and Comparative Examples are shown below.

(Conductive polymer compound (A))
As the conductive polymer compound (A), poly (3,4-ethylenedioxythiophene) doped with poly (4-styrenesulfonic acid) (“CLEVIOS (registered trademark) PH1000” manufactured by Heraeus) was used.

This PH1000 is an aqueous dispersion containing 1.1% by mass of a PEDOT / PSS polymer (PEDOT: PSS mass ratio is 1: 2.5). The number of moles of PEDOT / PSS was calculated from the following equation based on the PEDOT content, with the molecular weight of the smallest unit of PEDOT being 142.
PEDOT: Number of moles of PSS (mol) = PEDOT content (g) / Molecular weight of PEDOT minimum unit 142 (g / mol)

(Methylolated phenol compound (B))
The methylolated phenol compound (B) used in the examples is shown below.
B-1: 2,6-dihydroxymethyl-4-methylphenol ("26DMPC" from Asahi Organic Materials Co., Ltd., molecular weight 168)
B-2: 4,6-dihydroxymethyl-2-methylphenol ("46DMOC" from Asahi Organic Materials Co., Ltd., molecular weight 168)
B-3: 4-ethyl-2,6-dihydroxymethylphenol ("26DMPEP" from Asahi Organic Materials Co., Ltd., molecular weight 182)
B-4: 2-ethyl-4,6-dihydroxymethylphenol ("46DMOEP" from Asahi Organic Materials Co., Ltd., molecular weight 182)
B-5: 4-Fluoro-2,6-dihydroxymethylphenol ("26DMPFP" manufactured by Asahi Organic Materials Co., Ltd., molecular weight 172)
B-6: 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane ("TM-BIP-A" from Asahi Organic Materials Co., Ltd., molecular weight 348)

(Polyhydric phenol compound (C))
The polyhydric phenol compound (C) used in Examples and Comparative Examples is shown below.
C-1: pyrogallol (Kishida Chemical Co., molecular weight 126)
C-2: Catechol (Kishida Chemical Co., molecular weight 110)
C-3: Bis (4-hydroxyphenyl) sulfone (“BS-PN”, Konishi Chemical Industries, Ltd., molecular weight 250)
C-4: Bis (4-hydroxyphenyl) ether (Sakai Kogyo Co., Ltd., molecular weight 202)
C-5: Bis (3,4-dihydroxy-6-methylphenyl) methane (Asahi Organic Materials Corporation, molecular weight 260)

(Crosslinking agent)
The crosslinking agents used in Examples and Comparative Examples are shown below.
E-1: Diethylene glycol diglycidyl ether (“EX-850L”, Nagase ChemteX Corporation, epoxy equivalent 122 g / eq)
E-2: Trimethylolpropane triglycidyl ether ("SR-TMP" of Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent of 137 g / eq)

(Silane coupling agent)
As the silane coupling agent, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd., molecular weight 246) was used.

(Curing catalyst)
As a curing catalyst, 2-methylimidazole (“2MZ-H” of Shikoku Kasei Kogyo Co., Ltd., molecular weight 82) was used.

(Additive)
Ethylene glycol (Wako Pure Chemical Industries, molecular weight 62) was used as an additive having an effect of improving conductivity.

(Binder resin)
As the binder resin, a water-dispersed high molecular weight copolymer polyester resin (Toyobo Co., Ltd., “Vylonal (registered trademark) MD-1200”, solid content concentration: 34% by mass) was used.

(Solvent (D))
As the solvent (D), a mixed solvent of water and isopropyl alcohol (Wako Pure Chemical Industries, Ltd., boiling point 82.5 ° C.) (described as “IPA” in Table 1) was used.

<Formation of conductive film>
300 μL of the coating compositions of the above examples and comparative examples were applied to one surface of a PET film (“Lumirror (registered trademark) T60” manufactured by Toray Industries, Inc., 125 μm thick), and Select-Roller L-60 and OPS-42. (OSG System Products) was used to form a film by the bar coater method. Then, the electroconductive film in which the electroconductive layer was formed was obtained by drying at 120 degreeC for 2 minute (s).

[Evaluation]
<550 nm light transmittance>
The 550 nm light transmittance of the conductive films of Examples and Comparative Examples was measured at room temperature using an ultraviolet-visible spectrophotometer ("U-2800 type spectrophotometer" manufactured by Hitachi High-Technologies Corporation). The results are shown in Table 2.

<Surface resistance value>
The surface resistance values of the conductive films of Examples and Comparative Examples were measured in accordance with JIS-K7194 (1994) using a low resistivity meter ("Loresta-GP MCP-T610" manufactured by Mitsubishi Chemical Analytech Co., Ltd.). Measured at room temperature by the four-terminal method. The results are shown in Table 2.

<Heat and heat resistance>
The moisture and heat resistance of the conductive films of Examples and Comparative Examples is performed by using a thermo-hygrostat (“HIFLEX NEO FX410N” from Enomoto Kasei Co., Ltd.) for 240 hours in an environment of an air temperature of 60 ° C. and a humidity of 95%. The surface resistance value of the sample film before the test was measured, the initial value was compared with the surface resistance value after the test, and the change was evaluated. The initial value of the surface resistance value was taken as 1, and the ratio of the value after the test to the initial value was shown. The results are shown in Table 2.

<Light resistance>
The light resistance of the conductive films of Examples and Comparative Examples was tested by irradiating with ultraviolet light having an irradiation intensity of 10 mW / cm ² for 24 hours using a high-pressure mercury lamp (“HLR100T-2” manufactured by Sen Special Light Company). The surface resistance value of the previous sample film was measured, the initial value was compared with the surface resistance value after the test, and the change was evaluated. The initial value of the surface resistance value was taken as 1, and the ratio of the value after the test to the initial value was shown. The results are shown in Table 2.

<Scratch resistance>
About the damage resistance of the electroconductive film of an Example and a comparative example, it measured with the following method. A load of 100 gf / cm ² was applied to a paper towel (Nippon Paper Crecia Co., Ltd. “Kimwipe (registered trademark)”), and the surface of the conductive layer was rubbed 20 times back and forth, and then the conductive layer was visually evaluated based on the following criteria. did. The results are shown in Table 2.
A: No scratch B: Dozens of scratches C: Countless scratches D: The coating film peels off and disappears completely

<Pencil hardness>
The pencil hardness of the conductive films of Examples and Comparative Examples was measured according to JIS-K5600-5-4: 1999. The conductive layer was visually observed after the scratch test, and the hardness of the hardest pencil that did not cause a state in which the conductive layer cohesively fractured and partly peeled from the base film or partly destroyed was evaluated. The results are shown in Table 2.

  As can be seen from the results in Table 2, the conductive films of Examples 1 to 17 containing the methylolated phenol compound (B) have a light transmittance of 550 nm, surface resistance, moisture and heat resistance, light resistance, scratch resistance, and pencil. It was excellent in both hardness. Thus, it turns out that the electroconductive film of an Example can make electroconductivity and coating-film hardness compatible on a high level.

  On the other hand, the conductive film of Comparative Example 1 containing no methylolated phenol compound (B) and polyhydric phenol compound (C) had low conductivity, heat and humidity resistance, light resistance, and coating film hardness. Further, the conductive film of Comparative Example 2 was excellent in conductivity because it contains ethylene glycol, which is a conventional conductivity improving component, but due to the high boiling point of ethylene glycol, the heat and moisture resistance and the coating film hardness are It was inferior. Moreover, in the electroconductive film of Comparative Examples 3-7 containing only a polyhydric phenol compound (C), although electroconductivity was excellent, the coating-film hardness was inferior. Thus, the conductive film of the comparative example was not able to achieve both conductivity and coating film hardness.

  According to the present invention, a conductive film excellent in conductivity and coating film hardness can be formed at low cost. Moreover, since the conductive film of the present invention is excellent in conductivity, transparency, coating film hardness, light resistance, and moisture and heat resistance, for example, transparent electrodes and electromagnetic wave shielding materials in touch panels, solar cells, electronic paper, flexible light control materials, etc. It can use suitably for etc.

Claims (19)

A conductive film in which a conductive layer containing a conductive polymer compound and a methylolated phenol compound represented by the following formula (1) is laminated on at least one surface of a base film.

(In formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, an alkyl group, an alkoxy group, a cycloalkyl group, an allyl group, or a phenyl group. ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group, and X ¹ is an amide group, an ether group, a carbonyl group, a xyenyl group, a sulfide group, a sulfonyl group, a disulfide group, a cycloalkylene group, or a phenylene group. Or a group represented by the following formula (2): a, b and d are each independently 1 or 2. c is an integer of 0 to 2, and k is 0 to 2. C and k are not simultaneously 0. j is 0 or 1. Further, a, b, c, d and k are represented by the following formulas (I) and (II). ) R ³ , R ⁴ , R ⁵ , when R ⁶ and X ¹ are plural, plural R ³ may be the same or different, plural R ⁴ may be the same or different, and plural R ⁵ may be the same or different. The plurality of R ⁶ may be the same or different, and the plurality of X ¹ may be the same or different.)
2 ≦ a + c + k ≦ 4 (I)
2 ≦ b + d ≦ 3 (II)

(In Formula (2), R ⁷ is a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, or a phenyl group. Y ¹ is a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, or a phenyl group. An adamantyl group or a group represented by the following formula (3), provided that Y ¹ and R ⁷ may be bonded to each other to form a cycloalkane structure or a fluorene structure.)

(In the formula (3), ^{R 8} and ^{R 9} are each independently hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group, a cycloalkyl group, ^{.R 10} an allyl group or a phenyl group, A hydrogen atom, an alkyl group, a cycloalkyl group, a phenyl group or a benzyl group, R ¹¹ is a hydrogen atom or an alkyl group, and e and f are each independently an integer of 0 or more and 2 or less. (III) is satisfied. When e is 2, the plurality of R ¹⁰ may be the same or different. When f is 2, the plurality of R ¹¹ may be the same or different.)
0 ≦ e + f ≦ 3 (III)   In the said Formula (1), k is 0 and c is 2, or k is 1 and c is 1 or 2, The electroconductive film of Claim 1 characterized by the above-mentioned. R ^{1 to} R ⁴ in the above formula (1) are each independently a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, X ¹ is an ether group, a carbonyl group, a sulfide group, a sulfonyl group or the above formula (2). A group represented by
R ⁷ in the above formula (2) is a hydrogen atom, an alkyl group or a fluoroalkyl group, Y ¹ is a hydrogen atom, an alkyl group, a fluoroalkyl group or a group represented by the above formula (3),
The conductive film according to claim 1, wherein R ^{8 to} R ¹¹ in the formula (3) are each independently a hydrogen atom or an alkyl group. The conductive film according to claim 3, wherein the methylolated phenol compound is represented by the following formula (4).

The conductive film according to claim 3, wherein the methylolated phenol compound is represented by the following formula (5).

The conductive film according to claim 3, wherein the methylolated phenol compound is represented by the following formula (6).

  The conductive film according to claim 1, further comprising a dopant that oxidizes or reduces the conductive polymer compound.   The conductive film according to claim 7, wherein the conductive polymer compound is polythiophene or a derivative thereof, and the dopant is an organic sulfonic acid, an organic sulfonic acid metal salt, or an organic sulfonic acid anion.   The conductive film according to claim 8, wherein the conductive polymer compound is poly (3,4-ethylenedioxythiophene) and the dopant is poly (4-styrenesulfonic acid). The conductive film according to any one of claims 1 to 9, wherein the conductive layer further contains a polyhydric phenol compound represented by the following formula (7).

(In the formula ^{(7), R} 12 ~R ¹⁵ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group, an alkoxy group, a cycloalkyl group, an allyl group or a phenyl group .X ² is an amide group, an ether group, a carbonyl group, a xylenyl group, a sulfide group, a sulfonyl group, a disulfide group, a cycloalkylene group, a phenylene group, or a group represented by the following formula (8): g and h are respectively Independently, it is an integer of 1 to 3. n is an integer of 0 to 3. m is an integer of 1 or 2. Further, g and n satisfy the following formula (IV). ^14, when R ¹⁵ and X ² are a plurality of each of the plurality of R ¹⁴ may be the same or different, a plurality of R ¹⁵ may be the same or different, even if a plurality of X ² may be the same or different It has.)
2 ≦ g + n ≦ 4 (IV)

(In the formula (8), R ¹⁶ is a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, or a phenyl group. Y ² is a hydrogen atom, an alkyl group, a fluoroalkyl group, a cycloalkyl group, or a phenyl group. An adamantyl group or a group represented by the following formula (9), provided that Y ² and R ¹⁶ may be bonded to each other to form a cycloalkane structure or a fluorene structure.

(In the formula ^{(9), R 17} and ^{R 18} are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group, a cycloalkyl group, ^{.R 19} an allyl group or a phenyl group, A hydrogen atom, an alkyl group, a cycloalkyl group, a phenyl group or a benzyl group, i is an integer of 0 or more and 3 or less, and when i is 2 or more, a plurality of R ¹⁹ may be the same or different. Good.)   The conductive film according to claim 10, wherein g and h in the formula (7) are 1 or 2, and n is 1. R ^{12 to} R ¹⁵ in the above formula (7) are each independently represented by a hydrogen atom, an alkyl group or an alkoxy group, X ² is represented by an ether group, a carbonyl group, a sulfide group, a sulfonyl group or the above formula (8). Is a group,
R ¹⁶ in the above formula (8) is a hydrogen atom, an alkyl group or a fluoroalkyl group, Y ² is a hydrogen atom, an alkyl group, a fluoroalkyl group or a group represented by the above formula (9),
The conductive film according to claim 10, wherein R ^{17 to} R ¹⁹ in the formula (9) are each independently a hydrogen atom or an alkyl group, and i is 0 or more and 2 or less. The conductive film according to claim 12, wherein the polyhydric phenol compound is represented by the following formula (10).

The conductive film according to claim 12, wherein the polyhydric phenol compound is represented by the following chemical formula (11).

The conductive film according to claim 12, wherein the polyhydric phenol compound is represented by the following formula (12).

  The conductive film according to any one of claims 1 to 15, wherein the conductive layer further contains a solvent, and the solvent is water, an organic solvent, or a mixed solvent of water and an organic solvent.   The conductive film according to any one of claims 1 to 16, wherein the conductive layer further contains a cross-linking agent, and the cross-linking agent is a compound having a group capable of reacting with active hydrogen.   The conductive film according to any one of claims 1 to 17, wherein the conductive layer further contains a binder resin.   The light transmittance at a wavelength of 550 nm is 70% or more, and the surface resistance value measured according to JIS-K7194 (1994) is 1,000 Ω / □ or less. The electroconductive film of description.