JP6130181B2 - Conductive polymer composition and conductor - Google Patents

Description

  The present invention relates to a conductive polymer composition and a conductor formed from the conductive polymer composition.

  As the conductive compound, many organic and inorganic compounds are known.

  As a representative inorganic conductive compound, 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 equipment such as a liquid crystal display, a transparent touch panel, and a solar cell. Such transparent electrodes, electromagnetic shielding materials, and the like are formed by forming an ITO film on the surface of a substrate such as glass or plastic film by a vacuum deposition method, a sputtering method, or the like.

  However, an ITO film formed by a vacuum deposition method, a sputtering method, or the like has a high productivity because of poor productivity. Moreover, since the ITO film is inferior in flexibility, cracks due to bending tend to occur. Furthermore, since indium used for the ITO film is a rare metal, it is disadvantageous in terms of cost.

  On the other hand, π-conjugated polymers such as polypyrrole, polyaniline, and polythiophene are known as organic conductive compounds. Such a π-conjugated polymer is made into a coating solution in which it is dissolved or dispersed in an appropriate solvent, and this is formed by coating, printing, etc., thereby forming a flexible conductive polymer film. (See Patent Document 1).

  However, although the conductive polymer film is superior in productivity and flexibility as compared with an ITO film formed by a vacuum film formation method or the like, the conductivity is low.

  Therefore, as a technique for improving the conductivity of the conductive polymer film, 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. For example, a method using a dispersion of a conductive polymer using a glycol-containing compound such as ethylene glycol as a solvent (see Patent Document 2), or a method of adding a small amount of ethylene glycol to a dispersion of a conductive polymer (non- Patent Document 1) has been proposed.

  When forming a conductive polymer film with a dispersion, it is necessary to dry the coating film formed on the substrate and evaporate the solvent. However, since a solvent such as ethylene glycol has a relatively high boiling point and polarity, when dried in a state containing such a polar solvent, sufficient film hardness cannot be obtained, and consequently, the conductive performance is low. There is an inconvenience of lowering.

  Therefore, while enjoying the advantage of forming a conductive film with an organic conductive compound, that is, the advantage that a flexible conductive film can be formed advantageously in terms of manufacturing cost, higher conductivity is achieved. It is desired that it can be expressed.

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 conductive polymer composition and conductor which can express high electroconductivity.

（式（１）中、Ｒ^１〜Ｒ^６は、それぞれ独立して、水素原子、ハロゲン原子、カルボキシル基、アルキル基、アルコキシ基又はアルコキシカルボニル基である。
Ｒ^７及びＲ^８は、それぞれ独立して、水素原子又はアルキル基である。
Ｘは、アルキレン基、シクロアルキレン基又は下記式（２）で表される基である。
Ｙ^１及びＹ^２は、それぞれ独立して水素原子、アルキル基、シクロアルキル基、フルオレン基、アダマンチル基又は下記式（３）で表される基である。
Ｙ^１とＲ^７とは互いに、又はＹ^２とＲ^８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。
ａ及びｂは、それぞれ独立して１以上３以下の整数、ｍは、０以上３以下の整数、ｎは、０又は１である。）

（式（２）中、Ｒ^９及びＲ^１０は、それぞれ独立して、水素原子、アルキル基、アルコキシ基又はシクロアルキル基であり、ｃは、０以上３以下の整数である。）

（式（３）中、Ｒ^１１及びＲ^１２は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルコキシカルボニル基又はシクロアルキル基であり、ｄは、０以上３以下の整数である。） The invention made to solve the above problems is
It is a conductive polymer composition containing a conductive polymer and a polyhydric phenol compound represented by the following formula (1).

(In Formula (1), R < ¹ > -R < ⁶ > is respectively independently a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.
R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group.
X is an alkylene group, a cycloalkylene group or a group represented by the following formula (2).
Y ¹ and Y ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorene group, an adamantyl group, or a group represented by the following formula (3).
Y ¹ and R ⁷ may be bonded to each other, or Y ² and R ⁸ may be bonded to each other to form a cycloalkane structure or a fluorene structure.
a and b are each independently an integer of 1 to 3, m is an integer of 0 to 3, and n is 0 or 1. )

(In Formula (2), R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or a cycloalkyl group, and c is an integer of 0 or more and 3 or less.)

(In Formula (3), R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group, and d is an integer of 0 or more and 3 or less. .)

The said conductive polymer composition contains the polyhydric phenol compound represented by the said Formula (1). Therefore, the conductive polymer composition can provide a conductor such as a conductive film that can exhibit high conductivity.
Moreover, since the said conductive polymer composition can express high electroconductivity, the target electroconductivity is realizable with a small addition amount. Therefore, the manufacturing cost of the conductor can be suppressed.
Furthermore, since the conductive polymer composition does not use a rare metal such as indium, a flexible conductive film can be formed advantageously in terms of manufacturing cost.

  In the above formula (1), a and b are preferably 2 or 3, and m is preferably 0 or 1. By containing such a polyhydric phenol compound, a conductor such as a conductive film that can exhibit high conductivity can be provided more reliably. In particular, when m is 0 or 1, the solubility in a solvent is increased and the handling becomes easy. Further, by setting a and b to 2 or 3, in addition to increasing the solubility in a solvent, it is possible to more effectively express higher conductivity.

R ^{1 to} R ⁸ in the above formula (1) are each independently a hydrogen atom or an alkyl group, Y ¹ is a hydrogen atom, an alkyl group or a group represented by the above formula (3), and Y ² is a hydrogen atom. An atom or an alkyl group, X is a group represented by the above formula (2);
R ⁹ and R ¹⁰ in the above formula (2) are each independently a hydrogen atom or an alkyl group, c is an integer of 0 or more and 2 or less,
R ¹¹ and R ¹² in the above formula (3) are each independently a hydrogen atom or an alkyl group, and d is preferably an integer of 0 or more and 2 or less.

  When the above formula (1), the above formula (2), and the above formula (3) satisfy the above conditions, the solubility in a solvent is increased, the handleability can be improved, and a conductive film that can exhibit high conductivity, etc. In addition to being able to advantageously provide the conductive material in terms of production cost, it is possible to provide a stable composition with less hue change in the air and in the solvent.

As the polyhydric phenol compound, 2,6-bis [(2,4-dihydroxyphenyl) methyl] -4-methylphenol represented by the following formula (4) is preferable, and represented by the following formula (5). [Bis (3,4-dihydroxy-6-methylphenyl) methyl] benzene is preferred. By containing such a polyhydric phenol compound, a composition having high stability and solubility can be provided, and a conductor capable of exhibiting high conductivity can be advantageously provided in terms of production cost.

  The conductive polymer composition may further contain a dopant that oxidizes or reduces the conductive polymer. By containing such a dopant, the conductivity of the conductor formed from the conductive polymer composition can be further improved.

  The conductive polymer and the dopant form a poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonic acid) complex (hereinafter sometimes abbreviated as “PEDOT / PSS”). It is preferable. By containing such a composite, a conductor capable of exhibiting high conductivity can be advantageously provided in terms of production cost.

  The conductive polymer composition further contains a solvent, and the solvent is preferably a mixed solvent of alcohol and water. Such a solvent has a relatively high volatility and a relatively low polarity. By containing such a solvent, sufficient hardness can be obtained, so that a conductor that can exhibit high conductivity can be provided more reliably.

  The conductive polymer composition may further contain a binder resin. By containing such a binder resin, sufficient film hardness can be obtained, so that a conductor that can exhibit high conductivity can be provided. In addition, when a conductor is formed on the surface of a substrate or the like, it is possible to improve adhesion with the substrate or the like while achieving sufficient strength.

Another invention made to solve the above problems is as follows:
It is the conductor formed from the said conductive polymer composition.

  Since the said conductor is formed from the said conductive polymer composition, it has high electroconductivity and flexibility and can be manufactured advantageously in cost.

  The conductor is preferably a stacked body in which a plurality of conductive layers are stacked. Such a laminate is applied to electrodes, wirings, pads, etc. of circuit boards and wiring boards. Therefore, a conductor such as an electrode having high conductivity can be advantageously provided in terms of cost.

  The conductor is preferably formed as a conductive film. Such a conductive film is applied to electrodes, wirings, pads, etc. of circuit boards and wiring boards. Therefore, a conductor such as an electrode having high conductivity can be advantageously provided in terms of cost.

  ADVANTAGE OF THE INVENTION According to this invention, the electroconductive polymer composition which can manufacture the conductor which has high electroconductivity and flexibility advantageously in cost can be provided.

It is typical sectional drawing for demonstrating the laminated body which is an example of the conductor of this invention. It is typical sectional drawing for demonstrating the electroconductive film and via conductor which are the other examples of the conductor of this invention. It is typical sectional drawing for demonstrating the via conductor which is another example of the conductor of this invention. It is the graph which plotted the compound molar ratio of component (B) / component (A) on the X-axis, and the surface resistance value (Ω / □) of the conductive film on the Y-axis.

  Hereinafter, the conductive polymer composition (X) and the conductor of the present invention will be described in detail.

[Conductive polymer composition (X)]
The conductive polymer composition (X) contains the conductive polymer (A) and the polyhydric phenol compound (B) represented by the above formula (1). The conductive polymer composition (X) may contain suitable components such as a dopant, a solvent, a binder resin, and other optional components as long as the gist of the present invention is not impaired. Hereinafter, these components will be described in detail.

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

(Conjugated polymer)
Conjugated polymers include polyacetylene, polydiacetylene, polyparaphenylene, polyfluorene, polyazulene, polyparaphenylene sulfide, polypyrrole, polythiophene, polyisothianaphthene, polyaniline, polyparaphenylene vinylene, poly (2,5-thienylene. Vinylene), double-chain conjugated polymers (such as polyperinaphthalene), metal phthalocyanine 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 in this case include an alkyl group, a carboxyl group, a sulfo group, an alkoxyl group, a hydroxyl group, and a cyano group.

  Examples of the conjugated polymer into which such a 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-bromo Thiophene), 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), polyaniline, poly (2-methylaniline), poly (3-isobutylaniline) , Poly (2-anilinesulfonic acid), poly (3-anilinesulfonic acid) and the like.

  Among the conjugated polymers, a polymer containing at least one selected from the group consisting of polythiophene, poly (3,4-ethylenedioxythiophene), polypyrrole, and polyaniline is preferable in terms of conductivity and reactivity. . As the conjugated polymer, poly (3,4-ethylenedioxythiophene) and polypyrrole are more preferable from the viewpoint of higher electrical conductivity and improved heat resistance, and poly (3,4-ethylenedioxythiophene). Is particularly preferred.

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

In said formula (1), R < ¹ > -R < ⁶ > is respectively independently a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group, and a hydrogen atom or an alkyl group is preferable.
R ⁷ and R ⁸ are each independently a hydrogen atom or an alkyl group.
X is an alkylene group, a cycloalkylene group or a group represented by the following formula (2), and a group represented by the above formula (2) is preferable.
Y ¹ and Y ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorene 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, or Y ² and R ⁸ may be bonded to each other to form a cycloalkane structure or a fluorene structure. Y ¹ is preferably a hydrogen atom, an alkyl group or a group represented by the above formula (3), and Y ² is preferably a hydrogen atom or an alkyl group.
a and b are each independently an integer of 1 to 3, m is an integer of 0 to 3, and n is 0 or 1. a and b are preferably 2 or 3, and m is preferably 0 or 1. If a and b are 2 or 3, in addition to the high solubility to a solvent, the effect of a higher electroconductivity improvement can be expressed. On the other hand, if m is 0 or 1, the solubility in a solvent is high and handling is easy.

In said formula (2), R < ⁹ > and R < ¹⁰ > are respectively independently a hydrogen atom, an alkyl group, an alkoxy group, or a cycloalkyl group. R ⁹ and R ¹⁰ are preferably a hydrogen atom or an alkyl group. c is an integer of 0 or more and 3 or less. c is preferably an integer of 0 or more and 2 or less.

In the above formula (3), R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or a cycloalkyl group. R ¹¹ and R ¹² are each independently preferably a hydrogen atom or an alkyl group. d is an integer of 0 or more and 3 or less. d is preferably an integer of 0 or more and 2 or less.

Examples of the halogen atom represented by R ^{1 to} R ⁶ include a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. Is mentioned.
Examples of the alkoxy group include 1 to 4 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group. Of the alkoxy group.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, sec-
Examples thereof include alkoxycarbonyl groups having 2 to 5 carbon atoms such as butoxycarbonyl group and tert-butoxycarbonyl group.

Examples of the alkyl group represented by R ⁷ and R ⁸ include the same groups as R ^{1 to} R ⁶ .

Examples of the alkylene group represented by X include alkylene groups having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, and a butylene group.
Examples of the cycloalkylene group include a cyclohexylene group.

Examples of the alkyl group represented by Y ¹ and Y ² include the same groups as R ^{1 to} R ⁶ .
Examples of the cycloalkyl group include a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.

Examples of the alkyl group and alkoxy group represented by R ⁹ and R ¹⁰ include the same groups as R ^{1 to} R ⁶ .
Examples of the cycloalkyl group include those similar to Y ¹ and Y ⁶ .

Examples of the halogen atom, alkyl group, alkoxy group and alkoxycarbonyl group in R ¹¹ and R ¹² include the same groups as those in R ^{1 to} R ⁶ .
Examples of the cycloalkyl group include those similar to Y ¹ and Y ⁶ .

Examples of the polyhydric phenol compound (B) represented by the above formula (1) include
Bis (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, bis (3,4-dihydroxyphenyl) 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 (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 (2,4-dihydroxyphenyl) propane, 1,1-bis (3 -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-methylphenyl) 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 (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-dihydroxy Phenyl) butane, [bis (4-hydroxyphenyl) 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-methyl) Phenyl) 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] , [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 (2,4-dihydroxyphenyl) methyl] phenol, 2- [bis (3,4-dihydroxyphenyl) methyl] phenol, 2- [bis (2,5-dihydroxy) Phenyl) methyl] phenol, 2- [bis (2,3,4-trihydroxyphenyl) methyl] phenol, 2- [bis (3,4-dihydroxy-6-methylphenyl) methyl] phenol, 2- [bis ( 2,4-dihydroxy-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 (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 (2,4-dihydroxyphenyl) methyl] 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- [bis (4-hydroxyphenyl) 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-dihydro) Ci-3-methylphenyl) methyl] resorcinol, 4- [bis (2,4-dihydroxy-5-methylphenyl) methyl] resorcinol, 4- [bis (3-hexyl-4,6-dihydroxyphenyl) methyl] 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 (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-methylphenyl) 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 (2,4-dihydroxyphenyl) methyl]- 2-methoxyphenol, 4- [bis (3,4-dihydroxyphenyl) methyl] -2-methoxyphenol, 4- [bis (2,5-dihydroxyphenyl) 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, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, α, α, α ′, α′-tetrakis (4-hydroxyphenyl) -p-xylene, α, α, α ′ , Α′-tetrakis (3,4-dihydroxy-6-methylphenyl) -p-xylene, α, α-bis (2,4-dihydroxyphenyl) -α ′, α′-bis (3,4-dihydroxy- 6-methylphenyl) -p-xylene, α, α-bis (2,3,4-trihydroxyphenyl) -α ′, α′-bis (3,4-dihydroxy-6-methylphenyl) -p-xylene , Α, α-bis (2,4-dihydroxy-3-methylphenyl) -α ′, α′-bis (3,4-dihydroxy-6-methylphenyl) -p-xylene, 2,2-bis (4 -Hydroxy-phenyl) 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 (3,4-dihydroxy-6-methylphenyl) cyclohexane, 9,9-bis (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- Hydroxy-6-methylphenyl) -1-adamantylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (2,4-dihydroxyphenyl) -1-phenylethane, , 1-bis (3,4-dihydride)
Loxyphenyl) -1-phenylethane, 1,1-bis (2,5-dihydroxyphenyl) -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, 1,1-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 (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, 1,1,1-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) ethane, 1,1-bis (3,4-dihydroxy-6-methylphenyl) -1- (2,4-dihydroxyphenyl) ethane, 1,1-bi (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, 2,4-bis [(4-hydroxyphenyl) methyl] -6-methylphenol, 2,4-bis [(2,4-dihydroxyphenyl) Methyl] -6-methylphenol, 2,4-bis [(3,4-dihydroxyphenyl) methyl] -6-methylphenol, 2,4-bis [(2,5-dihydroxyphenyl) Nyl) methyl] -6-methylphenol, 2,4-bis [(2,3,4-trihydroxyphenyl) methyl] -6-methylphenol, 2,4-bis [(3,4-dihydroxy-6- Methylphenyl) methyl] -6-methylphenol, 2,4-bis [(2,4-dihydroxy-3-methylphenyl) methyl] -6-methylphenol, 2,4-bis [(2,4-dihydroxy- 5-methylphenyl) methyl] -6-methylphenol, 2,4-bis [(3-hexyl-4,6-dihydroxyphenyl) methyl] -6-methylphenol, 2,4-bis [(3-chloro- 4,6-dihydroxyphenyl) methyl] -6-methylphenol, 2,6-bis [(4-hydroxyphenyl) 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-methylphenol, 2,6-bis [(2,4-dihydroxy-5-methyl) Phenyl) 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, 2,6-bis [(4-hydroxyphenyl) 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-butylphenol, 2,6-bis [(2,4-dihydroxy-3- Tylphenyl) 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, 2,4-bis [(4 -Hydroxyphenyl) methyl] -6-cyclohexylphenol, 2,4-bis [(2,4-dihydroxyphenyl) methyl] -6-cyclohexylphenol, 2,4-bis [(3,4-dihydroxyphenyl) methyl] -6-cyclohexylphenol, 2,4-bis [(2,5-dihydroxyphenyl) methyl] 6-cyclohexylphenol, 2,4-bis [(2,3,4-trihydroxyphenyl) methyl] -6-cyclohexylphenol, 2,4-bis [(3,4-dihydroxy-6-methylphenyl) methyl] -6-cyclohexylphenol, 2,4-bis [(2,4-dihydroxy-3-methylphenyl) methyl] -6-cyclohexylphenol, 2,4-bis [(2,4-dihydroxy-5-methylphenyl) Methyl] -6-cyclohexylphenol, 2,4-bis [(3-hexyl-4,6-dihydroxyphenyl) methyl] -6-cyclohexylphenol, 2,4-bis [(3-chloro-4,6-dihydroxy) Phenyl) methyl] -6-cyclohexylphenol, 2,6-bis [(4-hydroxyphenyl) methyl] -4 -Cyclohexylphenol, 2,6-bis [(2,4-dihydroxyphenyl) methyl] -4-cyclohexylphenol, 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-cyclohexylpheno 2,6-bis [(3-hexyl-4,6-dihydroxyphenyl) methyl] -4-cyclohexylphenol, 2,6-bis [(3-chloro-4,6-dihydroxyphenyl) methyl] -4 -Cyclohexylphenol, bis [4-hydroxy-3- (4-hydroxyphenyl) methyl-5-methylphenyl] methane, bis [4-hydroxy-3- (2,4-dihydroxyphenyl) methyl-5-methylphenyl] Methane, bis [4-hydroxy-3- (3,4-dihydroxyphenyl) methyl-5-methylphenyl] methane, bis [4-hydroxy-3- (2,5-dihydroxyphenyl) methyl-5-methylphenyl] Methane, bis [4-hydroxy-3- (2,3,4-trihydroxyphenyl) methyl-5-methylphenyl] Tan, bis [4-hydroxy-3- (3,4-dihydroxy-6-methylphenyl) methyl-5-methylphenyl] methane, bis [4-hydroxy-3- (2,4-dihydroxy-3-methylphenyl) ) Methyl-5-methylphenyl] methane, bis [4-hydroxy-3- (2,4-dihydroxy-5-methylphenyl) methyl-5-methylphenyl] methane, bis [4-hydroxy-3- (3- Hexyl-4,6-dihydroxyphenyl) methyl-5-methylphenyl] methane, bis [4-hydroxy-3- (3-chloro-4,6-dihydroxyphenyl) methyl-5-methylphenyl] methane, bis [2 -Hydroxy-3- (4-hydroxyphenyl) methyl-5-methylphenyl] methane, bis [2-hydroxy-3- (2,4-dihydro) Droxyphenyl) methyl-5-methylphenyl] methane, bis [2-hydroxy-3- (3,4-dihydroxyphenyl) methyl-5-methylphenyl] methane, bis [2-hydroxy-3- (2,5 -Dihydroxyphenyl) methyl-5-methylphenyl] methane, bis [2-hydroxy-3- (2,3,4-trihydroxyphenyl) methyl-5-methylphenyl] methane, bis [2-hydroxy-3- ( 3,4-dihydroxy-6-methylphenyl) methyl-5-methylphenyl] methane, bis [2-hydroxy-3- (2,4-dihydroxy-3-methylphenyl) methyl-5-methylphenyl] methane, bis [2-Hydroxy-3- (2,4-dihydroxy-5-methylphenyl) methyl-5-methylphenyl] methane, bis [ -Hydroxy-3- (3-hexyl-4,6-dihydroxyphenyl) methyl-5-methylphenyl] methane, bis [2-hydroxy-3- (3-chloro-4,6-dihydroxyphenyl) methyl-5- Methylphenyl] methane, 1,4-bis [(4-hydroxyphenyl) 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, 1,3-bis (4-hydroxy-α, α-dimethylbenzyl) benzene, 1,3-bis (2,4-dihydroxy- α, α-dimethylbenzyl) benzene, 1,3-bis (3,4-dihydroxy-α, α-dimethylbenzyl) benzene, 1,3-bis (2,5-dihydroxy-α, α-dimethylbenzyl) benzene 1,3-bis (2,3,4-trihydroxy-α, α-dimethylbenzyl) benzene, 1,3-bis (3,4-dihydroxy-6-methyl-α, α-dimethylbenzyl) ) Benzene, 1,3-bis (2,4-dihydroxy-3-methyl-α, α-dimethylbenzyl) benzene, 1,3-bis (2,4-dihydroxy-5-methyl-α, α-dimethylbenzyl) ) Benzene, 1,3-bis (3-hexyl-4,6-dihydroxy-α,
α-dimethylbenzyl) benzene, 1,3-bis (3-chloro-4,6-dihydroxy-α, α-dimethylbenzyl) benzene, 1,4-bis (4-hydroxy-α, α-dimethylbenzyl) benzene 1,4-bis (2,4-dihydroxy-α, α-dimethylbenzyl) benzene, 1,4-bis (3,4-dihydroxy-α, α-dimethylbenzyl) benzene, 1,4-bis (2 , 5-Dihydroxy-α, α-dimethylbenzyl) benzene, 1,4-bis (2,3,4-trihydroxy-α, α-dimethylbenzyl) benzene, 1,4-bis (3,4-dihydroxy-) 6-methyl-α, α-dimethylbenzyl) benzene, 1,4-bis (2,4-dihydroxy-3-methyl-α, α-dimethylbenzyl) benzene, 1,4-bis (2,4-dihydroxy) -5-methyl-α, α-dimethylbenzyl) benzene, 1,4-bis (3-hexyl-4,6-dihydroxy-α, α-dimethylbenzyl) benzene, 1,4-bis (3-chloro-4) , 6-dihydroxy-α, α-dimethylbenzyl) benzene and the like.

Above all, because there is little coloring and solubility in a solvent is high,
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-methyl) Phenyl) methyl] catechol, 2,2-bis (3,4-dihydroxy-6-methylphenyl) propane, 2,2-bis (2,4-dihydroxy-3-methylphenyl) propane, 2,4-bis [ (2,4-dihydroxyphenyl) methyl] -6-methylphenol, 2,4-bis [(2,3,4-trihydroxyphenyl) methyl] 6-methylphenol, 2,4-bis [(3,4-dihydroxy-6-methylphenyl) methyl] -6-methylphenol, 2,4-bis [(2,4-dihydroxy-3-methylphenyl) methyl ] -6-methylphenol, 2,6-bis [(2,4-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-Methylphenol is preferred.

  The polyhydric phenol compound (B) is 2,6-bis [(2,4-dihydroxyphenyl) methyl] -4-methylphenol represented by the following formula (4), represented by the following formula (5). [Bis (3,4-dihydroxy-6-methylphenyl) methyl] benzene is more preferred. These polyhydric phenol compounds (B) are preferable because, in addition to the above characteristics, there is little change in hue in the air and in the solution, and the stability is high.

(Production method of polyhydric phenol compound (B))
The polyhydric phenol compound (B) can be produced, for example, by a condensation reaction of phenols and aldehydes. Such a condensation reaction is known and is performed in the presence of an acid catalyst or a base catalyst.

  For example, an excess amount in the range of 1 mol to 30 mol of phenol with respect to 1 mol of aldehyde is dissolved in a solvent such as water or an organic solvent (alcohol, ether, etc.), and an acid catalyst (hydrochloric acid, sulfuric acid, phosphoric acid, etc.) And a cocatalyst (such as mercaptoacetic acid, 3-mercaptopropionic acid) or a base catalyst (such as sodium hydroxide, potassium hydroxide, potassium carbonate, triethylamine) that suppresses by-products is 0 at 30 ° C. to 150 ° C. .React for 5 hours to 48 hours. The remaining amount of aldehydes or phenols was tracked by a known method such as gas chromatography, thin layer chromatography, liquid chromatography, gel filtration chromatography, IR analysis, etc., and the peak area indicating the remaining amount was not decreased. The end point of the reaction is determined by the time point.

  After completion of the reaction, the reaction mixture is cooled to about room temperature, neutralized with a neutralizing agent, and 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 (B) is obtained by separating the precipitate by filtration, purifying it by washing with water, recrystallization, etc., if necessary, and drying.

As the above phenols,
Phenol, orthocresol, metacresol, paracresol, hydroquinone, methylhydroquinone, methoxyhydroquinone, catechol, 3-methylcatechol, 3-methoxycatechol, 4-methylcatechol, 4-tert-butylcatechol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, 4-hexylresorcinol, 4-methoxyresorcinol, 4-chlororesorcinol, 5-methylresorcinol, 5-methoxyresorcinol, pyrogallol, 5-methylpyrogallol, phloroglicidol, 1,2,4-trihydroxybenzene, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,4,6-trihis Loxybenzoic acid, 3,4,5-trihydroxybenzoic acid, methyl 2,4-dihydroxybenzoate, methyl 2,6-dihydroxybenzoate, methyl 3,4-dihydroxybenzoate, methyl 3,5-dihydroxybenzoate , Methyl 2,4,6-trihydroxybenzoate, methyl 3,4,5-trihydroxybenzoate and the like.

  Among them, since a polyhydric phenol compound (B) having high reactivity with aldehydes and high solubility in a solvent can be obtained, phenol, hydroquinone, catechol, 4-methylcatechol, resorcinol, 2-methylresorcinol, pyrogallol Is preferred. You may use the said phenols individually or in combination of 2 or more types.

As the aldehydes,
Aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, n-hexylaldehyde, cyclohexanecarbaldehyde, glyoxal, glutaraldehyde;
Benzaldehyde, 4-ethylbenzaldehyde, 4-tert-butylbenzaldehyde, salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, vanillin, Aromatic aldehydes such as cinnamylaldehyde, terephthalaldehyde, isophthalaldehyde;
Etc.

  Among them, formaldehyde, benzaldehyde, and 3,4-dihydroxybenzaldehyde are preferable because a product with less coloration can be obtained in the reaction with the phenols.

Also, ketones can be used in place of the aldehydes.
As ketones in this case,
Aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 1-acetyladamantane;
Acetophenone, 4-hydroxyacetophenone, 2,4-dihydroxyacetophenone, 3,5-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 2,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyacetophenone Aromatic ketones such as fluorenone and 1,4-diacetylbenzene;
Etc.

  Among these, acetone, cyclohexanone, acetophenone, 4-hydroxyacetophenone, and 2,4-dihydroxyacetophenone are preferable because a product having high solubility in a solvent can be obtained in the reaction with the phenols.

Furthermore, methylolated phenols can be used in place of the aldehydes or the ketones.
As methylolated phenols in this case,
2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, 2,6-dihydroxymethyl-3,4-dimethylphenol, 2,4-dihydroxymethyl-5,6-dimethyl Phenol, 4-tert-butyl-2,6-dihydroxymethylphenol, 4-cyclohexyl-2,6-dihydroxymethylphenol, 2-cyclohexyl-4,6-dihydroxymethylphenol, 4-ethyl-2,6-dihydroxy Methylphenol, 2-ethyl-4,6-dihydroxymethylphenol, 2-isopropyl-4,6-dihydroxymethylphenol, 2-cyclohexyl-4,6-dihydroxymethyl-3-methylphenol, bis (2-hydroxy-3 -Hydroxymethyl-5-methyl Enyl) methane, bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, bis (4-hydroxy-3-hydroxymethyl-5,6-dimethylphenyl) methane, 2,2-bis (4- Hydroxy-3,5-dihydroxymethylphenyl) propane and the like.

  Among these, 2,6-dihydroxymethyl-4-methylphenol and 2,4-dihydroxymethyl-6 can be obtained in the reaction with the above phenols because a product with little coloring and high solubility in a solvent can be obtained. -Methylphenol is preferred.

  In addition to the aldehydes, the ketones, and the methylolated phenols, paraxylene glycol, 1,4-bis (1-hydroxy-1-methylethyl) benzene, 1,3-bis (1-hydroxy-1- Aromatic methanol such as methylethyl) benzene may be used.

  The content of the polyhydric phenol compound (B) in the conductive polymer composition (X) is preferably 0.001 mol or more and 10 mol or less with respect to 1 mol of the conductive polymer (A), 0.01 mol More preferably, it is 5 mol or less. When the content is within the above range, the conductivity can be appropriately improved.

<Dopant>
A dopant is a suitable component in electroconductive polymer composition (X), and is added in order to improve electroconductivity more. Since this dopant oxidizes or reduces the conductive polymer (A), the dispersibility of the conjugated polymer in the solvent is improved. Since conductors such as conductive films are often formed by coating and drying, the conductive film having uniform conductivity can be obtained by improving the dispersibility of the conjugated polymer in the solvent. It becomes possible to form.

  As a dopant, both a donor dopant and an acceptor dopant can be used as long as the conductive polymer (A) can be oxidized or reduced.

  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 acceptor dopants include halogen compounds (Cl ₂ , Br ₂ , I ₂ , ICl, IBr, IF, etc.), Lewis acids (PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , BBr ₃ , SO _3, etc.). ), Protonic acid (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, phenols ), Transition metal compounds (FeCl ₃ , FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaCl ₅ , MoF ₅ , MoCl ₅ , WF ₆ , WCl _6, etc.), electrolyte anions (Cl ^{_{-, Br -, I -,}} ClO 4 -, PF 6 -, AsF 6 -, SbF 6 -, BF 4 -, inorganic sul Acid anions, organic sulfonate anions, etc.), fullerenes (hydrogenated fullerene, hydroxide fullerene, carboxylic acid fullerene, sulfonated fullerene, etc.), organic cyano compounds (tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, etc.), etc. Is mentioned.

  Although it does not specifically limit as content of a dopant, 0.00001 mass part or more and 1000 mass parts or less are preferable with respect to 100 mass parts of conductive polymers (A), and it says that the stability of dope state and electroconductivity are made compatible. From the point, 0.001 to 500 parts by mass is more preferable.

  When the dopant is added, the conductive polymer (A) has high stability in the doped state, so that polythiophenes (polythiophene and its derivatives), organic sulfonic acid, organic sulfonic acid metal salt, organic sulfonic acid anion A combination with a sulfonic acid compound such as is preferred. Among them, the aqueous dispersion can be adjusted, the conductive thin film can be easily adjusted by coating, and the transparency after forming the coating film is high, so that poly (3-styrenesulfonic acid) doped poly (3, 4-ethylenedioxythiophene) (hereinafter referred to as “PEDOT / PSS”) is more preferable. Moreover, as PEDOT / PSS, the commercial item (for example, product number "483095" by Aldrich) containing the water dispersion containing 1.3 weight% of PEDOT / PSS polymers can be obtained.

<Solvent>
The solvent is a suitable component in the conductive polymer composition (X). For example, the conductive polymer (A) is dissolved or dispersed in the conductive polymer composition (X), and the polyhydric phenol compound (B ) Is used for the purpose of dissolving.

  Examples of the solvent include water, an organic solvent, a mixed solvent of water and an organic solvent, and the like, and a mixed solvent of water and an organic solvent is preferable. According to this mixed solvent, the polyphenol compound (B) is excellent in solubility and a good conductive film can be obtained.

The organic solvent is preferably soluble in water. As the organic solvent soluble in water, any solvent can be used as long as it becomes a uniform solution when mixed with water.
Alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol;
Ketones such as acetone;
Ethylene glycols such as ethylene glycol methyl ether; propylene glycols such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol propyl ether;
Amides such as N, N-dimethylformamide and N, N-dimethylacetamide;
Pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; Two or more kinds of these water-soluble organic solvents may be used in combination. Among these, isopropyl alcohol is preferable from the viewpoint of drying the conductive polymer composition and safety.

  When a mixed solvent of water and alcohol is used, the ratio of water and alcohol is not particularly limited, but the conductive polymer (A) is dissolved or dispersed to dissolve the polyhydric phenol compound (B). From the point of achieving both, it is preferable that alcohol is 5 mass parts or more and 500 mass parts or less with respect to 100 mass parts of water, and 10 mass parts or more and 200 mass parts or less are more preferable.

  The content of the conductive polymer (A) in the conductive polymer composition (X) is preferably 0.001 to 20 parts by mass, and 0.005 to 10 parts by mass with respect to 100 parts by mass of the solvent. Less than the mass part is more preferable. When the content is 0.001 part by mass or more, sufficient conductivity is exhibited, and when it is 20 parts by mass or less, the viscosity of the resin composition can be prevented from becoming too high, and the handling is easy.

<Binder resin>
The binder resin is a suitable component in the conductive polymer composition (X). For example, to increase the scratch resistance, surface hardness, etc. of a conductor such as a conductive film formed from the conductive polymer composition (X). To be added. Further, the binder resin can play a role of improving the adhesion between the conductor and the substrate when the conductor is formed on the substrate or the like.

The binder resin may be a thermosetting resin or a thermoplastic resin. As the binder resin, for example,
Polyvinyl alcohol, polyvinyl acetal, polyvinyl ether, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl resin such as polyvinyl chloride, polyacetal resin, polyester resin, acrylic resin, polyacrylamide resin, polyimide resin, polyamide resin, alkyd resin, xylene resin, aramid Resin, polyimide silicone resin, 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.

  The binder resin may be added as it is when the conductive polymer composition (X) is prepared. However, the binder resin is added with a functional group such as a sulfonic acid group or a carboxylic acid group dissolved in an organic solvent. What is necessary is just to add in the state disperse | distributed in water like the emulsion state and emulsion.

  Among the binder resins, one or more of polyester resins, acrylic resins, polyimide resins, polyamide resins, epoxy resins, and urethane resins are preferable because they can be easily mixed.

  When the conductive polymer composition (X) contains a binder resin and a solvent, the content of the binder resin is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the solvent, and 1 part by mass or more and 30 parts by mass. Less than the mass part is more preferable. When the content of the binder resin is 1 mass or more, the strength of the obtained conductive film is improved, and when it is 50 mass parts or less, the increase in viscosity of the conductive polymer composition (X) due to the binder resin can be prevented. Easy to handle.

<Method for producing conductive polymer composition (X)>
The conductive polymer composition (X) can be produced by mixing the conductive polymer (A), the polyhydric phenol compound (B), and, if necessary, a dopant and a binder resin with a solvent in an arbitrary order. . A known stirrer can be used for mixing each component.

  In addition to the dopant, the solvent, and the binder resin, the conductive polymer composition (X) may be mixed with a known additive, a known conductivity improving component, and the like as optional components.

  The known additives include surfactants, thickeners, dyes, curing catalysts, rheology control agents, resin fine particles, inorganic fine particles, silane coupling agents, antifoaming agents, surface conditioners, ultraviolet absorbers, and antioxidants. Agents, antiseptics, fungicides, plasticizers and the like.

  As the known conductivity improving component, a known component can be used. For example, a compound containing two or more hydroxy groups in the molecule can be used. Examples of such conductivity improving components include ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, sugar (such as fructose), hydroquinone, catechol, pyrogallol, gallic acid and the like.

  As content of the said electroconductivity improvement component, 0.01 mol or more and 10 mol or less are preferable with respect to 1 mol of conductive polymers (A), and 0.1 mol or more and 5 mol or less are more preferable.

  Since conductive polymer composition (X) contains a polyhydric phenol compound (B), it can express high electroconductivity. About this reason, it guesses as follows.

  Since the polyhydric phenol compound (B) contains two or more hydroxyl groups in the molecule, like ethylene glycol which is a known conductivity improving component, it forms a hydrogen bond with the conductive polymer (A). . As a result, the conductive polymers (A) come closer to each other, and the energy required for electrical conduction is reduced. Therefore, it is considered that the electrical resistance of the conductive film is reduced and the conductivity is increased. Since the polyhydric phenol compound (B) interacts more strongly with the conductive polymer (A), it is considered that a higher conductivity improvement effect is exhibited.

  Moreover, since the polyhydric phenol compound (B) contains two or more hydroxy groups, it has radical scavenging ability and acts as an antioxidant. Therefore, radicals generated by oxidative degradation of the conductive polymer (A) can be deactivated, and progress of the degradation can be suppressed, so that the heat resistance and stability of the conductive film are considered to be increased.

  Furthermore, the polyhydric phenol compound (B) has a structure containing two or more aromatic rings in the molecule, but is less colored and highly soluble in a solvent. Therefore, it is considered that the coating characteristics are excellent and the hardness of a conductor such as a conductive film is increased.

[conductor]
The conductor of the present invention is formed from the conductive polymer composition (X). The said conductor is formed in the surface of a base material as a laminated body, a electrically conductive film, etc. which consist of a some conductive layer, for example. Of course, the conductor can be formed on a surface other than the surface of the base material as in a via conductor described later.

  It does not specifically limit as said base material, What is necessary is just to select according to a use. Examples of the base material include a polymer compound, wood, paper material, ceramics, and glass.

  Examples of the polymer compound include polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyester, polyamide, polyimide, polyaramid, polyphenylene sulfide, poly Examples include ether ether ketone, polyphenylene ether, polyether nitrile, polyamide imide, polyether sulfone, polysulfone, polyether imide, polyethylene terephthalate, polybutylene terephthalate, and polyurethane.

  Examples of the form of the substrate include a film shape, a plate shape, and a block shape, and can also be configured as a foam, an elastomer, and the like. These base materials may be subjected to surface treatment such as corona discharge treatment or plasma treatment for the purpose of improving the adhesion of the conductor on the surface on which the conductor such as a conductive film is formed.

  As a method for applying the conductive polymer composition (X) to the substrate, a method used for general coating can be used. Examples of coating methods include gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, phanten coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, screen coater, etc. Application such as spraying, spraying such as spray coating, dipping or the like is used.

  Drying after applying the conductive polymer composition (X) to the substrate may be performed by allowing it to stand at room temperature or by performing a heat treatment. As the heat treatment, for example, a normal method such as hot air heating or infrared heating is used. The temperature for the heat treatment is preferably 40 ° C. or higher and 250 ° C. or lower. When heating temperature is less than 40 degreeC, when conductive polymer composition (X) contains a solvent, there exists a possibility that the solvent may remain so that electroconductivity may not fully be exhibited. Moreover, when heating temperature exceeds 250 degreeC, there exists a possibility that degradation of a conductive polymer (A) may arise and electroconductivity may fall.

  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 ultra high 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.

  Since the conductor of the present invention is excellent in conductivity, it can be suitably used as a circuit board, wiring board, wiring for electronic parts, pads, and the like. In addition, since the conductor of the present invention can be formed by coating, it is easy to produce a large-area electrode and is suitable for application to electrodes on various substrates. As a result, the conductive polymer composition (X) and the conductor of the present invention are a flexible electroluminescence device (organic EL), a touch screen, a touch panel, an organic TFT, an actuator, a sensor, electronic paper, a flexible light control material, and the sun. It can be suitably used for various devices such as batteries.

  Next, specific examples of the conductor will be described with reference to FIGS.

  The conductor is formed, for example, as the multilayer body 1 shown in FIG. 1 or the wirings 20 and 21, the pads 22, and the via conductors 23 in the wiring board 2 shown in FIG. 2. The wirings 20 and 21 and the pad 22 correspond to an example of a conductive film.

  A laminate 1 in FIG. 1 is formed on a substrate 12 and is formed by laminating a plurality of conductive layers 10 and 11. Such a laminate 1 is applied, for example, to circuit boards, wiring boards, wiring of electronic components, pads, and the like, and is applied as an electromagnetic shielding material for liquid crystal displays, transparent touch panels, solar cells, and the like.

  Laminate 1 applies a coating solution prepared from conductive polymer composition (X) onto substrate 12, and dries it to form one conductive layer 10, 11 according to the number of layers. Can be formed by repeating the process a plurality of times. Since the laminate 1 has two layers, it can be formed by applying and drying twice.

  1 has two layers, the laminate may have three or more layers, and a part of the plurality of conductive layers constituting the laminate is a conductive polymer composition. It may be formed of a composition other than (X) or a metal.

  The wiring board 2 in FIG. 2 has a wiring 20 formed between two insulating layers 24 and 25 and a wiring 21 and a pad 22 formed on the insulating layer 25. The wiring 20 and the pad 22 are conductively connected via the via conductor 23. The wirings 20 and 21, the pads 22 and the via conductors 23 are formed from the conductive polymer composition (X).

  The wirings 20 and 21 and the pad 22 can be formed by applying a coating liquid formed from the conductive polymer composition (X) and drying it. The application in this case is performed by printing using a mask in which a predetermined opening is patterned. On the other hand, the via conductor 23 can be formed by filling the through hole 26 with the conductive polymer composition (X) by coating with a squeegee or the like and then drying it.

  The via conductor does not need to be entirely formed of the conductive polymer composition (X), and a part of the via conductor constitutes a conductor formed of the conductive polymer composition (X). It may be a thing. Specifically, as shown in FIG. 3, the via conductor 3 fills a space 32 formed by the inner surface of the metal layer 31 after the metal layer 31 is formed on the inner surface of the through hole 30 by electroless plating or the like. Alternatively, the conductor 33 may be formed of the conductive polymer composition (X).

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

[Examples 1 to 10, Comparative Examples 1 to 11]
<Preparation of conductive polymer composition>
The conductive polymer composition is prepared by adding the polyhydric phenol compound or polyhydric alcohol shown in Table 1 (described as component (B) in Table 1) to a solvent and dissolving the component (B) at room temperature (25 ° C.). This was prepared by adding a conductive polymer (described as component (A) in Table 1) and mixing at room temperature.

(Conductive polymer)
As the conductive polymer, poly (3,4-ethylenedioxythiophene) doped with poly (4-styrenesulfonic acid) (“PEDOT / PSS 1.3 wt% dispersion in H ₂ O, conductive grade (product number: 483095) "; manufactured by Aldrich) (described as" PEDOT / PSS "in Table 1).
This PEDOT / PSS is an aqueous dispersion containing 1.3% by mass of PEDOT / PSS polymer (0.5% by mass of PEDOT and 0.8% by mass of PSS). The number of moles of PEDOT / PSS was calculated from the following formula with the molecular weight of the PEDOT minimum unit as 142 based on the PEDOT content.
PEDOT / PSS moles (mol) = PEDOT content (g) / PEDOT minimum unit formula weight 142 (g / mol)

(Polyhydric phenol compound (B))
As the polyhydric phenol compound, 2,6-bis [(2,4-dihydroxyphenyl) methyl] -4-methylphenol (“BIR-PC” (molecular weight 352); manufactured by Asahi Organic Materials Co., Ltd.) (in Table 1) "BIR-PC"), or [bis (3,4-dihydroxy-6-methylphenyl) methyl] benzene ("BI4MC-BZ" (molecular weight 336); manufactured by Asahi Organic Materials Co., Ltd.) BI4MC-BZ ”) was used.

  In a comparative example, instead of the polyhydric phenol compound (B), ethylene glycol (manufactured by Wako Pure Chemical Industries, molecular weight 62) (described as “EG” in Table 1), or pyrogallol (manufactured by Wako Pure Chemical Industries, Molecular weight 126) (described as “PyG” in Table 1) was used.

(solvent)
As a solvent, water (including water in which PEDOT / PSS is dispersed) or water and isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., boiling point: 82.5 ° C.) (described as “IPA” in Table 1) A mixed solvent was used.

<Formation of conductive film>
The conductive film was prepared by applying 750 μL of the previously prepared conductive polymer composition onto a glass substrate (2.5 cm × 2 cm) and drying at 70 ° C. for 30 minutes, and then at 30 ° C. for 30 minutes. Formed by drying for minutes.

[Evaluation]
<Surface resistance value>
The surface resistance value of the conductive film was measured at room temperature using “Loresta-GP MCP-T610” (manufactured by Mitsubishi Chemical Corporation). The results are shown in Table 1. FIG. 4 shows a graph in which the compound (B) / component (A) molar ratio is plotted on the X axis and the surface resistance value (Ω / □) of the conductive film is plotted on the Y axis.

  As can be seen from the results in Table 1, the conductive films obtained using the conductive compositions of Examples 1 to 10 have lower surface resistance values and improved conductivity as compared with Comparative Examples 1 to 11. did.

  Moreover, from the result of FIG. 4, Examples 1-10 which use a polyhydric phenol compound ("BIR-PC" or "BI4MC-BZ") as a component (B) are "EG" which is a conventional electroconductivity improvement component. As compared with Comparative Examples 1 to 11 using “PyG”, it was confirmed that the conductivity improvement effect was excellent when the same molar amount was added.

  ADVANTAGE OF THE INVENTION According to this invention, the electroconductive polymer composition which can manufacture the conductor which has high electroconductivity and flexibility advantageously in cost can be provided.

1 Laminate (an example of a conductor)
10, 11 Conductive layer 12 Base material 2 Wiring board 20, 21 Wiring (an example of a conductive film as a conductor)
22 Pad (an example of a conductive film as a conductor)
23 Via conductor (an example of a conductor)
24, 25 Insulating layer 3 Via conductor 30 Through hole 31 Metal layer 32 Space 33 Conductor

Claims (11)

A conductive polymer composition comprising a conductive polymer and a polyhydric phenol compound represented by the following formula (1).

(In Formula (1), R < ¹ > -R < ⁶ > is respectively independently a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.
R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group or a phenyl group.
X is an alkylene group, a cycloalkylene group or a group represented by the following formula (2).
Y ¹ and Y ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorene group, an adamantyl group, or a group represented by the following formula (3).
Y ¹ and R ⁷ may be bonded to each other, or Y ² and R ⁸ may be bonded to each other to form a cycloalkane structure or a fluorene structure.
a and b are each independently 2 or 3 , m is 0 or 1 , and n is 0 or 1. )

(In Formula (2), R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, an alkoxy group, or a cycloalkyl group. C is an integer of 0 or more and 3 or less.)

(In Formula (3), R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group, and d is an integer of 0 or more and 3 or less. .) R ^{1 to} R ⁸ in the above formula (1) are each independently a hydrogen atom or an alkyl group, Y ¹ is a hydrogen atom, an alkyl group or a group represented by the above formula (3), and Y ² is a hydrogen atom. An atom or an alkyl group, X is a group represented by the above formula (2);
R ⁹ and R ¹⁰ in the above formula (2) are each independently a hydrogen atom or an alkyl group, c is an integer of 0 or more and 2 or less,
2. The conductive polymer composition according to claim 1, wherein R ¹¹ and R ¹² in Formula (3) are each independently a hydrogen atom or an alkyl group, and d is an integer of 0 or more and 2 or less. The conductive polymer composition according to claim 2 , wherein the polyhydric phenol compound is 2,6-bis [(2,4-dihydroxyphenyl) methyl] -4-methylphenol represented by the following formula (4). object.

The conductive polymer composition according to claim 2 , wherein the polyhydric phenol compound is [bis (3,4-dihydroxy-6-methylphenyl) methyl] benzene represented by the following formula (5).

Electroconductive polymer composition according to any one of claims 1 to 4, further comprising a dopant for the oxidation or reduction of the conductive polymer. The conductive polymer composition according to claim 5 , wherein the conductive polymer and the dopant form a poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonic acid) complex. . Further containing a solvent,
The conductive polymer composition according to any one of claims 1 to 6 , wherein the solvent is a mixed solvent of water and alcohol. The conductive polymer composition according to any one of claims 1 to 7 , further comprising a binder resin. The conductor formed from the conductive polymer composition of any one of Claims 1-8 . The conductor according to claim 9 , which is a laminate in which a plurality of conductive layers are laminated. The conductor according to claim 9 formed as a conductive film.

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