JP2008056765A - Carbon nanotube-containing structure and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a structure which enables dispersion of carbon nanotubes without adversely affecting the properties of carbon nanotubes as such and excels in electrical conductivity, film formability, and moldability and a method for manufacturing the structure which can be easily coated to cover a base material by a simple method, the coated film being excellent in electrical conductivity, transparency, water resistance, weatherability, mechanical strength, thermal conductivity, mar resistance, and hardness. <P>SOLUTION: The structure comprises an electrically conductive polymer (a), carbon nanotubes (b), and a particulate substance (c). The structure further comprises a polyfunctional (meth)acrylate unit-containing polymer (I). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a structure containing carbon nanotubes and a method for producing the same.

  Since carbon nanotubes were first discovered by Iijima et al. In 1991 (Non-Patent Document 1), their physical properties have been evaluated and their functions have been elucidated, and research and development relating to their applications have been actively conducted. However, since carbon nanotubes are manufactured in an entangled state, there is a problem that handling becomes very complicated. When mixed in a resin or solution, the carbon nanotubes further agglomerate, and there is a problem that the original characteristics of the carbon nanotubes cannot be exhibited.

For this reason, attempts have been made to uniformly disperse or dissolve carbon nanotubes in a solvent or resin by physically treating or chemically modifying carbon nanotubes.
For example, a method has been proposed in which single-walled carbon nanotubes are ultrasonically treated in a strong acid to cut and disperse the single-walled carbon nanotubes shortly (Non-Patent Document 2). However, since the treatment is carried out in a strong acid, the operation becomes complicated, and it is not an industrially suitable method, and the dispersion effect is not sufficient.

  Therefore, paying attention to the fact that the single-walled carbon nanotubes cut as proposed above are open at both ends and terminated with an oxygen-containing functional group such as a carboxyl group, the carboxyl group is converted to an acid chloride. Subsequently, it has been proposed to react with an amine compound to introduce a long-chain alkyl group and solubilize in a solvent (Non-patent Document 3). However, in this method, long-chain alkyl groups are introduced into single-walled carbon nanotubes by covalent bonds, which leaves problems such as damage to the graphene sheet structure of carbon nanotubes and the characteristics of carbon nanotubes themselves. Yes.

  Another attempt is to introduce a substituent containing ammonium ions into the pyrene molecule by utilizing the fact that the pyrene molecule is adsorbed on the surface of the carbon nanotube by a strong interaction. A method for producing water-soluble single-walled carbon nanotubes by sonication and non-covalently adsorbing the single-walled carbon nanotubes has been reported (Non-Patent Document 4). According to this method, damage to the graphene sheet or the like is suppressed due to non-covalent chemical modification, but there is a problem that the conductive performance of the carbon nanotube is lowered because of the non-conductive pyrene compound.

    There is a method to obtain a dispersion by dispersing or solubilizing carbon nanotubes in various solvents such as water and organic solvents without impairing the characteristics of the carbon nanotubes themselves, using general-purpose surfactants and polymer dispersants. It has been proposed (Patent Document 1, Patent Document 2). Although there is a description that carbon nanotubes are stably dispersed in the dispersion in the state of the dispersion, the dispersion state of carbon nanotubes in the coating film or composite formed from the dispersion and the electrical conductivity thereof are still not known. It is insufficient.

  In addition, a composition comprising a carbon nanotube, a conductive polymer and a solvent, and a composite produced therefrom have been proposed (Patent Document 3). The composition and composite can coexist with a conductive polymer to disperse or solubilize carbon nanotubes in a solvent such as water, organic solvent, water-containing organic solvent, etc. without damaging the properties of the carbon nanotube itself, and stable for long-term storage It is reported to be excellent. A carbon nanotube composition in which a conductive polymer coexists is excellent in conductivity, film formability, and moldability, and can be applied and coated on a substrate by a simple method. There was a limitation in use that application to materials requiring transparency was difficult.

On the other hand, a conductive resin composition in which conductive particles and carbon nanotubes are dispersed in a thermoplastic resin has been proposed (Patent Document 4). The carbon nanotubes in the thermoplastic resin serve to conduct electricity between the conductive particles, thereby expressing high conductivity with a small amount of conductive particles. However, the dispersion of the carbon nanotubes itself is simply converted into a mill. Therefore, the conductivity is not sufficiently improved due to poor dispersion of the carbon nanotubes. In addition, the expression of conductivity depends on the conductive fine particles, and the carbon nanotubes themselves are only used for the conduction of these particles, and it cannot be said that the high conductivity of the carbon nanotubes is sufficiently expressed. .
WO2002 / 016257 JP 2005-35810 A WO2004 / 039873 JP 2003-34751 A S. Iijima, Nature, 354, 56 (1991) R. E. Smalley et al., Science, 280, 1253 (1998) J. et al. Chen et al., Science, 282, 95 (1998). Nakajima et al., Chem. Lett. 638 (2002)

  The object of the present invention is to disperse or solubilize carbon nanotubes without impairing the characteristics of the carbon nanotubes themselves, and the carbon nanotubes do not separate and aggregate even during long-term storage, and are conductive and film-forming. An object of the present invention is to provide a structure having excellent moldability. In addition, as a method for producing the structure, it can be applied and coated on a substrate by a simple method, and the coating film has conductivity, transparency, water resistance, weather resistance, mechanical strength, thermal conductivity, and scratch resistance. And providing a production method excellent in hardness.

  As a result of intensive studies to solve these problems, the present inventor has a structure in which carbon nanotubes are dispersed and has excellent conductivity, film formability, and moldability by allowing a particulate material and a conductive polymer to coexist with carbon nanotubes. It was found that the structure can be further formed, and by further coexisting a polymer containing a polyfunctional (meth) acrylate unit, the scratch resistance of the structure is improved, and a more effective coating film can be formed. .

  That is, the first aspect of the present invention relates to a structure containing a conductive polymer (a), a carbon nanotube (b), and a granular material (c). In addition, the structure of the present invention can further improve performance by allowing a polymer containing a polyfunctional (meth) acrylate unit to coexist.

  In the second aspect of the present invention, a carbon nanotube-containing composition containing a conductive polymer (a), a carbon nanotube (b), and a particulate material (c) is applied on at least one surface of a substrate, and active energy is applied. The present invention relates to a method of manufacturing a structure that is irradiated and / or left at room temperature or heat-treated. The carbon nanotube-containing composition of the present invention has improved scratch resistance by allowing the polyfunctional (meth) acrylate (d) and the polymerization initiator (e) to coexist, and dispersibility by containing the solvent (f). By improving the conductivity and the like and further containing the polymer compound (g), the strength and the adhesion to the substrate can be improved.

  The structure of the present invention can disperse or solubilize carbon nanotubes without impairing the properties of the carbon nanotubes themselves, and the carbon nanotubes are not separated or aggregated even during long-term storage. Excellent in moldability and moldability. In addition, the structure production method of the present invention can be applied and coated on a substrate by a simple method, and the structure is conductive, transparent, water resistant, weather resistant, mechanical strength, thermal conductivity, Excellent scratch resistance and hardness.

  Hereinafter, the present invention will be described in detail.

<Conductive polymer (a)>
In the present invention, by containing a conductive polymer, the solubility and dispersibility of carbon nanotubes are improved, and a stable carbon nanotube-containing composition is obtained. As a result, physical properties such as strength and hardness of the coating film, and conductivity are obtained. Etc. can be further improved. The conductive polymer (a) used in the present invention is a π-conjugated polymer containing phenylene vinylene, vinylene, thienylene, pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene, carbazolylene or the like as a repeating unit. Among these, a conductive polymer having a skeleton containing thienylene, pyrrolylene, iminophenylene, phenylene vinylene, carbazolylene, and isothianaphthene is particularly preferably used.

Among the conductive polymers (a), a π-conjugated water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group or a salt thereof is preferably used from the viewpoint of solubility, conductivity, film-forming property, etc. ammonium salts of sulfonic acid group (-SO ₃ ^- M ⁺⁾ and / or ammonium salt of a carboxyl group ^- [pi-conjugated polymer having a (-COO M ⁺⁾ is preferably used. Here, the conductive polymer having a sulfonic acid group (ammonium salt thereof) and / or a carboxyl group (ammonium salt thereof) is a sulfonic acid group on a skeleton of a π-conjugated polymer or a nitrogen atom in the polymer. (Ammonium salt) and / or a carboxyl group (ammonium salt thereof), an alkyl group substituted with a sulfonic acid group (ammonium salt thereof) and / or a carboxyl group (ammonium salt thereof) or an alkyl group containing an ether bond. Examples thereof include conductive polymers. Here, the ammonium ion (M ⁺ ) of the ammonium salt is represented by the following general formula (2).

（式（２）中、Ｒ^４８〜Ｒ^５１は各々独立に水素、炭素数１〜２４のアルキル、アリールまたはアラルキル基、フェニル基、ベンジル基、Ｒ³⁵ＯＨ、ＣＯＮＨ_２またはＮＨ_２であり、Ｒ^４８〜Ｒ^５１うのうち少なくとも一つが炭素数５以上の基である。なお、Ｒ³⁵は炭素数１〜２４のアルキレン、アリーレンまたはアラルキレン基である。）

(In the formula (2), R ^{48 to} R ⁵¹ are each independently hydrogen, alkyl having 1 to 24 carbon atoms, aryl or aralkyl group, phenyl group, benzyl group, R ³⁵ OH, CONH ₂ or NH ₂ ; ^At least one of ^{48 to} R ⁵¹ is a group having 5 or more carbon atoms, and R ³⁵ is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms.

  Examples of the water-soluble conductive polymer having a sulfonic acid and / or a carboxyl group include, for example, JP-A-61-197633, JP-A-63-39916, JP-A-01-301714, JP-A-05-504153. JP, 05-503953, JP 04-32848, JP 04-328181, JP 06-145386, JP 06-56987, JP 05-226238. JP, 05-178890, JP 06-293828, JP 07-118524, JP 06-32845, JP 06-87949, JP 06-256516, Japanese Laid-Open Patent Publication Nos. 07-41756, 07-48436, 04-26833 JP, Hei 09-59376, JP 2000-172384, JP-A No. 06-49183, JP-was disclosed in JP-A-10-60108 water-soluble electroconductive polymer is preferably used.

  In addition, the water-soluble conductive polymer having a sulfonic acid and / or a carboxyl group is reacted with an ammonium salt and / or an amine to produce an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxyl group used in the present invention. It can also be used as a raw material when synthesizing a conductive polymer having.

  A preferable water-soluble conductive polymer having a sulfonic acid and / or carboxyl group or a conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxyl group is selected from the following general formulas (3) to (11). Further, the conductive polymer contains 20 to 100% of at least one or more repeating units in the total number of repeating units of the entire polymer.

（式（３）中、Ｒ¹ 、Ｒ² は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃ ^-Ｍ⁺ 、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ Ｈ、−ＯＣＨ₃ 、−ＣＨ₃ 、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ³⁵）₂ 、−ＮＨＣＯＲ³⁵、−ＯＨ、−Ｏ^- 、−ＳＲ³⁵、−ＯＲ³⁵、−ＯＣＯＲ³⁵、−ＮＯ₂ 、−ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＲ³⁵、−ＣＯＲ³⁵、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ³⁵は炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはアルキレン、アリーレンまたはアラルキレン基であり、かつＲ¹ 、Ｒ² のうち少なくとも一つが−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ からなる群より選ばれた基である。）

(In formula (3), R ¹ and R ² are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ ⁻ M _{^{+, -R 35 SO 3 H,}} -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, ^{-O -, -SR 35, -OR 35} , -OCOR 35, -NO 2, -COO - M +, -COOH, -R 35 COOH, -R 35 COO - M +, -COOR 35, -COR 35, Selected from the group consisting of —CHO and —CN, wherein M ⁺ is an ammonium ion, R ³⁵ is an alkyl, aryl or aralkyl group or alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and R ^1, at least one of R ² is _{^{-SO 3 -, -SO 3 H,}} -R 35 SO 3 -, -R 35 SO 3 , -COOH, -R ³⁵ COOH, and _{^{-SO 3 - M +, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO - is a group selected from the group consisting of M ^+. )

（式（４）中、Ｒ³ 、Ｒ⁴ は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃ ^-Ｍ⁺ 、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ Ｈ、−ＯＣＨ₃ 、−ＣＨ₃ 、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ³⁵）₂ 、−ＮＨＣＯＲ³⁵、−ＯＨ、−Ｏ^- 、−ＳＲ³⁵、−ＯＲ³⁵、−ＯＣＯＲ³⁵、−ＮＯ₂ 、−ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＲ³⁵、−ＣＯＲ³⁵、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ³⁵は炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはアルキレン、アリーレンまたはアラルキレン基であり、かつＲ³ 、Ｒ⁴ のうち少なくとも一つが−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ からなる群より選ばれた基である。）

(In the formula (4), R ³ and R ⁴ are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ ⁻ M _{^{+, -R 35 SO 3 H,}} -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, ^{-O -, -SR 35, -OR 35} , -OCOR 35, -NO 2, -COO - M +, -COOH, -R 35 COOH, -R 35 COO - M +, -COOR 35, -COR 35, Selected from the group consisting of —CHO and —CN, wherein M ⁺ is an ammonium ion, R ³⁵ is an alkyl, aryl or aralkyl group or alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and R ^3, at least one of -SO ₃ of _{^{R 4 -, -SO 3 H,}} -R 35 SO 3 -, -R 35 SO 3 , -COOH, -R ³⁵ COOH, and _{^{-SO 3 - M +, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO - is a group selected from the group consisting of M ^+. )

（式（５）中、Ｒ⁵ 〜Ｒ⁸ は各々独立にＨ、−ＳＯ₃ ^-、−ＳＯ₃ ^-Ｍ⁺ 、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ Ｈ、−ＯＣＨ₃ 、−ＣＨ₃ 、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ³⁵）₂ 、−ＮＨＣＯＲ³⁵、−ＯＨ、−Ｏ^- 、−ＳＲ³⁵、−ＯＲ³⁵、−ＯＣＯＲ³⁵、−ＮＯ₂ 、−ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＲ³⁵、−ＣＯＲ³⁵、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ³⁵は炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはアルキレン、アリーレンまたはアラルキレン基であり、かつＲ⁵ 〜Ｒ⁸ のうち少なくとも一つが−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ からなる群より選ばれた基である。）

(In the formula (5), R ^{5 to} R ⁸ are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ ⁻ M ^{+. _{, -R 35 SO 3 H, -OCH}} 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, - ^{O -, -SR 35, -OR 35} , -OCOR 35, -NO 2, -COO - M +, -COOH, -R 35 COOH, -R 35 COO - M +, -COOR 35, -COR 35, - Selected from the group consisting of CHO and —CN, wherein M ⁺ is an ammonium ion, R ³⁵ is an alkyl, aryl or aralkyl group or alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and R ⁵ at least one of to R ⁸ are _{^{-SO 3 -, -SO 3 H,}} -R 35 SO 3 -, -R 35 SO 3 H -COOH, -R ³⁵ COOH, and _{^{-SO 3 - + M, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO - is a group selected from the group consisting of M ^+).

（式（６）中、Ｒ⁹ 〜Ｒ¹³は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃ ^-Ｍ⁺ 、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ Ｈ、−ＯＣＨ₃ 、−ＣＨ₃ 、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ³⁵）₂ 、−ＮＨＣＯＲ³⁵、−ＯＨ、−Ｏ^- 、−ＳＲ³⁵、−ＯＲ³⁵、−ＯＣＯＲ³⁵、−ＮＯ₂ 、−ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＲ³⁵、−ＣＯＲ³⁵、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ³⁵は炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはアルキレン、アリーレンまたはアラルキレン基であり、かつＲ⁹ 〜Ｒ¹³のうち少なくとも一つが−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ からなる群より選ばれた基である。）

(In the formula (6), R ^{9 to} R ¹³ are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ ⁻ M _{^{+, -R 35 SO 3 H,}} -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, ^{-O -, -SR 35, -OR 35} , -OCOR 35, -NO 2, -COO - M +, -COOH, -R 35 COOH, -R 35 COO - M +, -COOR 35, -COR 35, Selected from the group consisting of —CHO and —CN, wherein M ⁺ is an ammonium ion, R ³⁵ is an alkyl, aryl or aralkyl group or alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and R ^At least one of ^{9 to} R ¹³ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO _3. H, -COOH, -R ³⁵ COOH, and _{^{-SO 3 - M +, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO - is M ⁺ group selected from the group consisting of .)

（式（７）中、Ｒ¹⁴は、−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ⁸³ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 及び−Ｒ⁸³ＣＯＯ^-Ｍ⁺ からなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ⁸³は炭素数１〜２４のアルキレン、アリーレンまたはアラルキレン基である。）

(In the formula (7), R ¹⁴ represents —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH, —R ³⁵ COOH, and —SO ₃ ⁻ M ^{+. _{, -R 83 SO 3 - + M}} , -COO - M + and -R ⁸³ COO ^- selected from the group consisting of M ^+, wherein, M ⁺ is an ammonium ion, R ⁸³ is 1 to 24 carbon atoms Alkylene, arylene or aralkylene groups.)

（式（８）中、Ｒ⁵²〜Ｒ⁵⁷は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃ ^-Ｍ⁺ 、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ Ｈ、−ＯＣＨ₃ 、−ＣＨ₃ 、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ³⁵）₂ 、−ＮＨＣＯＲ³⁵、−ＯＨ、−Ｏ^- 、−ＳＲ³⁵、−ＯＲ³⁵、−ＯＣＯＲ³⁵、−ＮＯ₂ 、−ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＲ³⁵、−ＣＯＲ³⁵、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ³⁵は炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはアルキレン、アリーレンまたはアラルキレン基であり、かつＲ⁵²〜Ｒ⁵⁷のうち少なくとも一つが−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ からなる群より選ばれた基であり、Ｈｔは、ＮＲ⁸²、Ｓ、Ｏ、Ｓｅ及びＴｅよりなる群から選ばれたヘテロ原子基であり、Ｒ⁸²は水素及び炭素数１〜２４の直鎖または分岐のアルキル基、もしくは置換、非置換のアリール基を表し、Ｒ⁵²〜Ｒ⁵⁷の炭化水素鎖は互いに任意の位置で結合して、かかる基により置換を受けている炭素原子と共に少なくとも１つ以上の３〜７員環の飽和または不飽和炭化水素の環状構造を形成する二価鎖を形成してもよく、このように形成される環状結合鎖にはカルボニル、エーテル、エステル、アミド、スルフィド、スルフィニル、スルホニル、イミノの結合を任意の位置に含んでもよく、ｎはヘテロ環と置換基Ｒ⁵³〜Ｒ⁵⁶を有するベンゼン環に挟まれた縮合環の数を表し、０または１〜３の整数である。）

(In the formula (8), R ^{52 to} R ⁵⁷ are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ ⁻ M _{^{+, -R 35 SO 3 H,}} -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, ^{-O -, -SR 35, -OR 35} , -OCOR 35, -NO 2, -COO - M +, -COOH, -R 35 COOH, -R 35 COO - M +, -COOR 35, -COR 35, Selected from the group consisting of —CHO and —CN, wherein M ⁺ is an ammonium ion, R ³⁵ is an alkyl, aryl or aralkyl group or alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and R at least one of -SO ₃ out of _{^{52 ~R 57 -, -SO 3 H}} , -R 35 SO 3 -, -R 35 SO ^{_{3 H, -COOH, -R 35 COOH}} , and _{^{-SO 3 - M +, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO - with M ⁺ selected from the group consisting of the groups And Ht is a heteroatom group selected from the group consisting of NR ⁸² , S, O, Se and Te, R ⁸² is hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituent, Represents an unsubstituted aryl group, wherein the hydrocarbon chains of R ^{52 to} R ⁵⁷ are bonded to each other at any position, and saturated with at least one or more 3 to 7 membered rings together with carbon atoms substituted by such groups. Alternatively, a divalent chain that forms a cyclic structure of an unsaturated hydrocarbon may be formed, and the thus formed cyclic bond chain may include a bond of carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino. It may be included at any position, and n Represents the number of condensed rings sandwiched between a heterocyclic ring and a benzene ring having substituents R ^{53 to} R ⁵⁶ , and is an integer of 0 or 1 to 3).

（式（９）中、Ｒ⁵⁸〜Ｒ⁶⁶は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃ ^-Ｍ⁺ 、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ Ｈ、−ＯＣＨ₃ 、−ＣＨ₃ 、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ³⁵）₂ 、−ＮＨＣＯＲ³⁵、−ＯＨ、−Ｏ^- 、−ＳＲ³⁵、−ＯＲ³⁵、−ＯＣＯＲ³⁵、−ＮＯ₂ 、−ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＲ³⁵、−ＣＯＲ³⁵、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ³⁵は炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはアルキレン、アリーレンまたはアラルキレン基であり、かつＲ⁵⁸〜Ｒ⁶⁶のうち少なくとも一つが−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ からなる群より選ばれた基であり、ｎは置換基Ｒ⁵⁸及びＲ⁵⁹を有するベンゼン環と置換基Ｒ⁶¹〜Ｒ⁶⁴を有するベンゼン環に挟まれた縮合環の数を表し、０または１〜３の整数である。）

(In the formula (9), R ^{58 to} R ⁶⁶ are independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ ⁻ M _{^{+, -R 35 SO 3 H,}} -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, ^{-O -, -SR 35, -OR 35} , -OCOR 35, -NO 2, -COO - M +, -COOH, -R 35 COOH, -R 35 COO - M +, -COOR 35, -COR 35, Selected from the group consisting of —CHO and —CN, wherein M ⁺ is an ammonium ion, R ³⁵ is an alkyl, aryl or aralkyl group or alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and R at least one of -SO ₃ out of _{^{58 ~R 66 -, -SO 3 H}} , -R 35 SO 3 -, -R 35 SO ^{_{3 H, -COOH, -R 35 COOH}} , and _{^{-SO 3 - M +, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO - with M ⁺ selected from the group consisting of the groups And n represents the number of condensed rings sandwiched between the benzene ring having the substituents R ⁵⁸ and R ⁵⁹ and the benzene ring having the substituents R ^{61 to} R ⁶⁴ , and is an integer of 0 or 1 to 3).

（式（１０）中、Ｒ⁶⁷〜Ｒ⁷⁶は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃ ^-Ｍ⁺ 、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ Ｈ、−ＯＣＨ₃ 、−ＣＨ₃ 、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ³⁵）₂ 、−ＮＨＣＯＲ³⁵、−ＯＨ、−Ｏ^- 、−ＳＲ³⁵、−ＯＲ³⁵、−ＯＣＯＲ³⁵、−ＮＯ₂ 、−ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＲ³⁵、−ＣＯＲ³⁵、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ³⁵は炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはアルキレン、アリーレンまたはアラルキレン基であり、かつＲ⁶⁷〜Ｒ⁷⁶のうち少なくとも一つが−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ からなる群より選ばれた基であり、ｎは置換基Ｒ⁶⁷〜Ｒ⁶⁹を有するベンゼン環とベンゾキノン環に挟まれた縮合環の数を表し、０または１〜３の整数である。）

(In the formula (10), R ^{67 to} R ⁷⁶ are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ ⁻ M _{^{+, -R 35 SO 3 H,}} -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, ^{-O -, -SR 35, -OR 35} , -OCOR 35, -NO 2, -COO - M +, -COOH, -R 35 COOH, -R 35 COO - M +, -COOR 35, -COR 35, Selected from the group consisting of —CHO and —CN, wherein M ⁺ is an ammonium ion, R ³⁵ is an alkyl, aryl or aralkyl group or alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and R at least one of -SO ₃ out of _{^{67 ~R 76 -, -SO 3 H}} , -R 35 SO 3 -, -R 35 S ^{_{3 H, -COOH, -R 35 COOH}} , and _{^{-SO 3 - M +, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO - with M ⁺ selected from the group consisting of the groups And n represents the number of condensed rings sandwiched between a benzene ring having substituents R ^{67 to} R ⁶⁹ and a benzoquinone ring, and is an integer of 0 or 1 to 3).

（式（１１）中、Ｒ⁷⁷〜Ｒ⁸¹は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃ ^-Ｍ⁺ 、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ Ｈ、−ＯＣＨ₃ 、−ＣＨ₃ 、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ³⁵）₂ 、−ＮＨＣＯＲ³⁵、−ＯＨ、−Ｏ^- 、−ＳＲ³⁵、−ＯＲ³⁵、−ＯＣＯＲ³⁵、−ＮＯ₂ 、−ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＲ³⁵、−ＣＯＲ³⁵、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ³⁵は炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはアルキレン、アリーレンまたはアラルキレン基であり、かつＲ⁷⁷〜Ｒ⁸¹のうち少なくとも一つが−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ からなる群より選ばれた基であり、Ｘ^a-は、塩素イオン、臭素イオン、ヨウ素イオン、フッ素イオン、硝酸イオン、硫酸イオン、硫酸水素イオン、リン酸イオン、ほうフッ化イオン、過塩素酸イオン、チオシアン酸イオン、酢酸イオン、プロピオン酸イオン、メタンスルホン酸イオン、ｐ−トルエンスルホン酸イオン、トリフルオロ酢酸イオン、及びトリフルオロメタンスルホン酸イオンよりなる１〜３価の陰イオン群より選ばれた少なくとも一種の陰イオンであり、ａはＸのイオン価数を表し、１〜３の整数であり、ｐはドープ率であり、その値は０．００１〜１である。）

(In the formula (11), R ^{77 to} R ⁸¹ are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ ⁻ M _{^{+, -R 35 SO 3 H,}} -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, ^{-O -, -SR 35, -OR 35} , -OCOR 35, -NO 2, -COO - M +, -COOH, -R 35 COOH, -R 35 COO - M +, -COOR 35, -COR 35, Selected from the group consisting of —CHO and —CN, wherein M ⁺ is an ammonium ion, R ³⁵ is an alkyl, aryl or aralkyl group or alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and R at least one of ⁷⁷ to R ⁸¹ is _{^{-SO 3 -, -SO 3 H,}} -R 35 SO 3 -, -R 35 S ^{_{3 H, -COOH, -R 35 COOH}} , and _{^{-SO 3 - M +, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO - with M ⁺ selected from the group consisting of the groups ^Xa- is chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, And at least one anion selected from the group of 1 to 3 anions consisting of propionate ions, methanesulfonate ions, p-toluenesulfonate ions, trifluoroacetate ions, and trifluoromethanesulfonate ions, Represents the ionic valence of X, is an integer of 1 to 3, p is the doping rate, and the value is 0.001 to 1.)

Polyethylene dioxythiophene polystyrene sulfate is also used as another preferable water-soluble conductive polymer having a sulfonic acid and / or carboxyl group. This water-soluble conductive polymer has a structure in which polystyrene sulfonic acid is added as a dopant, although no sulfonic acid group is introduced into the skeleton of the conductive polymer.
In addition, as a conductive polymer having a preferable ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxyl group, polyethylene dioxythiophene polystyrene sulfonate ammonium salt or substituted ammonium salt is also used. This conductive polymer has a structure in which ammonium sulfonate group is not introduced into the skeleton of the conductive polymer, but polystyrene sulfonate ammonium salt is added as a dopant. These polymers are polyethylene dioxythiophene and polystyrene produced by polymerizing 3,4-ethylenedioxythiophene (Baytron M manufactured by Bayer) with an oxidizing agent such as iron toluenesulfonate (Baytron C manufactured by Bayer). It can be produced by reacting an adduct of sulfonic acid or this adduct with amines or ammonia. This polymer can also be produced by reacting Baytron P or Baytron P manufactured by Bayer with amines and / or ammoniums.

（式（１２）中、ｙは０＜ｙ＜１の任意の数を示し、Ｒ¹⁵〜Ｒ³²は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃ ^-Ｍ⁺ 、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ Ｈ、−ＯＣＨ₃ 、−ＣＨ₃ 、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ³⁵）₂ 、−ＮＨＣＯＲ³⁵、−ＯＨ、−Ｏ^- 、−ＳＲ³⁵、−ＯＲ³⁵、−ＯＣＯＲ³⁵、−ＮＯ₂ 、−ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＲ³⁵、−ＣＯＲ³⁵、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ³⁵は炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはアルキレン、アリーレンまたはアラルキレン基であり、Ｒ¹⁵〜Ｒ³²のうち少なくとも一つが−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ からなる群より選ばれた基である。） Among the above conductive polymers having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxyl group, the repeating unit represented by the following general formula (12) is 20 to 100 in the total number of repeating units of the whole polymer. % Is more preferably used.

(In the formula (12), y represents an arbitrary number of 0 <y <1, and R ^{15 to} R ³² are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, _{^{-R 35 SO 3 -, -R 35}} SO 3 - M +, -R 35 SO 3 H, -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, - N (R ³⁵ ) ₂ , —NHCOR ³⁵ , —OH, —O ⁻ , —SR ³⁵ , —OR ³⁵ , —OCOR ³⁵ , —NO ₂ , —COO ⁻ M ⁺ , —COOH, —R ³⁵ COOH, —R ³⁵ COO ⁻ M ⁺ , —COOR ³⁵ , —COR ³⁵ , —CHO and —CN, wherein M ⁺ is an ammonium ion and R ³⁵ is alkyl having 1 to 24 carbon atoms, aryl or aralkyl group or an alkylene, arylene or aralkylene group, at least one of -SO ₃ of R ¹⁵ to R ^{32 -,} -SO _{3 ^{, -R 35 SO 3 -, -R}} 35 SO 3 H, -COOH, -R 35 COOH, and _{^{-SO 3 - M +, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO ^- it is a group selected from the group consisting of M ^+).

  Here, the conductive polymer having a repeating unit content of 50% or more having a sulfonic acid group and / or a carboxyl group or an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxyl group with respect to the total number of repeating units of the polymer, It is preferably used because it has very good solubility in solvents such as organic solvents and hydrous organic solvents. The content of the repeating unit having a sulfonic acid group and / or a carboxyl group or an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxyl group is more preferably 70% or more, still more preferably 90% or more, and particularly preferably 100. %.

（式（１３）中、Ｒ³³は、スルホン酸基、カルボキシル基、及びこれらのアルカリ金属塩、アンモニウム塩及び置換アンモニウム塩からなる群より選ばれた１つの基であり、そのうち少なくとも一つがスルホン酸基、カルボキシル基、及びスルホン酸基のアンモニウム塩、カルボキシル基のアンモニウム塩からなる群より選ばれた基であり、Ｒ³⁴は、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ドデシル基、テトラコシル基、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉｓｏ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ヘプトキシ基、ヘクソオキシ基、オクトキシ基、ドデコキシ基、テトラコソキシ基、フルオロ基、クロロ基及びブロモ基からなる群より選ばれた１つの基を示し、Ｘは０＜Ｘ＜１の任意の数を示し、ｎは重合度を示し３以上である。） In addition, the substituent added to the aromatic ring is preferably an alkyl group, an alkoxy group, a halogen group or the like from the viewpoint of conductivity and solubility, and particularly preferably a conductive polymer having an alkoxy group. Among these combinations, the most preferable water-soluble conductive polymer is represented by the following general formula (13).

(In the formula (13), R ³³ is one group selected from the group consisting of a sulfonic acid group, a carboxyl group, and alkali metal salts, ammonium salts and substituted ammonium salts thereof, at least one of which is a sulfonic acid group. R ³⁴ is a group selected from the group consisting of a group, a carboxyl group, an ammonium salt of a sulfonic acid group, and an ammonium salt of a carboxyl group, and R ³⁴ is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, n -Butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group , Heptoxy group, hexoxy group, octoxy group, dodecoxy group, tetracosoxy group, fluoro group, chloro And shows one group selected from the group consisting of bromo group, X is 0 <show any number of X <1, n is 3 or more indicates a polymerization degree.)

（式（１４）中、Ｒ³⁶〜Ｒ⁴¹は各々独立に、Ｈ、−ＳＯ₃ ^-、−ＳＯ₃ ^-Ｍ⁺ 、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ Ｈ、−ＯＣＨ₃ 、−ＣＨ₃ 、−Ｃ₂Ｈ₅、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−Ｎ（Ｒ³⁵）₂ 、−ＮＨＣＯＲ³⁵、−ＯＨ、−Ｏ^- 、−ＳＲ³⁵、−ＯＲ³⁵、−ＯＣＯＲ³⁵、−ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ 、−ＣＯＯＲ³⁵、−ＣＯＲ³⁵、−ＣＨＯ及び−ＣＮからなる群より選ばれ、ここで、Ｍ⁺ はアンモニウムイオンであり、Ｒ³⁵は炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはアルキレン、アリーレンまたはアラルキレン基であり、Ｒ³⁶〜Ｒ⁴¹のうち少なくとも一つが−ＳＯ₃ ^-、−ＳＯ₃ Ｈ、−Ｒ³⁵ＳＯ₃ ^-、−Ｒ³⁵ＳＯ₃ Ｈ、−ＣＯＯＨ、−Ｒ³⁵ＣＯＯＨ、及び−ＳＯ₃ ^-Ｍ⁺ 、−Ｒ³⁵ＳＯ₃ ^-Ｍ⁺ 、−ＣＯＯ^-Ｍ⁺ 、−Ｒ³⁵ＣＯＯ^-Ｍ⁺ からなる群より選ばれた基である。） As the conductive polymer in the present invention, polymers obtained by various synthetic methods such as chemical polymerization or electrolytic polymerization can be used. For example, the synthesis methods described in Japanese Patent Application Laid-Open Nos. 7-196791 and 7-324132 proposed by the present inventors are applied. That is, one compound selected from the group consisting of an acidic group-substituted aniline represented by the following general formula (14), an alkali metal salt thereof, an ammonium salt, and a substituted ammonium salt is oxidized in a solution containing a basic compound. It is the conductive polymer obtained by making it superpose | polymerize by.

(In the formula (14), R ^{36 to} R ⁴¹ are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ ⁻ M _{^{+, -R 35 SO 3 H,}} -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, ^{-O -, -SR 35, -OR 35} , -OCOR 35, -COO - M +, -COOH, -R 35 COOH, -R 35 COO - M +, -COOR 35, -COR 35, -CHO and - Selected from the group consisting of CN, wherein M ⁺ is an ammonium ion, R ³⁵ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group, and R ^{36 to} R ⁴¹ out at least one of _{^{-SO 3 -, -SO 3 H,}} -R 35 SO 3 -, -R 35 SO 3 H, -CO H, -R ³⁵ COOH, and _{^{-SO 3 - + M, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO - is a group selected from the group consisting of M ^+).

  As a particularly preferred conductive polymer, a conductive polymer obtained by polymerizing an alkoxy group-substituted aminobenzenesulfonic acid, its alkali metal salt, ammonium salt, or substituted ammonium salt with a oxidizing agent in a solution containing a basic compound. Is used.

  In addition, as a synthesis method of a water-soluble conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxyl group from a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group, the following general formula ( The purpose is to react the ammonium salt represented by 15) and / or the amine represented by the following general formula (16) with a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group in a solution. A conductive polymer is easily obtained.

（式（１５）中、Ｒ^１４８〜Ｒ^１５１は各々独立に水素、Ｒ³⁵ＯＨ、炭素数１〜２４のアルキル、アリールまたはアラルキル基あるいはフェニル基、ベンジル基、ＣＯＮＨ_２またはＮＨ_２であり、かつＲ^１４８〜Ｒ^１５１のうち少なくとも一つが炭素数５以上の基であり、Ｒ³⁵は炭素数１〜２４のアルキレン、アリーレンまたはアラルキレン基であり、Ｘ_ｋ ^Ｚ- は水酸化物イオン、塩素イオン、臭素イオン、ヨウ素イオン、フッ素イオン、硝酸イオン、硫酸イオン、硫酸水素イオン、アミド硫酸イオン、亜硫酸イオン、ホスフィン酸イオン、リン酸イオン、ピロリン酸イオン、トリポリリン酸イオン、ほうフッ化イオン、過塩素酸イオン、チオシアン酸イオン、酢酸イオン、プロピオン酸イオン、メタンスルホン酸イオン、ｐ−トルエンスルホン酸イオン、吉草酸イオン、ドデシルベンゼンスルホン酸イオン、カンファースルホン酸イオン、酪酸イオン、蟻酸イオン、トリメチル酢酸イオン、ブロモ酢酸イオン、乳酸イオン、クエン酸イオン、コハク酸イオン、シュウ酸イオン、酒石酸イオン、フマル酸イオン、マレイン酸イオン、マロン酸イオン、アスコルビン酸イオン、アニス酸イオン、アントラニル酸イオン、安息香酸イオン、ケイ皮酸イオン、フェニル酢酸イオン、フタル酸イオン、アニリンスルホン酸イオン、チオカルボン酸イオン、メチルスルフィン酸イオン、トリフルオロ酢酸イオン、及びトリフルオロメタンスルホン酸イオンよりなる１〜３価の陰イオン群より選ばれた少なくとも１種の陰イオンを示す。また、ＺはＸ_ｋのイオン価数であり、１〜３の整数を示し、ｊは１〜３の整数を示す。）

(In the formula (15), R ^{148 to} R ¹⁵¹ are each independently hydrogen, R ³⁵ OH, alkyl having 1 to 24 carbon atoms, aryl or aralkyl group, phenyl group, benzyl group, CONH ₂ or NH ₂ , and At least one of R ^{148 to} R ¹⁵¹ is a group having 5 or more carbon atoms, R ³⁵ is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, X _k ^Z− is a hydroxide ion, a chlorine ion, Bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, amide sulfate ion, sulfite ion, phosphinate ion, phosphate ion, pyrophosphate ion, tripolyphosphate ion, borofluoride ion, perchloric acid Ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-tolue Sulfonate ion, valerate ion, dodecylbenzene sulfonate ion, camphor sulfonate ion, butyrate ion, formate ion, trimethyl acetate ion, bromoacetate ion, lactate ion, citrate ion, succinate ion, oxalate ion, tartaric acid ion , Fumarate ion, maleate ion, malonate ion, ascorbate ion, anisate ion, anthranilate ion, benzoate ion, cinnamic acid ion, phenylacetate ion, phthalate ion, aniline sulfonate ion, thiocarboxylate ion And at least one anion selected from the group of 1 to 3 anions consisting of methylsulfinate ion, trifluoroacetate ion, and trifluoromethanesulfonate ion, and Z _represents the valence of X _k And an integer from 1 to 3 Shown, j is an integer of 1-3.)

（式（１６）中、Ｒ^１４５〜Ｒ^１４７は各々独立に水素、炭素数１〜２４（Ｃ_１〜Ｃ_２４）のアルキル、アリールまたはアラルキル基あるいは、フェニル基、ベンジル基、Ｒ³⁵ＯＨ、ＣＯＮＨ_２またはＮＨ_２であり、かつＲ^１４５〜Ｒ^１４７のうち少なくとも一つが炭素数５以上の基である。なお、Ｒ³⁵は炭素数１〜２４のアルキレン、アリーレンまたはアラルキレン基である。）

(In the formula (16), R ^{145 to} R ¹⁴⁷ are each independently hydrogen, alkyl having 1 to 24 carbon atoms (C _{1 to} C ₂₄ ), aryl or aralkyl group, phenyl group, benzyl group, R ³⁵ OH, CONH. ₂ or NH ₂ and at least one of R ^{145 to} R ¹⁴⁷ is a group having 5 or more carbon atoms, and R ³⁵ is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms.)

  Preferred ammonium salts include halogenated alkyldimethylbenzylammonium chlorides such as benzalkonium chloride and trimethylbenzylammonium chloride, alkyldiethylbenzylammonium halides such as alkyldiethylbenzylammonium chloride and triethylbenzylammonium bromide, trioctylmethylammonium chloride and the like. The tetraalkylammonium halides and trimethylbenzylammonium hydroxide are used.

  Preferred amines include benzylamine, tri-n-octylamine, di-n-octylamine, 2-ethylhexylamine, 3- (2-ethylhexyloxy) propylamine, aniline, dimethylaniline, diethylaniline, di- Anilines such as n-propylaniline and di-iso-propylaniline are used.

  As the conductive polymer in the present invention, those having a mass average molecular weight of 2000 to 3 million in terms of GPC polyethylene glycol are excellent in conductivity, film formability and film strength and are preferably used. Those having a molecular weight of 3,000 to 1,000,000 are more preferred, and those having a molecular weight of 5,000 to 500,000 are most preferred.

  Although the conductive polymer (a) can be used as it is, a polymer to which an external dopant is added by performing a doping treatment method using an acid by a known method can be used. For example, the doping treatment can be performed by a treatment such as immersing a conductor containing the conductive polymer (a) in an acidic solution. Specifically, the acidic solution used for the doping treatment includes inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as p-toluenesulfonic acid, camphorsulfonic acid, benzoic acid, and derivatives having these skeletons; polystyrene sulfonic acid An aqueous solution containing a polymer acid such as polyvinyl sulfonic acid, poly (2-acrylamido-2-methylpropane) sulfonic acid, polyvinyl sulfuric acid and derivatives having these skeletons, or a mixed solution of water and an organic solvent. These inorganic acids, organic acids, and polymer acids may be used alone or in admixture of two or more at any ratio.

<Carbon nanotube (b)>
The carbon nanotube (b) that is an essential component of the carbon nanotube-containing composition of the present invention is not particularly limited, and is a normal carbon nanotube, that is, a single-walled carbon nanotube, and several layers are concentrically overlapped. Multi-walled carbon nanotubes, those in which these are coiled, and the like can be used.

  The carbon nanotube (b) will be described in more detail. A cylinder formed by rounding a graphite-like carbon atomic plane having a thickness of several atomic layers has a single-layer structure or a plurality of nested structures, and has an extremely small outer diameter on the order of nm. Examples of such substances are exemplified. Further, carbon nanohorns having a shape in which one side of the carbon nanotube is closed, a cup-shaped nanocarbon material having a hole in the head thereof, and the like can also be used.

  In addition, fullerene, metal-encapsulated fullerene, onion-like fullerene, carbon nanofiber, vapor grown carbon (VGCF), peapod, carbon nanoparticle, and the like, which are analogs of carbon nanotube (b), can also be used.

  The method for producing the carbon nanotube (b) in the present invention is not particularly limited. Specifically, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, vapor phase growth method, gas phase flow method, carbon monoxide is reacted with iron catalyst at high temperature and high pressure in the gas phase. Examples include HiPco method for growth.

  The carbon nanotubes (b) obtained by these production methods are preferably single-walled carbon nanotubes and multi-walled carbon nanotubes, and various purifications such as washing methods, centrifugal separation methods, filtration methods, oxidation methods, chromatographic methods, etc. Carbon nanotubes that are more highly purified by the method are preferably used because they exhibit various functions sufficiently.

  Further, as the carbon nanotube (b), those that are pulverized using a ball-type kneading apparatus such as a ball mill, a vibration mill, a sand mill, and a roll mill, and those that are cut short by chemical and physical treatment are used. be able to.

<Particulate matter (c)>
The particulate material (c) used in the present invention is not particularly limited as long as it is in the form of particles, and organic particles, inorganic particles, ceramic particles, metal oxide particles, metal particles, dyes, A pigment or the like is used. Specifically, resin particles such as acrylic, silica, colloidal silica, plate-like alumina, fibrous alumina, zirconia, spinel, talc, mullite, cordierite, silicon carbide, yttrium oxide, cerium oxide, samarium oxide, lanthanum oxide, Terbium oxide, europium oxide, neodymium oxide, zinc oxide, titanium oxide, gnesium fluoride, tin oxide, indium oxide, antimony-containing tin oxide (ATO), tin-containing indium oxide (ITO), antimonic acid zinc, antimony pentoxide, gold And metal particles such as silver, copper and nickel, hematite, cobalt blue, cobalt violet, cobalt green, magnetite, Mn-Zn ferrite, Ni-Zn ferrite and barium titanate. Among these particulate materials, from the viewpoint of conductivity, yttrium oxide, cerium oxide, samarium oxide, lanthanum oxide, terbium oxide, europium oxide, neodymium oxide, zinc oxide, titanium oxide, gnesium fluoride, tin oxide, indium oxide, antimony Metal particles such as tin-containing oxide (ATO), tin-containing indium oxide (ITO), zinc antimoate, antimony pentoxide, gold, silver, copper and nickel are preferably used.

  In the structure of the present invention, when the granular material (c) is contained in the carbon nanotube-containing composition during the production, an efficient conduction path can be formed between the granular material (c) in the structure. Conductivity is improved because it is possible. In addition, since the portion where the carbon nanotube (b) exists in the structure and the portion where the carbon nanotube (b) does not exist are clearly separated by the granular material (c), light absorption and scattering by the carbon nanotube (b) In addition, the reflection is suppressed, the transparency of the structure is improved, and the characteristics of the carbon nanotubes such as mechanical strength and thermal conductivity tend to be improved.

  The particulate material (c) used in the present invention is not particularly limited, but those dispersed in water, an organic solvent or a mixed solvent of water and an organic solvent are preferably used. Examples of the organic solvent include, but are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, and pentanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone; ethylene glycol, Ethylene glycols such as ethylene glycol methyl ether and ethylene glycol mono-n-propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether are preferably used. .

  As the particulate material (c), those having a particle diameter of 1 nm to 50 μm are used, preferably those having a particle diameter of 1 nm to 10 μm, more preferably 1 nm to 1 μm. If the particle size is too large, the transparency is insufficient, and the solution stability of the granular material (c) itself is also lowered.

<Polyfunctional (meth) acrylate (d) and polymer containing polyfunctional (meth) acrylate unit (l)>
The polyfunctional (meth) acrylate (d) used in the present invention is not particularly limited as long as it contains two or more (meth) acryloyloxy groups and can be dissolved or dispersed in the carbon nanotube (b). It is more preferable if the soluble polymer (a) is dissolved or dispersed. Specific examples include, for example, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. , Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, polyethoxylated cyclohexanedimethanol di (meth) acrylate, polypropoxylated cyclohexanedimethanol di (meth) ) Acrylate, polyethoxylated bisphenol A di (meth) acrylate, polypropoxylated bisphenol A di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, polyester Xylated hydrogenated bisphenol A di (meth) acrylate, polypropoxylated hydrogenated bisphenol A di (meth) acrylate, bisphenoxyfluoreneethanol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, hydroxypivalin Di (meth) acrylate of ε-caprolactone adduct of acid neopentyl glycol (n + m = 2 to 5), di (meth) acrylate of γ-butyrolactone adduct of neopentyl glycol hydroxypivalate (n + m = 2 to 5), Di (meth) acrylate of caprolactone adduct of neopentyl glycol (n + m = 2 to 5), di (meth) acrylate of caprolactone adduct of butylene glycol (n + m = 2 to 5), cyclohexane Di (meth) acrylate of caprolactone adduct of methanol (n + m = 2 to 5), caprolactone adduct of dicyclopentanediol (n + m = 2 to 5), caprolactone adduct of bisphenol A (n + m = 2-5) di (meth) acrylate, hydrogenated bisphenol A caprolactone adduct (n + m = 2-5) di (meth) acrylate, bisphenol F caprolactone adduct (n + m = 2-5) di (meth) ) Acrylate, bis (2-acryloyloxyethyl) hydroxyethyl isocyanurate, bis (2-acryloyloxypropyl) hydroxypropyl isocyanurate, bis (2-acryloyloxybutyl) hydroxybutyl isocyanurate, bis (2-methacryloyloxyethyl) ) Hydroxyethyl isocyanurate, bis (2-methacryloyloxypropyl) hydroxypropyl isocyanurate, bis (2-methacryloyloxybutyl) di (meth) acrylic acid esters such as hydroxybutyl isocyanurate;
Trimethylolpropane tri (meth) acrylate, trisethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated Pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified Dipentaerythritol hexa (meth) acrylate, modified aliphatic hydrocarbon having 2 to 5 carbon atoms Methylolpropane triacrylate, C2-C5 aliphatic hydrocarbon-modified dipentaerythritol penta (meth) acrylate, C2-C5 aliphatic hydrocarbon-modified dipentaerythritol tetra (meth) acrylate, Tris (2- ( (Meth) acryloyloxyethyl) isocyanurate, tris (2- (meth) acryloyloxypropyl) isocyanurate, tris (2- (meth) acryloyloxybutyl) isocyanurate, bis (2- (meth) acryloyloxyethyl) -2 -Trifunctional or higher functional groups such as hydroxyethyl isocyanurate, bis (2- (meth) acryloyloxypropyl) -2-hydroxyethyl isocyanurate, bis (2- (meth) acryloyloxybutyl) -2-hydroxyethyl isocyanurate Functional (meth) acrylic acid esters;
Polyester (meth) acrylates obtained by reaction with polyhydric alcohols such as ethylene glycol, hexanediol, polyethylene glycol, polytetramethylene glycol and (meth) acrylic acid or derivatives thereof;
Epoxy (meth) acrylates obtained by reacting bisphenol type epoxy resin obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A and epichlorohydrin with (meth) acrylic acid or a derivative thereof;
Compounds containing at least three epoxy groups in the molecule, such as epoxy poly (meth) acrylates obtained by reacting a compound containing at least three epoxy groups in the molecule with (meth) acrylic acid;
One kind of organic diisocyanate compound or a mixture of two or more kinds of hydroxy group-containing (meth) acrylic acid ester having one or more (meth) acryloyloxy groups and one hydroxy group in the molecule Urethane (meth) acrylates obtained by reacting one kind alone or a mixture of two or more kinds;
Urethane obtained by adding an organic diisocyanate compound to the hydroxyl group of an alcohol composed of one or a mixture of two or more of alkanediol, polyether diol, polybutadiene diol, polyester diol, polycarbonate diol, amide diol, spiroglycol compound, etc. Urethane (meth) acrylates in which the isocyanate group of the prepolymer is reacted with one (meth) acryloyloxy group and one hydroxy group-containing (meth) acrylic acid ester having one hydroxy group in the molecule. It is done.
These polyfunctional (meth) acrylates can be used alone or in combination of two or more. Also, in combination with these polyfunctional (meth) acrylates, monofunctional (meth) acrylates such as methyl (meth) acrylate and butyl methacrylate; vinyl ester monomers such as vinyl acetate, vinyl butyrate and divinyl adipate Vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt-butyl Acrylamides such as acrylamide, acryloylmorpholine, hydroxyethylacrylamide, methylenebisacrylamide, etc .; N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-bi N-vinyl amides such as lucaprolactam; one or more of other vinyl monomers such as styrene sulfonic acid, sulfoethyl (meth) acrylate, acrylamido-2-methylpropane sulfonic acid and sulfonic acid group-containing vinyl monomers such as salts thereof It can also be used. The polymer (l) containing a polyfunctional (meth) acrylate unit used in the present invention is a polymer or copolymer containing one or more of the above polyfunctional (meth) acrylates, or one or more of the above polyfunctional (meth) acrylate units. It is a copolymer of a functional (meth) acrylate and another vinyl monomer.

<Polymerization initiator (e)>
As the polymerization initiator (e) used in the present invention, a photopolymerization initiator or a thermal polymerization initiator can be used depending on the constituent components and applications of the carbon nanotube-containing composition.
A photoinitiator is a component which provides the composition of this invention with the polymerization promotion effect by an active energy ray. Specific examples of the photopolymerization initiator include, for example, benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophene, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin isobutyl ether, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Tanone-1, diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6 -Trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, Examples include 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone and 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) -butan-1-one. These can be used alone or in combination of two or more. Furthermore, the composition of the present invention may contain a known photosensitizing agent such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, as necessary. A sensitizer may be blended.

Examples of the thermal polymerization initiator include thermal polymerization initiators such as azo compounds and organic peroxides.
As the azo compound, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyric acid) dimethyl, 4,4 ′ -Azobis (4-cyanovaleric acid), 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis {2-methyl-N- [2- (1-hydroxybutyl)]- Propionamide} and the like. Examples of the organic peroxide include benzoyl peroxide and lauroyl peroxide. A thermal polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  The polymerization initiator (e) is a carbon nanotube-containing composition comprising a conductive polymer (a), a carbon nanotube (b), a particulate material (c), a polyfunctional (meth) acrylate (d), and a solvent (f). In addition, it can be mixed from the beginning, or can be mixed before use, and the mixing timing can be appropriately selected according to the purpose of use and the situation.

<Solvent (f)>
When the carbon nanotube-containing composition of the present invention contains the solvent (f) as a constituent component, the dispersibility of the carbon nanotube (b) is further improved, and the coating property and operability are also improved. The solvent (f) is not particularly limited as long as it dissolves or disperses the carbon nanotubes (b), but dissolves the conductive polymer (a), the polyfunctional (meth) acrylate (d), and the polymerization initiator (e). Or it is more preferable if it disperse | distributes and a granular material (c).

  Examples of the solvent (f) include alcohols such as water, methanol, ethanol, isopropyl alcohol, propyl alcohol, and butanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone, and diacetone alcohol; ethyl acetate, n acetate -Esters such as butyl, isobutyl acetate, n-amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate; ethylene glycols such as ethylene glycol, ethylene glycol methyl ether, ethylene glycol mono-n-propyl ether; propylene glycol, propylene Glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol propyl ether , Propylene glycols such as propylene glycol monomethyl ether acetate; amides such as dimethylformamide and dimethylacetamide; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; dimethylsulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate, Hydroxyesters such as methyl β-methoxyisobutyrate and methyl α-hydroxyisobutyrate; anilines such as aniline and N-methylaniline, aromatic hydrocarbons such as benzene, toluene and xylene, m-cresol, acetonitrile, tetrahydro Furan, 1,4-dioxane, ethyl cellosolve, butyl cellosolve, and methoxypropanol are preferably used.

  As a preferable solvent (f) when a conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxyl group is used as the conductive polymer (a), solubility of the conductive polymer (a), carbon nanotube From the viewpoint of dispersibility of (b), an organic solvent or a water-containing organic solvent is preferably used.

  Moreover, as a preferable solvent (f) when using a water-soluble conductive polymer having a sulfonic acid and / or carboxyl group as the conductive polymer (a), the solubility of the conductive polymer (a), the carbon nanotube (b) From the viewpoint of dispersibility, water or a water-containing organic solvent is preferably used as the solvent (f).

<Polymer compound (g)>
In the carbon nanotube-containing composition of the present invention, the substrate adhesion and strength of the coating film are further improved by adding the polymer compound (g). The polymer compound (g) that can be used in the present invention is not particularly limited as long as it can be dissolved or dispersed in the carbon nanotube-containing composition of the present invention. Specifically, polyvinyl alcohol, polyvinyl formal, Polyvinyl alcohols such as polyvinyl butyral; polyacrylamides such as polyacrylamide, poly (Nt-butylacrylamide), polyacrylamide methylpropanesulfonic acid; polyvinylpyrrolidones, polystyrenesulfonic acid and its soda salts, cellulose , Alkyd resin, melamine resin, urea resin, phenol resin, epoxy resin, polybutadiene resin, acrylic resin, urethane resin, vinyl ester resin, urea resin, polyimide resin, maleic acid resin, polycarbonate resin Vinyl acetate resin, chlorinated polyethylene resin, chlorinated polypropylene resin, styrene resin, acrylic / styrene copolymer resin, vinyl acetate / acrylic copolymer resin, polyester resin, styrene / maleic acid copolymer resin, fluorine resin and their co-polymerization Coalescence etc. are used. Further, these polymer compounds (g) may be a mixture of two or more of them in an arbitrary ratio.

  Among these polymer compounds (g), when a conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxyl group is used as the conductive polymer (a), an alkyd resin, a melamine resin, a urea resin, Phenol resin, epoxy resin, polybutadiene resin, acrylic resin, urethane resin, vinyl ester resin, urea resin, polyimide resin, maleic acid resin, polycarbonate resin, vinyl acetate resin, styrene resin, acrylic / styrene copolymer resin, vinyl acetate / acrylic A copolymer resin, a polyester resin, and a styrene / maleic acid copolymer resin are preferably used in terms of solubility in a solvent, stability of a composition, and conductivity, and among them, a phenol resin, an epoxy resin, and a polybutadiene resin are particularly preferable. , Acrylic resin, cormorant It is possible to use one or more of tan resin, acrylic / styrene copolymer resin, vinyl acetate / acrylic copolymer resin, and polyester resin in combination. Solubility in solvent, stability of composition, conductivity From the viewpoint of sex.

  Among these polymer compounds (g), when a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group is used, the water-soluble polymer compound or the polymer compound that forms an emulsion in an aqueous system is dissolved in the solvent. From the viewpoints of stability, stability of the composition, and conductivity, a polymer compound having an anionic group is particularly preferably used. Among them, it is preferable to use one or two or more of water-based acrylic resin, water-based polyester resin, water-based urethane resin, and water-based chlorinated polyolefin resin.

<Basic compound (h)>
By adding the basic compound (h) to the carbon nanotube-containing composition of the present invention, the conductive polymer (a), which is a constituent component, is dedoped, and there is an effect of further improving dissolution in the composition. Further, by forming a salt with free sulfonic acid groups and carboxyl groups, dissolution in the composition is particularly improved, and solubilization or dispersion of the carbon nanotube (b) in the composition is promoted.

（式（１７）中、Ｒ^２４５〜Ｒ^２４７は各々互いに独立に、水素、炭素数１〜４のアルキル基、ＣＨ₂ＯＨ 、ＣＨ₂ＣＨ₂ＯＨ、ＣＯＮＨ₂ またはＮＨ₂ を表す。） The basic compound (h) is not particularly limited, but, for example, ammonia, fatty amines, cyclic saturated amines, cyclic unsaturated amines, ammonium salts, inorganic bases and the like are preferably used. .
The structural formula of amines used as the basic compound (h) is shown in the following general formula (17).

(In formula (17), R ^{245 to} R ²⁴⁷ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, CH ₂ OH, CH ₂ CH ₂ OH, CONH ₂ or NH _2. )

（式（１８）中、Ｒ^２４８〜Ｒ^２５１は各々互いに独立に、水素、炭素数１〜４のアルキル基、ＣＨ₂ＯＨ 、ＣＨ₂ＣＨ₂ＯＨ、ＣＯＮＨ₂ またはＮＨ₂ を表し、Ｘ^- はＯＨ^- 、１／２・ＳＯ₄ ^2-、ＮＯ₃ ^-、１／２ＣＯ₃ ^2-、ＨＣＯ₃ ^-、１／２・（ＣＯＯ）₂ ^2-、またはＲ’ＣＯＯ^- を表し、Ｒ’は炭素数１〜３のアルキル基である。） The structural formula of ammonium salts used as the basic compound (h) is shown in the following formula (18).

(In the formula ^(18), the R 248 ^{to R 251} are each independently of one another, represent hydrogen, an alkyl group having 1 to 4 carbon _{atoms, CH 2 OH, CH 2 CH} 2 OH, a CONH ₂ or NH _2, X ^- is OH ⁻ , 1/2 · SO ₄ ²⁻ , NO ₃ ⁻ , 1 / 2CO ₃ ²⁻ , HCO ₃ ⁻ , 1/2 · (COO) ₂ ²⁻ , or R′COO ⁻ , where R ′ represents carbon (It is a C 1-3 alkyl group.)

As cyclic saturated amines, piperidine, pyrrolidine, morpholine, piperazine, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.
As the cyclic unsaturated amines, pyridine, α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline, pyrroline, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.
As the inorganic base, hydroxide salts such as sodium hydroxide, potassium hydroxide and lithium hydroxide are preferably used.

Two or more basic compounds (h) may be mixed and used. For example, the conductivity can be further improved by using a mixture of amines and ammonium salts. Specifically, NH ₃ / (NH ₄ ) ₂ CO ₃ , NH ₃ / (NH ₄ ) HCO ₃ , NH ₃ / CH ₃ COONH ₄ , NH ₃ / (NH ₄ ) ₂ SO ₄ , N (CH ₃ ) ₃ / CH ₃ COONH ₄ , N (CH ₃ ) ₃ / (NH ₄ ) ₂ SO _{4 and the} like. These mixing ratios can be used at an arbitrary ratio, but amines / ammonium salts = 1/10 to 10/0 are preferable.

<Surfactant (i)>
When the surfactant (i) is added to the carbon nanotube-containing composition of the present invention, further solubilization or dispersion is promoted, and flatness, coating property, conductivity, and the like are improved.

  Specific examples of the surfactant (i) include alkylsulfonic acid, alkylbenzenesulfonic acid, alkylcarboxylic acid, alkylnaphthalenesulfonic acid, α-olefinsulfonic acid, dialkylsulfosuccinic acid, α-sulfonated fatty acid, N-methyl-N. -Oleyl taurine, petroleum sulfonic acid, alkyl sulfuric acid, sulfated oil, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene styrenated phenyl ether sulfuric acid, alkyl phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphorus Anionic surfactants such as acids, naphthalenesulfonic acid formaldehyde condensates and their salts; primary to tertiary fatty amines, quaternary ammoniums, tetraalkylammoniums, trialkylbenzylammonium amines Rualkylpyridinium, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium, N, N-dialkylmorpholinium, polyethylene polyamine fatty acid amide, urea condensate of polyethylene polyamine fatty acid amide, urea condensate of polyethylene polyamine fatty acid amide Cationic surfactants such as quaternary ammonium and salts thereof; N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N, N, N-trialkyl-N-sulfoalkylene ammonium betaine, Betaines such as N, N-dialkyl-N, N-bispolyoxyethyleneammonium sulfate betaine, 2-alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine, N, N-dialkylaminoal Amphoteric surfactants such as aminocarboxylic acids such as lencarboxylate; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-poly Oxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylenated castor oil, fatty acid diethanolamide, polyoxyethylene alkylamine, Non-ionic surfactants such as triethanolamine fatty acid partial esters, trialkylamine oxides; and fluoroalkylcarbo Acid, perfluoroalkyl carboxylic acids, perfluoroalkyl benzene sulfonic acids, fluorine-based surfactants such as perfluoroalkyl polyoxyethylene ethanol is used. Here, the alkyl group preferably has 1 to 24 carbon atoms, and more preferably 3 to 18 carbon atoms. In addition, even if it uses 2 or more types of surfactant, it does not matter at all.

（式（１）中、Ｒ⁴²、Ｒ⁴³、Ｒ⁴⁴は各々独立に、水素、炭素数１〜６の直鎖または分岐のアルキル基、炭素数１〜６の直鎖または分岐のアルコキシ基、アミノ基、アセチル基、フェニル基、ハロゲン基よりなる群から選ばれた基であり、Ｘは、

を示し、ｌ及びｍは０〜６までの数であり、Ｙは、水酸基、チオール基、アミノ基、エポキシ基及びエポキシシクロヘキシル基よりなる群から選ばれた基である。） <Silane coupling agent (j)>
In the present invention, a silane coupling agent (j) can be used in combination with the carbon nanotube-containing composition. The water resistance of the coating film obtained from the carbon nanotube-containing composition combined with the silane coupling agent (j) is significantly improved. As the silane coupling agent (j), a silane coupling agent (j) represented by the following general formula (1) is used.

(In the formula (1), R ⁴² , R ⁴³ and R ⁴⁴ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, X is a group selected from the group consisting of an amino group, an acetyl group, a phenyl group, and a halogen group.

1 and m are numbers from 0 to 6, and Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, an epoxy group, and an epoxycyclohexyl group. )

Specifically, those having an epoxy group include γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropyltriethoxysilane, and the like.
Examples of those having an amino group include γ-aminopropyltriethoxysilane, β-aminoethyltrimethoxysilane, and γ-aminopropoxypropyltrimethoxysilane.
Examples of those having a thiol group include γ-mercaptopropyltrimethoxysilane and β-mercaptoethylmethyldimethoxysilane.
Examples of those having a hydroxyl group include β-hydroxyethoxyethyltriethoxysilane and γ-hydroxypropyltrimethoxysilane.
Examples of those having an epoxycyclohexyl group include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

<Stabilizers such as antioxidants and light stabilizers (k)>
In the present invention, a stabilizer (k) such as an antioxidant or a light stabilizer can be added to the carbon nanotube-containing composition. A cured coating film obtained from the carbon nanotube-containing composition in combination with a stabilizer (k) such as an antioxidant or a light stabilizer can prevent yellowing of the coating film over time. Specific examples of this include, for example, Sumitomo Chemical Co., Ltd. Sumitizer BHT, Summarizer S, Summarizer BP-76, Summarizer MDP-S, Summarizer GM, Summarizer BBM-S, Summarizer WX-R, Summarizer NW, Summarizer BP-179 , Sumilyzer BP-101, Sumilyzer GA-80, Sumilyzer TNP, Sumilyzer TPP-R, Sumilyzer P-16, Adeka Stub AO-20, Adeka Stub AO-30, Adeka Stub AO-40, Adeka Stub AO-50 by Asahi Denka Kogyo Co., Ltd. , ADK STAB AO-60AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB P-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 329K, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, CHIBIN SPECIALITY CHEMICALS CO., LTD. , Tinuvin 123, Tinuvin 292 and the like.

<Carbon nanotube-containing composition>
The composition ratio of the components of the carbon nanotube-containing composition of the present invention is 0.0001 to 40 parts by mass (preferably 0.001 to 20 parts by mass) of the carbon nanotube (b), 0.001 to 50 parts by mass of the conductive polymer (a). Part (preferably 0.01 to 30 parts by mass), and particulate matter (c) 0.0001 to 40 parts by weight (preferably 0.001 to 20 parts by mass). Further, a more preferable component composition ratio is 0.0001 to 40 parts by mass (particularly preferably 0.001 to 20 parts by mass) of the carbon nanotube (b) with respect to 100 parts by mass of the polyfunctional (meth) acrylate (d). , Polymerization initiator (e) 0.001 to 20 parts by mass (particularly preferably 0.05 to 10 parts by mass), conductive polymer (a) 0.001 to 50 parts by mass (particularly preferably 0.01 to 30 parts by mass) Part) and particulate matter (c) 0.0001 to 40 parts by weight (particularly preferably 0.001 to 20 parts by weight).

  The carbon nanotube-containing composition of the present invention is improved in solubility / dispersibility, coating property, operability and the like by using the solvent (f) as a constituent component, but the composition ratio in the case of using the solvent (f) is as follows: Street.

  The proportion of the conductive polymer (a) and the solvent (f) used is preferably 0.001 to 50 parts by mass of the conductive polymer (a) with respect to 100 parts by mass of the solvent (f), more preferably 0. 0.01 to 30 parts by mass. When the conductive polymer (a) is less than 0.001 part by mass, the conductivity is inferior, and the carbon nanotube (b) is solubilized or dispersed efficiently. On the other hand, when it exceeds 50 parts by mass, the conductivity reaches a peak and does not increase greatly, and the viscosity increases, so that the efficiency of solubilization or dispersion of the carbon nanotube (b) is lowered.

  The use ratio of the carbon nanotube (b) and the solvent (f) is preferably 0.0001 to 20 parts by mass, more preferably 0.001 with respect to 100 parts by mass of the solvent (f). -10 parts by mass. When the carbon nanotube (b) is less than 0.0001 part by mass, the performance of the carbon nanotube (b) such as conductivity is lowered. On the other hand, when it exceeds 20 parts by mass, the efficiency of solubilization or dispersion of the carbon nanotube (b) is lowered.

  The proportion of the particulate material (c) and the solvent (f) used is preferably such that the particulate material (c) is 0.0001 to 40 parts by weight, more preferably 0.001 with respect to 100 parts by weight of the solvent (f). ˜20 parts by mass. When the granular material (c) is less than 0.0001 part by mass, the carbon nanotubes (b) are dispersed in the structure and the composite, and an efficient conduction path is not formed. Therefore, conductivity and transparency are not lowered. Will not improve. On the other hand, if the amount exceeds 40 parts by mass, the efficiency of solubilization or dispersion of the carbon nanotube (b) decreases.

  The use ratio of the polyfunctional (meth) acrylate (d) and the solvent (f) is preferably 1 to 500 parts by mass of the polyfunctional (meth) acrylate (d) with respect to 100 parts by mass of the solvent (f). More preferably, it is 10-300 mass parts. When the polyfunctional (meth) acrylate (d) is 1 part by mass or more, the properties of the cured coating film are improved when it is applied. On the other hand, the amount of 500 parts by mass or less is preferable from the viewpoint of dispersibility of the carbon nanotube (b).

  The use ratio of the polymerization initiator (e) is 0.001 to 20 parts by mass with respect to 100 parts by mass of the total amount of the conductive polymer (a), the solvent (f) and the carbon nanotube (b) as constituent components. It is preferable to mix | blend in the range, and it is more preferable to mix | blend in the range of 0.01-10 mass parts. The blending amount of the polymerization initiator (e) is preferably 0.001 part by mass or more from the viewpoint of curability, and is preferably in the range of 10 parts by mass or less from the viewpoint of yellowing resistance.

  The use ratio of the polymer compound (g) and the solvent (f) is preferably 0.1 to 400 parts by mass, more preferably 0, to 100 parts by mass of the solvent (f). .5 to 300 parts by mass. When the polymer compound (g) is 0.1 part by mass or more, the film formability, moldability, and strength are further improved. On the other hand, when the polymer compound (g) is 400 parts by mass or less, the conductive polymer (a) and the carbon nanotube (b) There is little decrease in solubility, and high conductivity is maintained.

  The use ratio of the basic compound (h) and the solvent (f) is preferably 0.1 to 10 parts by mass, more preferably 0, with respect to 100 parts by mass of the solvent (f). .1 to 5 parts by mass. When the basic compound (h) is in this range, the solubility of the water-soluble conductive polymer is improved, solubilization or dispersion of the carbon nanotube (b) in the solvent (f) is promoted, and the conductivity is improved. To do.

  It is preferable that surfactant (i) is 0.0001-10 mass parts with respect to 100 mass parts of solvent (f), and, as for the usage-amount of surfactant (i) and solvent (f), More preferably, it is 0. 0.01 to 5 parts by mass. When the surfactant (i) exceeds 10 parts by mass, the coatability is improved, but a phenomenon such as poor conductivity occurs, and the efficiency of solubilization or dispersion of the carbon nanotube (b) is lowered.

  The use ratio of the silane coupling agent (j) and the solvent (f) is preferably 0.001 to 20 parts by mass of the silane coupling agent (j), more preferably 100 parts by mass of the solvent (f). Is 0.01 to 15 parts by mass. When the silane coupling agent (j) is less than 0.001 part by mass, the improvement in water resistance and / or solvent resistance is relatively small. On the other hand, when it exceeds 20 parts by mass, solubility, flatness, transparency, and conductivity are increased. Sexuality may worsen.

  The blending amount of the antioxidant and the stabilizer (k) for the light stabilizer is not particularly limited, but the total amount of the conductive polymer (a), the solvent (f) and the carbon nanotube (b) as the constituent components is 100 parts by mass. On the other hand, it is preferable to mix | blend in the range of 0.001-2 mass parts, and it is more preferable to mix | blend in the range of 0.01-1 mass part.

  Furthermore, the carbon nanotube-containing composition of the present invention includes, as necessary, a plasticizer, a dispersant, a coating surface modifier, a fluidity modifier, an ultraviolet absorber, a storage stabilizer, an adhesion aid, a thickener, Various known substances such as thermoplastic polymers other than the conductive polymer (a), slip agents, leveling agents, ultraviolet absorbers, polymerization inhibitors, antistatic agents, inorganic fillers, organic fillers, inorganic fillers subjected to surface organic treatment, etc. It can be added and used.

  In addition, the carbon nanotube-containing composition of the present invention can contain a conductive substance in order to further improve its conductivity. Examples of the conductive material include carbon-based materials such as carbon fiber, conductive carbon black, and graphite.

<Method for producing carbon nanotube-containing composition>
Conductive polymer (a), carbon nanotube (b), granular material (c), polyfunctional (meth) acrylate (d), polymerization initiator (e), solvent, which are essential components of the carbon nanotube-containing composition of the present invention (F) When mixing the polymer compound (g) and other components as necessary, stirring or kneading devices such as ultrasonic waves, homogenizers, spiral mixers, planetary mixers, dispersers, and hybrid mixers are used. In particular, when a carbon nanotube-containing composition having good dispersibility and coatability is obtained to obtain a high-performance composite, the combined use of the solvent (f) is effective. In this case, it is preferable that the conductive polymer (a), the solvent (f), the carbon nanotube (b), or other components are mixed and irradiated with ultrasonic waves. In this case, the ultrasonic irradiation and the homogenizer are performed. It is particularly preferable to carry out the treatment in combination (ultrasonic homogenizer).

The conditions for the ultrasonic irradiation treatment are not particularly limited, but it is sufficient if the ultrasonic wave intensity and the treatment time are sufficient to uniformly disperse or dissolve the carbon nanotube (b) in the solvent (f). . For example, the rated output in the ultrasonic oscillator is preferably 0.1 to 2.0 watt / cm ² per unit bottom area of the ultrasonic oscillator, more preferably in the range of 0.3 to 1.5 watt / cm ² . The oscillation frequency is preferably 10 to 200 KHz, more preferably 20 to 100 KHz. Further, the time of the ultrasonic irradiation treatment is preferably 1 minute to 48 hours, more preferably 5 minutes to 48 hours. Thereafter, it is desirable to further thoroughly disperse or dissolve using a ball-type kneader such as a ball mill, a bead mill, a vibration mill, a sand mill, or a roll mill.

  When mixing predetermined constituents, all the components may be added all at once. For example, when using a solvent, a small amount of the solvent (f) to be used is used to concentrate concentrated carbon. After preparing the nanotube-containing composition, it may be diluted to a predetermined concentration. When two or more kinds of solvents (f) are used in combination, a concentrated carbon nanotube-containing composition is prepared using one or more components of the solvent (f) to be used, and then other solvents ( It may be diluted with the component f).

  In addition, the temperature of the carbon nanotube-containing composition when performing the ultrasonic irradiation treatment is preferably 60 ° C. or less, and more preferably 40 ° C. or less, from the viewpoint of improving dispersibility.

<Structure>
The constituent composition ratio of the carbon nanotube (b), the conductive polymer (a), and the granular material (c) contained in the structure of the present invention is 0.0001 to 40 parts by mass (preferably 0.001) of the carbon nanotube (b). To 20 parts by weight), conductive polymer (a) 0.001 to 50 parts by weight (preferably 0.01 to 30 parts by weight), particulate substance (c) 0.0001 to 40 parts by weight (preferably 0.001 to 20 parts by mass). Further, a more preferable component composition ratio is 0.0001 to 40 parts by mass (particularly preferably 0.001) of carbon nanotube (b) with respect to 100 parts by mass of the polymer (l) containing a polyfunctional (meth) acrylate unit. To 20 parts by weight), conductive polymer (a) 0.001 to 50 parts by weight (particularly preferably 0.01 to 30 parts by weight), and particulate substance (c) 0.0001 to 40 parts by weight (particularly preferably 0.8. 001 to 20 parts by mass). The structure of the present invention is not limited as long as it contains the conductive polymer (a), the carbon nanotube (b), and the particulate material (c). For example, on the at least one surface of the base material The structure obtained by coating the carbon nanotube containing composition containing a conductive polymer (a), a carbon nanotube (b), and a granular material (c) is mentioned. In the present invention, the base material on which the carbon nanotube-containing composition is applied to form a coating film includes a polymer compound, plastic, wood, paper material, ceramics, fiber, nonwoven fabric, carbon fiber, carbon fiber paper, and these Films, foams, porous membranes, elastomers, glass plates and the like are used.
For example, as polymer compounds, plastics and films, polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyester, polyamide, polyimide, polyaramid, Examples include polyphenylene sulfide, polyether ether ketone, polyphenylene ether, polyether nitrile, polyamide imide, polyether sulfone, polysulfone, polyether imide, polybutylene terephthalate, polyurethane, these films, foams and elastomers. Since these films form a cured coating film on at least one surface thereof, the surface is preferably subjected to corona surface treatment or plasma treatment for the purpose of improving the adhesion of the cured coating film.

  The coating film in this invention is formed in the surface of a base material by the method used for general coating. For example, 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. Spraying methods such as spray coating such as air spray and airless spray, and dipping methods such as dipping are used.

<Method for manufacturing structure>
After coating the carbon nanotube-containing composition on the surface of the substrate, active energy rays may be irradiated, or a coating film can be formed by standing or heating treatment at room temperature. Since it can be cured in a short time without heating, it is preferable to cure using active energy rays.

        Although the composition of the present invention can be cured by active energy rays and / or heat, it can be cured in a short time without heating, and therefore it is preferably cured using active energy rays. The active energy ray here is not particularly limited, and examples thereof include α, β and γ rays. Among them, it is preferable to use ultraviolet rays because of excellent versatility.

        In addition, the irradiation atmosphere of active energy rays may be air or an inert gas such as nitrogen or argon.

        The generation source of ultraviolet rays used here is not particularly limited, but it is preferable to use a commonly used ultraviolet lamp from the viewpoint of practicality and economy.

        Specific examples of the ultraviolet lamp include, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, and a metal halide lamp. Further, an electrodeless UV lamp system may be used.

        On the other hand, the coating film can be formed by leaving the coating film at room temperature or by heat-treating the coating film. When polyfunctional (meth) acrylate (d), polymer compound (g), basic compound (h), and conductive polymer (a) are contained by heat treatment, the crosslinking reaction with them is further accelerated. Thus, it is preferable because water resistance can be imparted in a shorter time, the amount of the remaining solvent (f) can be further reduced, and the conductivity is further improved. The heat treatment temperature is preferably 20 ° C. or more and 250 ° C. or less, and particularly preferably heating at 40 ° C. to 200 ° C. When the temperature is higher than 250 ° C., the conductive polymer (a) itself is decomposed, and the conductivity may be remarkably lowered.

  The film thickness of the coating film is preferably in the range of 0.01 to 100 μm, more preferably in the range of 0.1 to 50 μm.

Although the structure of the present invention still has excellent conductivity, it is doped with an acid after coating a carbon nanotube-containing composition on at least one surface of the substrate to form a coating film. The conductivity can be further improved by performing the treatment and then leaving it at room temperature or performing a heat treatment.
The doping treatment method using an acid is not particularly limited, and a known method can be used. For example, the doping process can be performed by performing a process such as immersing a conductor in an acidic solution. Specifically, the acidic solution includes inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as p-toluenesulfonic acid, camphorsulfonic acid, benzoic acid and derivatives having these skeletons, polystyrene sulfonic acid, polyvinyl It is an aqueous solution containing a polymer acid such as sulfonic acid, poly (2-acrylamido-2-methylpropane) sulfonic acid, polyvinylsulfuric acid and derivatives having these skeletons, or a mixed solution of water and an organic solvent. In addition, these inorganic acids, organic acids, and polymer acids may be used alone or in admixture of two or more at any ratio.

  In the carbon nanotube-containing composition using the conductive polymer (a) of the present invention and the solvent (f) described above, the carbon nanotube (b) is added to the solvent (f) together with the conductive polymer (a). Therefore, the carbon nanotube (b) can be dispersed or solubilized in the solvent (f) without impairing the characteristics of the carbon nanotube (b) and the polyfunctional (meth) acrylate (c) itself, Does not separate or aggregate during storage. The reason for this is not clearly understood, but the carbon nanotube (b) is dispersed or solubilized together with the conductive polymer (a) by adsorbing or helically wrapping the conductive polymer (a) on the carbon nanotube (b). Presumed to be. In the carbon nanotube-containing composition of the present invention, the conductive polymer (a) and the carbon nanotube (b) are used in combination with the cured coating film formed from the polyfunctional (meth) acrylate (d). Since it is dispersed or dissolved, it has excellent conductivity, film formability and moldability, and its coating film is excellent in water resistance, weather resistance, mechanical strength and hardness.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, a following example does not limit the scope of the present invention. In addition, the multi-wall carbon nanotube manufactured by ILJIN company and the CVD method was used for the carbon nanotube of a raw material (Hereinafter, a carbon nanotube may be abbreviated as CNT.).
<Manufacture of conductive polymer>
(Production Example 1, water-soluble conductive polymer (A-1))
Synthesis of poly (2-sulfo-5-methoxy-1,4-iminophenylene):
100 mmol of 2-aminoanisole-4-sulfonic acid was stirred and dissolved in a 4 mol / L triethylamine aqueous solution at 25 ° C., and an aqueous solution of 100 mmol ammonium peroxodisulfate was added dropwise thereto. After completion of the dropping, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was filtered, washed and dried to obtain 15 g of polymer powder. The volume resistance value of this conductive polymer (A-1) was 9.0 Ω · cm.

(Production Example 2, conductive polymer (A-2) obtained by reaction of water-soluble conductive polymer (A-1) and benzalkonium chloride)
5 g of water-soluble conductive polymer (A-1) was stirred and dissolved in 95 g of water to prepare a water-soluble conductive polymer aqueous solution. Benzalkonium chloride aqueous solution obtained by stirring and dissolving 10 g of benzalkonium chloride in water 95 was added dropwise to the obtained aqueous solution of the water-soluble conductive polymer. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 1 hour, and then the reaction product was filtered, washed, and dried to obtain 10 g of a conductive polymer (A-2) having an ammonium sulfonate group.

<Curable composition>
Curable composition 1:
5 parts by mass of dipentaerythritol tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: Kayrad DPHA), 5 parts by weight of polyethylene glycol 600 diacrylate (trade name SR-610, manufactured by Sartomer), 1-hydroxycyclohexylphenyl A curable composition 1 was prepared by mixing 0.5 parts by mass of ketone (Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) with 10 parts by mass of ethanol at room temperature.

<Carbon nanotube-containing composition>
(Example 1) Carbon nanotube-containing composition 1:
1 part by mass of the conductive polymer (A-1) of Production Example 1 above, 0.1 part by mass of the carbon nanotube, acrylic resin particle “Finesphere E-102” (manufactured by Nippon Paint Co., Ltd., resin content 20% by mass, particle size 100 nm) ) 5 parts by mass was mixed with 100 parts by mass of water at room temperature, and subjected to ultrasonic homogenizer treatment (vibra cell 20 kHz, manufactured by SONIC) for 1 hour to prepare a carbon nanotube-containing composition 1.

(Example 2) Carbon nanotube-containing composition 2:
1 part by mass of the conductive polymer (A-1) of Production Example 1 above, 0.1 part by mass of carbon nanotubes, water-dispersed antimony double oxide colloid “CELNAX CX-Z330H-F2” (manufactured by Nissan Chemical Co., Ltd., solid content 20 (Mass%, particle size 15 nm) 5 parts by mass was mixed with 100 parts by mass of water at room temperature, and subjected to ultrasonic homogenizer treatment (Vibra cell 20 kHz, manufactured by SONIC) for 1 hour to prepare a carbon nanotube-containing composition 1.

(Example 3) Carbon nanotube-containing composition 3:
1 part by mass of the conductive polymer (A-2) of Production Example 1 above, 0.1 part by mass of carbon nanotubes, methanol-dispersed antimony double oxide colloid “CELNAX CX-Z610M-F2” (manufactured by Nissan Chemical Co., Ltd., solid content 60 (Mass%, particle size 15 nm) 1 part by mass was mixed with 100 parts by mass of dimethylacetamide at room temperature, and ultrasonic homogenizer treatment (vibra cell 20 kHz manufactured by SONIC) was performed for 1 hour to prepare a carbon nanotube-containing composition 2 .

Carbon nanotube-containing composition 4:
1 part by mass of the conductive polymer (A-1) of Production Example 1 above, 1 part by mass of carbon nanotubes, water-dispersed antimony double oxide colloid “CELNAX CX-Z330H-F2” (manufactured by Nissan Chemical Co., Ltd., solid content 20% by mass) In addition, 5 parts by mass of a particle size of 15 nm) was mixed with 100 parts by mass of water at room temperature, and subjected to ultrasonic homogenizer treatment (vibra cell 20 kHz manufactured by SONIC) for 1 hour to prepare a carbon nanotube-containing composition 1.

(Example 4) Carbon nanotube-containing composition 5:
The carbon nanotube-containing composition 5 was prepared by mixing and stirring 5 parts by mass of the carbon nanotube-containing composition 4 and 20.5 parts by mass of the curable composition 1.

(Example 5) Carbon nanotube-containing composition 6:
1.0 part by mass of the conductive polymer (A-1) of Production Example 1 above, 0.5 part by mass of carbon nanotubes, water-dispersed antimony double oxide colloid “CELNAX CX-Z330H-F2” (manufactured by Nissan Chemical Co., Ltd., solid 0.5 parts by mass of 20% by mass and 15 nm particle size), 22.5 parts by mass of water-based emulsion “Dainal MX-1845” (Mitsubishi Rayon Co., Ltd., resin content 40% by mass) 100 parts by mass of water The mixture was mixed at room temperature and subjected to ultrasonic homogenizer treatment (Vibra cell 20 kHz, manufactured by SONIC) for 1 hour to prepare a carbon nanotube-containing composition 6.

(Comparative Example 1) Carbon nanotube-containing composition 7:
1 part by mass of the conductive polymer (A-1) of Production Example 1 and 0.1 part by mass of carbon nanotubes were mixed with 100 parts by mass of water at room temperature, and subjected to ultrasonic homogenizer treatment (vibra cell 20 kHz, manufactured by SONIC). Carried out for a while, a carbon nanotube-containing composition 7 was prepared.

(Comparative Example 2) Carbon nanotube-containing composition 8:
1 part by mass of the conductive polymer (A-2) of Production Example 1 and 0.1 part by mass of the carbon nanotube are mixed with 100 parts by mass of dimethylacetamide at room temperature, and subjected to ultrasonic homogenizer treatment (vibra cell 20 kHz manufactured by SONIC). Carried out for 1 hour, a carbon nanotube-containing composition 8 was prepared.

Carbon nanotube-containing composition 9:
1 part by mass of the conductive polymer (A-1) of Production Example 1 and 1 part by mass of carbon nanotubes were mixed with 100 parts by mass of water at room temperature, and subjected to ultrasonic homogenizer treatment (vibra cell 20 kHz, manufactured by SONIC) for 1 hour. Then, a carbon nanotube-containing composition 9 was prepared.

(Comparative Example 3) Carbon nanotube-containing composition 10:
5 parts by mass of carbon nanotube-containing composition 9 and 20.5 parts by mass of curable composition 1 were mixed and stirred to prepare carbon nanotube-containing composition 10.

(Comparative Example 4) Carbon nanotube-containing composition 11:
1.0 part by mass of conductive polymer (A-1) of Production Example 1 above, 0.5 part by mass of carbon nanotube, acrylic resin “Dianar MX-1845” which is an aqueous emulsion (Mitsubishi Rayon Co., Ltd., resin part 40 mass) %) 22.5 parts by mass was mixed with 100 parts by mass of water at room temperature, and subjected to ultrasonic homogenizer treatment (vibra cell 20 kHz, manufactured by SONIC) for 1 hour to prepare a carbon nanotube-containing composition 11.

(Comparative Example 5) Carbon nanotube-containing composition 12:
Carbon nanotubes 0.5 parts by mass, water-dispersed antimony double oxide colloid “CELNAX CX-Z330H-F2” (manufactured by Nissan Chemical Co., Ltd., solid content 20% by mass, particle size 15 nm) 0.5 parts by mass, aqueous emulsion 22.5 parts by mass of acrylic resin “Dianar MX-1845” (Mitsubishi Rayon Co., Ltd., resin content 40% by mass) is mixed with 100 parts by mass of water at room temperature and subjected to ultrasonic homogenizer treatment (Vibra cell 20 kHz, manufactured by SONIC). Was carried out for 1 hour to prepare a carbon nanotube-containing composition 12.

<Evaluation method>
Example 4 and Comparative Example 3
An appropriate amount of the carbon nanotube-containing composition is dropped on a PET film (product name: A-4100, manufactured by Toyobo Co., Ltd.), applied by the bar coating method (bar coater # 10), and dried at 100 ° C. for about 1 minute by a dryer. . Next, a high pressure mercury lamp (Oak Manufacturing Co., Ltd., ultraviolet irradiation device, handy UV-1200, QRU-2161 type) was irradiated with ultraviolet rays for about 30 seconds for about 1000 mJ / cm ² to form a coating film. The surface resistance value and the total light transmittance were measured. The results are shown in Table 1.

Examples 1-3, 5 and Comparative Examples 1-2, 4-5
An appropriate amount of a carbon nanotube-containing composition is dropped on a glass substrate, applied by a bar coating method (bar coater # 5), dried at 80 ° C. for 5 minutes with a dryer, a coating film is formed, the appearance is observed, and the surface Resistance value and total light transmittance were measured. The results are shown in Table 1.

(Visual observation of solution state)
The solution states of the carbon nanotube-containing compositions obtained in the examples and comparative examples were visually observed immediately after the dispersion treatment and after standing for 1 day.
○: A visually uniform composition in a solution state.
X: A visually non-uniform composition in a solution state.
(Surface resistance value)
When measuring the surface resistance under the conditions of 23 ± 2 ° C and 50 ± 5% RH, use the two-probe method (distance between electrodes: 20 mm) when the surface resistance is 10 ⁸ Ω or more. Was 10 ⁷ Ω or less, a four-probe method (distance between each electrode: 5 mm) was used.
(Coating surface appearance)
The state of the coating film was observed visually.
○: A uniform coating film was formed.
X: A coating film in which carbon nanotubes exist non-uniformly was observed.
(Total light transmittance): The total light transmittance (%) was measured by Nippon Denshoku HAZEMETER NDH2000.

  The structure of the present invention includes a capacitor, a battery, a fuel cell and a polymer electrolyte membrane thereof, an electrode layer, a catalyst layer, a gas diffusion layer, a gas diffusion electrode layer, a member such as a separator, an EMI shield, a chemical sensor, and a display element. , Non-linear materials, anticorrosives, adhesives, fibers, spinning materials, antistatic paints, anticorrosion paints, electrodeposition paints, plating primers, conductive primers for electrostatic painting, anticorrosion, battery storage capacity improvement, semiconductors, electrical appliances Antistatic films such as industrial packaging materials such as electronic parts, film for overhead projectors, electrophotographic recording materials such as slide films, tapes for magnetic recording such as audio tapes, video tapes, computer tapes, floppy disks, LSI wiring for electronic devices, field emission display (FED) electronics (Source) and electrode, hydrogen storage agent, transparent touch panel, electroluminescence display, liquid crystal display, etc. Input and display device surface antistatic and transparent electrode, light emitting material forming organic electroluminescence element, buffer material, electron transport material , Hole transport materials and fluorescent materials, thermal transfer sheets, transfer sheets, thermal transfer image receiving sheets, and image receiving sheets.

Claims (6)

  A structure containing a conductive polymer (a), a carbon nanotube (b), and a particulate material (c).   Furthermore, the structure of Claim 1 containing the polymer (l) containing a polyfunctional (meth) acrylate unit.   A carbon nanotube-containing composition containing the conductive polymer (a), the carbon nanotube (b), and the particulate material (c) is applied onto at least one surface of the substrate, and irradiated with active energy rays and / or at room temperature. A method for producing a structure that is left to stand or heat-treated. The method for producing a structure according to claim 3, further comprising a polyfunctional (meth) acrylate (d) and a polymerization initiator (e) in the carbon nanotube-containing composition.   The method for producing a structure according to claim 2 or 4, wherein the carbon nanotube-containing composition further contains a solvent (f).   The method for producing a structure according to any one of claims 3 to 5, further comprising a polymer compound (g) in the carbon nanotube-containing composition.