JP2005314658A - Carbon nanotube-containing polymer, composite having coated film composed of the same and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbon nanotube-containing polymer dispersing and solubilizing the carbon nanotube in a polymerizable monomer without deteriorating characteristics of the carbon nanotube itself without separating, agglomerating the carbon nanotube over a long period by polymerizing the polymerizable monomer, having excellent electroconductivity, etc., coating and covering a substrate according to a simple method and affording the coated film having excellent water resistance, etc., to provide a composite having the coated film composed of the same and to provide a method for producing the same and a method for evaluating physical properties of the carbon nanotube. <P>SOLUTION: The carbon nanotube-containing polymer is obtained by carrying out a polymerization reaction of the polymerizable monomer (i) in a carbon nanotube-containing composition containing an electroconductive polymer (a), the polymerizable monomer (i), the carbon nanotube (c) and, as necessary, further a solvent (b), a polymer (d), a basic compound (e), a surfactant (f), a silane coupling agent (g) and a colloidal silica (h). The composite has the coated film composed of the polymer and the method for producing the same is provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a carbon nanotube-containing polymer, a composite having a coating film made thereof, and a method for producing them.

  Since carbon nanotubes were first discovered by Iijima et al. In 1991 (S. Iijima, Nature, 354, 56 (1991)) (Non-Patent Document 1), their physical properties were evaluated and their functions were elucidated. Research and development is also 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 aggregate 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 strong acid to cut and disperse the single-walled carbon nanotubes (RE Smalley et al., Science, 280, 1253 (1998)). (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, 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 carboxylic acid group, and the carboxylic acid group is converted into an acid chloride. Then, it is proposed to react with an amine compound to introduce a long-chain alkyl group and solubilize in a solvent (J. Chen et al., Science, 282, 95 (1998)) (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 to single-walled carbon nanotubes has been reported (Nakajima et al., Chem. Lett., 638 (2002)). 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.

  In addition, attempts to polymerize methyl methacrylate containing carbon nanotubes have been reported (Zhijie Jia et al., Materials Science and Engineering A271, 395 (1999)) (Non-patent Document 5). In this method, the carbon nanotube is simply mixed with methyl methacrylate to carry out the polymerization reaction. However, since the dispersion of the carbon nanotube is insufficient, there is a problem that the characteristics of the carbon nanotube are not sufficiently exhibited.

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) Zhijie Jia et al., Materials Science and Engineering A271, 395 (1999)

  Therefore, an object of the present invention is to disperse or solubilize carbon nanotubes in a polymerizable monomer without impairing the properties of the carbon nanotube itself, and to store the polymer nanotube for a longer period of time by polymerizing the polymerizable monomer. Also, carbon nanotubes are not separated and aggregated, and are excellent in conductivity, film formability and moldability, and can be applied to and coated on a substrate by a simple method, and the coating film has water resistance, weather resistance, mechanical strength and An object of the present invention is to provide a carbon nanotube-containing polymer having excellent hardness, a composite having a coating film comprising the same, and a method for producing them.

  As a result of intensive studies to solve these problems, the present inventor has found that carbon nanotubes are dispersed or solubilized in a polymerizable monomer by coexisting a conductive polymer, and the present invention has been achieved. .

That is, in the first aspect of the present invention, the polymerizable monomer (i) is subjected to a polymerization reaction in the carbon nanotube-containing composition containing the conductive polymer (a), the polymerizable monomer (i), and the carbon nanotube (c). This is a method for producing a carbon nanotube-containing polymer. In addition to the carbon nanotube-containing composition of the present invention, a solvent (b), a polymer compound (d), a basic compound (e), a surfactant (f), a silane coupling agent (g) and / or colloidal silica ( By containing h), the performance can be improved.
In addition, the conductive polymer (a) is preferably a conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group, or is preferably a water-soluble conductive polymer, and is further water-soluble. Among the conductive conductive polymers, a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group is desirable.
And a method of producing a carbon nanotube-containing polymer comprising irradiating a carbon nanotube-containing composition containing a conductive polymer (a), a polymerizable monomer (i), and a carbon nanotube (c) with ultrasonic waves. is there. By this ultrasonic treatment, the carbon nanotubes can be efficiently dispersed or solubilized in the polymerizable monomer, and the carbon nanotubes can be dispersed or solubilized in the polymerizable monomer in the resulting polymer. it can.
In the second aspect of the present invention, the polymerizable monomer (i) is subjected to a polymerization reaction in the carbon nanotube-containing composition containing the conductive polymer (a), the polymerizable monomer (i), and the carbon nanotube (c). A carbon nanotube-containing polymer produced by a method for producing a carbon nanotube-containing polymer.
3rd of this invention is a composite_body | complex characterized by having the coating film which consists of a carbon nanotube containing polymer of this invention on the at least 1 surface of a base material.

A fourth aspect of the present invention is a composite characterized in that the carbon nanotube-containing polymer of the present invention is coated on at least one surface of a base material, and a coating film is formed by standing at room temperature or heat treatment. It is a manufacturing method of a body.
The fifth aspect of the present invention is characterized in that the carbon nanotube-containing polymer of the present invention is applied onto at least one surface of a base material, and the coating film is formed by standing or heating treatment at room temperature. This is a physical property evaluation method such as conductivity, dispersion or solubilization of carbon nanotubes.

  The method for producing a carbon nanotube-containing polymer of the present invention and the carbon nanotube-containing polymer produced therefrom can disperse or solubilize carbon nanotubes in a polymerizable monomer without impairing the properties of the carbon nanotube itself. Since the polymerizable monomer is polymerized, it does not separate or aggregate even in long-term storage. Further, according to the carbon nanotube-containing polymer of the present invention, by applying the polymer to a base material, the characteristics of the conductive polymer and the carbon nanotube itself are exhibited, and there is no dependency on humidity and the conductivity, A coating film having excellent film properties can be obtained. Moreover, the coating film is excellent in water resistance, weather resistance, mechanical strength and hardness.

  Hereinafter, the present invention will be described in detail.

<Conductive polymer (a)>
Conductive polymers (a) of the present invention, the ammonium salts of sulfonic acid group _(-SO ³ - ^{M +)} and / or ammonium salt of a carboxylic acid group ^- [pi-conjugated polymer having a (-COO M ^+), or Examples thereof include π-conjugated polymers having a sulfonic acid group and / or a carboxyl group. Here, the ammonium ion (M ⁺ ) of the ammonium salt is represented by the following formula (2).

(In the formula (2), R ^{48 to} R ⁵¹ 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 ^{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.

A conductive polymer having a preferable ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group contains at least one repeating unit selected from the following formulas (3) to (11) as a repeating unit of the whole polymer. It is a conductive polymer containing 20 to 100% in the total number.
The conductive polymer (a) is a π-conjugated polymer containing phenylene vinylene, vinylene, thienylene, pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene, carbazolylene or the like as a repeating unit.
Among them, a conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group is used from the viewpoints of particularly improved solubility in a solvent in an organic solvent and the like, and conductivity and film formability. A water-soluble conductive polymer is preferably used in the present invention from the viewpoints of particularly improved solubility in a solvent in water and the like, and conductivity and film-forming properties. Here, the electrically conductive polymer having an ammonium salt of an ammonium salt and / or carboxylic acid groups of the sulfonic acid group, on the nitrogen atom of the backbone or in the polymer of the π-conjugated polymer, ammonium salts of sulfonic acid groups and / or ammonium salt of a carboxylic acid group or include a conductive polymer having an alkyl group containing an alkyl group or an ether bond which is substituted with an ammonium salt of sulfonic acid groups and / or ammonium salt of a carboxylic acid group, . Among these, a conductive polymer having a skeleton containing thienylene, pyrrolylene, iminophenylene, phenylene vinylene, carbazolylene, and isothianaphthene is particularly preferably used. A water-soluble conductive polymer is a conductive material having an alkyl group substituted with an acidic group or an alkyl group containing an ether bond on the skeleton of a π-conjugated polymer or a nitrogen atom in the polymer. It is a polymer.
A conductive polymer having a preferable ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group contains at least one repeating unit selected from the following formulas (3) to (11) as a repeating unit of the whole polymer. It is a conductive polymer containing 20 to 100% in the total number.

(In the formula ^{(3), R 1, 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 - M +, -R 35}} SO 3 - M + ^{-COO - M +, -R 35 COO} - is a group selected from the group consisting of M ^+).

(In the formula ^{(4), R 3, 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 R ⁴ is _{^{-SO 3 - M +, -R 35}} SO 3 - M + ^{-COO - M +, -R 35 COO} - is a group selected from the group consisting of M ^+).

(In the formula ^(5), R 5 ~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 -SO ₃ of ^{~R 8 - M +, -R 35} SO 3 - M +, ^{COO - M +, -R 35 COO} - is a group selected from the group consisting of M ^+).

(In the formula (6), R ⁹ ~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 ⁹ at least one of to R ¹³ is _{^{-SO 3 - M +, -R 35}} SO 3 - M + ^{, -COO - M +, -R 35} COO - as M ⁺ group selected from the group consisting of).

(In the formula (7), R ^{14 _{is, -SO 3 - M +, -R}} 83 SO 3 - M +, -COO - M + and -R ⁸³ COO ^- selected from the group consisting of M ^+, where M ⁺ represents an ammonium ion, and R ⁸³ represents an alkylene, arylene, or aralkylene group having 1 to 24 carbon atoms.)

(In the formula (8), each independently ^{R 52 ~R 57, 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 - M +, -R} 35 SO 3 - M ^{, -COO - M +, -R 35} COO - a M ⁺ group selected from the group consisting of, Ht is, NR ^82, S, O, heteroaryl atom group selected from the group consisting of Se and Te , R ⁸² represents hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms or a substituted or unsubstituted aryl group, and the hydrocarbon chains of R ^{52 to} R ⁵⁷ are bonded to each other at an arbitrary position; A divalent chain forming a cyclic structure of at least one or more 3- to 7-membered saturated or unsaturated hydrocarbons with carbon atoms substituted by such groups may be formed and is thus formed. The cyclic bond chain may contain a bond of carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino at any position, and n is sandwiched between a heterocycle and a benzene ring having substituents R ^{53 to} R ^56. Shrinkage It represents the number of rings, an integer of 0 or 1-3.)

(In the formula (9), R ⁵⁸ ~R ⁶⁶ 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 ^{58 ~R 66 - M +, -R} 35 SO 3 - M ^{, -COO - M +, -R 35} COO - a group selected from the group consisting of M ^+, n is a benzene ring having a substituent R ⁶¹ to R ⁶⁴ and the benzene ring having a substituent R ⁵⁸ and R ⁵⁹ Represents the number of condensed rings sandwiched between 0 and an integer of 0 or 1-3.)

(In the formula (10), each independently ^{R 67 ~R 76, 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 ⁶⁷ to R ⁷⁶ is _{^{-SO 3 - M +, -R 35}} SO 3 - ^{+, -COO - M +, -R} 35 COO - is a group selected from the group consisting of M ^+, n is the number of condensed rings sandwiched benzene ring and a benzoquinone ring having a substituent R ⁶⁷ to R ⁶⁹ Represents 0 or an integer of 1 to 3.)

(In the formula (11), R ⁷⁷ ~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 - M +, -R 35}} SO 3 - ^{+, -COO - M +, -R} 35 COO - a M ⁺ group selected from the group consisting of, X ^a- is chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, sulfate Hydrogen ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluenesulfonate ion, trifluoroacetate ion, and trifluoromethanesulfonate It is at least one kind of anion selected from a group of 1 to 3 anions made of ions, a represents the ionic valence of X, is an integer of 1 to 3, p is a doping rate, and its value Is 0.001-1.)

  In addition, as a conductive polymer having a preferable ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group, polyethylene dioxythiophene polystyrene sulfonate ammonium and / or substituted ammonium is also used. This conductive polymer has a structure in which an ammonium salt of a sulfonic acid group is not introduced into the skeleton of the conductive polymer, but an ammonium salt of polystyrene sulfonate is added as a dopant. This polymer is a polyethylenedioxythiophene polystyrene sulfate produced by polymerizing 3,4-ethylenedioxythiophene (Baytron M manufactured by Bayer) with an oxidizing agent such as iron sulfonate (Baytron C manufactured by Bayer). Can be produced by reacting with amines or / and ammoniums. The polymer can be produced by reacting Baytron P manufactured by Bayer and amines and / or ammoniums.

  Among the conductive polymers having the ammonium salt of the sulfonic acid group and / or the ammonium salt of the carboxylic acid group, the repeating unit represented by the following 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 is 0 <any number of y <1, the 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 An aralkyl group or an alkylene, arylene or aralkylene group, and at least one of R ^{15 to} R ³² is —SO _{^{3 - M +, -R 35 SO}} 3 - + M, -COO - M +, -R 35 COO - is a group selected from the group consisting of M ^+).

Here, the conductive polymer in which the content of the repeating unit having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group with respect to the total number of repeating units of the polymer is 50% or more is an organic solvent, a hydrous organic solvent, or the like. Since the solubility to a solvent is very good, it is preferably used. The content of the repeating unit having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group is more preferably 70% or more, still more preferably 90% or more, and particularly preferably 100%.

  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 formula (13).

(In 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 an ammonium salt of a group and an ammonium salt of a carboxylic acid group, and R ³⁴ is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group. 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, Selected from the group consisting of octoxy, dodecoxy, tetracosoxy, fluoro, chloro and bromo groups Shows one groups, X is 0 <show any number of X <1, n is 3 or more indicates a polymerization degree.)

  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, one compound selected from the group consisting of an acidic group-substituted aniline represented by the following formula (14), an alkali metal salt thereof, an ammonium salt, and a substituted ammonium salt is oxidized with an oxidizing agent in a solution containing a basic compound. This is a conductive polymer obtained by polymerization.

(In the formula (14), the 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 - M +, -R 35}} SO 3 - M +, -COO ^- M ^+, -R ³⁵ COO ^- is a group selected from the group consisting of M ^+).

  The conductive polymer having a preferable ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group is selected from the group consisting of an alkoxy group-substituted aminobenzenesulfonic acid, an alkali metal salt thereof, an ammonium salt, and a substituted ammonium salt, Among them, a conductive polymer obtained by polymerizing a compound in which at least one is an ammonium salt of a sulfonic acid group-substituted aniline or an ammonium salt of a carboxylic acid group-substituted aniline with a oxidizing agent in a solution containing a basic compound is used. .

  Further, as a particularly preferable synthesis method, an ammonium salt represented by the following formula (15) and / or an amine represented by the following formula (16) and a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group are used. A conductive polymer obtained by reacting in a solution is used.

(In the formula (15), R ^{148 to} R ¹⁵¹ are each independently hydrogen, R ³⁵ OH, alkyl having 1 to 24 carbon atoms (C _{1 to} C ₂₄ ), 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, and X _k ^Z− is water. Oxide ion, 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, boron Fluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion ON, p-toluenesulfonate ion, valerate ion, dodecylbenzenesulfonate ion, camphorsulfonate ion, butyrate ion, formate ion, trimethylacetate ion, bromoacetate ion, lactate ion, citrate ion, succinate ion, Shu Acid ion, tartrate ion, fumarate ion, maleate ion, malonate ion, ascorbate ion, anisate ion, anthranilate ion, benzoate ion, cinnamic acid ion, phenylacetate ion, phthalate ion, aniline sulfonic acid Z represents at least one anion selected from the group of 1 to 3 anions consisting of ions, thiocarboxylate ions, methylsulfinate ions, trifluoroacetate ions, and trifluoromethanesulfonate ions. with ion valence of _k Yes, an integer of 1 to 3 is shown, and j is an integer of 1 to 3.

(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. And tetraalkylammonium halides and trimethylbenzylammonium hydroxide.

  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.

In the present invention, among water-soluble conductive polymers, water-soluble conductive polymers having a sulfonic acid and / or a carboxyl group are preferably used in terms of solubility in a solvent such as water, conductivity, and film-forming properties. It is done.
The water-soluble conductive polymer having a sulfonic acid and / or 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 of a carboxylic acid group used in the present invention. It can be used as a raw material when synthesizing a conductive polymer having a salt.
Examples of the water-soluble conductive polymer having a sulfonic acid and / or 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, 04-2683 1, JP-A No. 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.

  Specific examples of water-soluble conductive polymers having sulfonic acid and / or carboxyl groups include unsubstituted and substituted phenylene vinylene, vinylene, thienylene, pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene and carbazolylene. A sulfonic acid group and / or carboxyl group, or a sulfonic acid group and / or carboxyl on the skeleton of a π-conjugated polymer containing at least one selected from the group consisting of repeating units as a repeating unit or a nitrogen atom in the polymer And a water-soluble conductive polymer having an alkyl group substituted with a group or an alkyl group containing an ether bond. Among these, water-soluble conductive polymers having a skeleton containing thienylene, pyrrolylene, iminophenylene, phenylene vinylene, carbazolylene, and isothianaphthene are particularly preferably used.

  A preferable water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group contains at least one repeating unit selected from the following formulas (17) to (25) in a total number of repeating units of 20 to 20 It is a water-soluble conductive polymer containing 100%.

(In Formula (17), R ¹⁰¹ and R ¹⁰² are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ¹⁰¹ and R ¹⁰² is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (18), R ¹⁰³ and R ¹⁰⁴ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ¹⁰³ and R ¹⁰⁴ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (19), R ^{105 to} R ¹⁰⁸ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{105 to} R ¹⁰⁸ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (20), R ^{109 to} R ¹¹³ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ^— , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Or an alkylene, arylene, or aralkylene group, and at least one of R ^{109 to} R ¹¹³ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH, and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (21), R ¹¹⁴ is selected from the group consisting of —SO ₃ ⁻ , —SO ₃ H, —R ⁴² SO ₃ ⁻ , —R ⁴² SO ₃ H, —COOH and —R ⁴² COOH, R ⁴² is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms.)

(In the formula (22), R ^{152 to} R ¹⁵⁷ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Or an alkylene, arylene, or aralkylene group, and at least one of R ^{152 to} R ¹⁵⁷ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH, and —R. ³⁵ is a group selected from the group consisting of COOH, and Ht is NR ⁸² , a heteroatom group selected from the group consisting of S, O, Se and Te, wherein R ⁸² represents hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group. And the hydrocarbon chains of R ^{152 to} R ¹⁵⁷ are bonded to each other at any position, and together with the carbon atoms substituted by such groups, at least one or more 3 to 7 membered saturated or unsaturated hydrocarbons. A bivalent chain forming a cyclic structure may be formed, and the thus formed cyclic bond chain may contain a bond of carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino at any position. Well, n represents the number of condensed rings sandwiched between a heterocycle and a benzene ring having substituents R ^{53 to} R ⁵⁶ , and is an integer of 0 or 1 to 3.)

(In the formula (23), R ^{158 to} R ¹⁶⁶ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{158 to} R ¹⁶⁶ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, and n is a substituent R The number of condensed rings sandwiched between the benzene ring having ¹⁵⁸ and R ¹⁵⁹ and the benzene ring having substituents R ^{161 to} R ¹⁶⁴ is 0 or an integer of 1 to 3)

(In the formula (24), R ^{167 to} R ¹⁷⁶ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{167 to} R ¹⁷⁶ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, and n is a substituent R Represents the number of condensed rings sandwiched between a benzene ring having ^{167 to} R ¹⁶⁹ and a benzoquinone ring, and is an integer of 0 or 1 to 3)

(In the formula (25), R ^{177 to} R ¹⁸¹ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{177 to} R ¹⁸¹ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. a group selected from the group consisting of ³⁵ COOH, X ^a- is chlorine ON, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion , P-toluenesulfonate ion, trifluoroacetate ion, and trifluoromethanesulfonate ion, at least one kind of anion selected from the group of 1 to 3 anions, and a represents the valence of X , 1-3, p is the doping rate, and the value is 0.001-1.)

  Among the above water-soluble conductive polymers having a sulfonic acid and / or carboxyl group, the water-soluble conductive polymer contains 20 to 100% of the repeating units represented by the following formula (26) in the total number of repeating units of the whole polymer. A polymer is more preferably used.

(In formula (26), y represents an arbitrary number of 0 <y <1, and R ^{115 to} R ¹³² are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , _{^{-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, -COOH, -R 35 COOH, -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, or an alkylene, arylene or aralkylene group, and at least one of R ^{115 to} R ¹³² is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ^—. , selected from the group consisting of -R ³⁵ SO ₃ H, -COOH and -R ³⁵ COOH The is a group.)

Here, the water-soluble conductive polymer in which the content of the repeating unit having a sulfonic acid group and / or a carboxyl group with respect to the total number of repeating units of the polymer is 50% or more has solubility in a solvent such as water or a water-containing organic solvent. Since it is very good, it is preferably used. The content of the repeating unit having a sulfonic acid group and / or a carboxyl group is more preferably 70% or more, still more preferably 90% or more, and particularly preferably 100%.
The substituent added to the aromatic ring is preferably an alkyl group, an alkoxy group, a halogen group or the like from the viewpoints of conductivity and solubility, and particularly preferably a water-soluble conductive polymer having an alkoxy group. Among these combinations, the most preferable water-soluble conductive polymer is represented by the following formula (27).

(In the formula (27), R ¹³³ is a sulfonic acid group, a carboxyl group, and one group selected from the group consisting of alkali metal salts, ammonium salts and substituted ammonium salts thereof, and R ³⁴ is a methyl group. , Ethyl group, n-propyl group, 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 A group selected from the group consisting of iso-butoxy, sec-butoxy, tert-butoxy, heptoxy, hexoxy, octoxy, dodecoxy, tetracosoxy, fluoro, chloro and bromo X represents an arbitrary number of 0 <X <1, and n represents the degree of polymerization and is 3 or more.)
Here, at least a part of R ¹³³ is preferably a free acid type sulfonic acid group and / or a carboxyl group from the viewpoint of improving conductivity.

  As the water-soluble 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, an aqueous solution obtained by polymerizing an acidic group-substituted aniline represented by the following formula (28), its alkali metal salt, ammonium salt and / or substituted ammonium salt with an oxidizing agent in a solution containing a basic compound. Conductive polymer.

(In the formula (28), R ^{136 to} R ¹⁴¹ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene, or aralkylene group, and at least one of R ^{136 to} R ¹⁴¹ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH, and —R ^35. A group selected from the group consisting of COOH.)

A particularly preferable water-soluble conductive polymer is obtained by polymerizing an alkoxy group-substituted aminobenzenesulfonic acid, an alkali metal salt thereof, an ammonium salt and / or a substituted ammonium salt with an oxidizing agent in a solution containing a basic compound. Water-soluble conductive polymers are used.
As the conductive polymer in the present invention, those having a mass average molecular weight of 2000 or more and 3 million or less in terms of polyethylene glycol of GPC are excellent in conductivity, film formability and film strength, and are preferably used. A molecular weight of 3,000 to 1,000,000 is more preferred, and a molecular weight of 5,000 to 500,000 is 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. Specific examples of the acidic solution used for the doping treatment include 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.

<Polymerizable monomer (i)>
The polymerizable monomer (i) which is an essential constituent of the carbon nanotube-containing composition of the present invention is obtained by radical polymerization, cationic polymerization, anionic polymerization, ionic polymerization, ring-opening polymerization, elimination polymerization, polyaddition reaction, polycondensation reaction, etc. The polymerizable monomer used in the polymerization reaction is not particularly limited.
The polymerizable monomer (i) used in the present invention includes polyvinyl alcohols such as polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral; polyacrylamide, poly (Nt-butylacrylamide), polyacrylamide methylpropanesulfonic acid, and the like. Polyacrylamides: Polyvinyl pyrrolidone, polystyrene sulfonic 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 resin, polycarbonate resin, vinyl acetate resin, chlorinated polyethylene resin, chlorinated polypropylene resin, styrene resin, acrylic / styrene copolymer resin, vinegar Vinyl / acrylic copolymer resins, polyester resins, styrene / maleic acid copolymer resin, fluorine resin and the polymerizable monomer constituting these copolymer (i).

  Among these polymerizable monomers (i), 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, styrene resin, acrylic / styrene copolymer resin, vinyl acetate / acrylic copolymer resin, polyester resin, styrene / maleic acid copolymer resin are soluble in solvents, stable in composition, and conductive. Among them, a polymerizable monomer (i) constituting a phenol resin, an epoxy resin, a polybutadiene resin, an acrylic resin, a urethane resin, an acrylic / styrene copolymer resin, a vinyl acetate / acrylic copolymer resin, or a polyester resin is particularly preferable. ) Is preferably used It is.

Examples of the polymerizable monomer (i) include methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n- Butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, methoxymethyl (meth) acrylate, n-propoxyethyl (meth) acrylate, iso-propoxyethyl (meth) acrylate, n-butoxy Ethyl (meth) acrylate, iso-butoxyethyl (meth) acrylate, tert-butoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxy-n-propyl (meth) acrylate, 2- Droxy-n-propyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, 4- (meth) acryloyloxy-2- Methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxy-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxy-2-cyclohexyl-1,3- Dioxolane, tetrahydrofurfuryl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoro-n-propyl (meth) acrylate, 2,2,3,3 , 3-pentafluoro-n-propyl (meth) acrylate, cyclohexyl (meth) acrylate, isovo Runyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, α- (tri) fluoromethyl acrylate methyl ester, α- (tri) fluoromethyl acrylate Ethyl ester, α- (tri) fluoromethyl acrylate 2-ethylhexyl ester, α- (tri) fluoromethyl acrylate-n-propyl ester, α- (tri) fluoromethyl acrylate-iso-propyl ester, α- (tri) fluoro Methyl acrylate-n-butyl ester, α- (tri) fluoromethyl acrylate-iso-butyl ester, α- (tri) fluoromethyl acrylate-tert-butyl ester, α- (tri)
Fluoromethyl acrylate methoxymethyl ester, α- (tri) fluoromethyl acrylate ethoxyethyl ester, α- (tri) fluoromethyl acrylate-n-propoxyethyl ester, α- (tri) fluoromethyl acrylate-iso-propoxyethyl ester, α A linear or branched skeleton structure such as-(tri) fluoromethyl acrylate n-butoxyethyl ester, α- (tri) fluoromethyl acrylate-iso-butoxyethyl ester, α- (tri) fluoromethyl acrylate tert-butoxyethyl ester (Meth) acrylic acid ester; styrene, α-methylstyrene, vinyltoluene, p-hydroxystyrene, 3,5-di-tert-butyl-4-hydroxystyrene, 3,5-dimethyl-4-hydride Aromatic alkenyl compounds such as loxystyrene, p-tert-perfluorobutylstyrene, p- (2-hydroxy-iso-propyl) styrene; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride Unsaturated carboxylic acids such as: (meth) acrylonitrile, acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, vinyl chloride, vinyl acetate, ethylene, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, vinylpyrrolidone, etc. Can be mentioned. These may be used alone or in combination of two or more as required. In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate.

<Carbon nanotube (c)>
The carbon nanotube (c), which is another essential constituent of the carbon nanotube-containing composition of the present invention, is not particularly limited. Multi-walled carbon nanotubes overlapped in the form of a coil, or those in the form of a coil, can be used.

  The carbon nanotube (c) will be described in more detail. A plurality of cylinders each having a thickness of several atomic layers with a rounded graphite-like carbon atom surface formed into a nested structure. Illustrated. 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, carbon nanofiber, and the like, which are analogs of carbon nanotube (c), can also be used.

The method for producing the carbon nanotube (c) 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, HiPco method in which carbon monoxide is reacted with an iron catalyst at high temperature and high pressure to grow in the gas phase, etc. Is mentioned.
The carbon nanotubes (c) obtained by the above production method are preferably single-walled carbon nanotubes, and can be further purified by various purification methods such as a washing method, a centrifugal separation method, a filtration method, an oxidation method, and a chromatographic method. Highly purified carbon nanotubes are preferably used because they sufficiently exhibit various functions.

  Further, as the carbon nanotube (c), those which 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 which are cut short by chemical and physical treatment are used. be able to.

<Solvent (b)>
In the method for producing a carbon nanotube-containing polymer of the present invention, the polymerization reaction can be carried out with the polymerizable monomer (i), but by adding the solvent (b), the carbon nanotube (c) can be dispersed. Improves the solubilization and improves the polymerizability of the polymerizable monomer (i).
Solvent (b) is conductive polymer (a), polymerizable monomer (i), carbon nanotube (c), polymer compound (d), basic compound (e), surfactant (f), silane coupling The agent (g) and the colloidal silica (h) are not particularly limited as long as they dissolve or disperse. Moreover, what melt | dissolves the polymerization initiator and chain transfer agent used for a polymerization reaction is used preferably.
Examples of the solvent (b) include water, methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol and other alcohols; acetone, methyl ethyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone and other ketones; ethylene glycol, ethylene glycol methyl ether, ethylene Ethylene glycols such as glycol mono-n-propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol propyl ether, propylene glycol monomethyl ether acetate; dimethylformamide, dimethyl Amides such as acetamide; N-methylpyrrolidone, N-ethyl Pyrrolidones such as pyrrolidone; hydroxyesters such as dimethylsulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate, methyl β-methoxyisobutyrate, methyl α-hydroxyisobutyrate; anilines such as aniline and N-methylaniline, Aromatic hydrocarbons such as benzene, toluene and xylene, m-cresol, acetonitrile, tetrahydrofuran, and 1,4-dioxane are preferably used.

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

  In addition, as a preferable solvent (b) when a water-soluble conductive polymer having a sulfonic acid and / or a carboxyl group is used as the conductive polymer (a), a solvent is preferable in terms of solubility and dispersibility of the carbon nanotube (c). As (b), water or a water-containing organic solvent is preferably used.

<Polymer compound (d)>
In the carbon nanotube-containing composition of the present invention, the use of the polymer compound (d) further improves the substrate adhesion and strength of the coating film.
The polymer compound (d) in the present invention is not particularly limited as long as it can be dissolved or dispersed (emulsion formation) in the solvent (b) used in 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, vinegar Vinyl 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, fluororesin and copolymers thereof Etc. are used. In addition, these polymer compounds (d) may be a mixture of two or more kinds at an arbitrary ratio.

  Among these polymer compounds (d), when a conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group is used as the conductive polymer (a), an alkyd resin, a melamine resin, or a urea resin is used. , 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 copolymer resins, polyester resins, and styrene / maleic acid copolymer resins are preferably used in terms of solubility in solvents, composition stability, and conductivity, and among them, phenol resins, epoxy resins, and polybutadienes are particularly preferable. Resin, acrylic resin, resin Mixing and using one or more of tan resin, acrylic / styrene copolymer resin, vinyl acetate / acrylic copolymer resin, and polyester resin, solubility in solvent, stability of composition, conductivity From the viewpoint of sex.

  Among these polymer compounds (d), when a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group is used, a water-soluble polymer compound or a polymer compound that forms an emulsion in an aqueous system is dissolved in a 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 (e)>
The basic compound (e) constituting the carbon nanotube-containing composition of the present invention is added to the carbon nanotube-containing composition to dedope the conductive polymer and further improve the solubility in the solvent (b). effective. Further, by forming a salt with a free sulfonic acid group and a carboxyl group, the solubility in a solvent is particularly improved, and the solubilization or dispersion of the carbon nanotube (c) in the solvent (b) is promoted. .

The basic compound (e) 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 (e) is shown in the following formula (29).

(In the formula (29), R ^{245 to} R ²⁴⁶ are independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms (C _{1 to} C ₄ ), CH ₂ OH, CH ₂ CH ₂ OH, CONH ₂ or NH. ₂ )

  The structural formula of ammonium salts used as the basic compound (e) is shown in the following formula (30).

(In the formula (30), R ^{248 to} R ²⁵¹ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms (C _{1 to} C ₄ ), CH ₂ OH, CH ₂ CH ₂ OH, CONH ₂ or NH. ₂ and X ⁻ represents OH ⁻ , 1/2 · SO ₄ ²⁻ , NO ₃ ⁻ , 1 / 2CO ₃ ²⁻ , HCO ₃ ⁻ , 1/2 · (COO) ₂ ²⁻ , or R′COO ^−. R ′ represents an alkyl group having 1 to 3 carbon atoms (C _{1 to} C ₃ ).

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 (e) 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 (f)>
In the carbon nanotube-containing composition of the present invention, the carbon nanotube (c) can be obtained by using only the conductive polymer (a), the solvent (b), the carbon nanotube (c), the polymer compound (d), and the basic compound (e). Although it is solubilized or dispersed, the polymer after the polymerization reaction of the polymerizable monomer (i) does not separate or aggregate even during long-term storage, and can form a film or a composite with good performance. When the surfactant (f) is added, solubilization or dispersion is further promoted, and flatness, coating property, conductivity and the like are improved.

Specific examples of the surfactant (f) 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-sulfoalkyleneammonium betaine, Betaines such as N, N-dialkyl-N, N-bispolyoxyethylene ammonium sulfate betaine, 2-alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine, N, N-dialkylaminoal Amphoteric surfactants such as aminocarboxylic acids such as lencarboxylates; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl 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.

<Silane coupling agent (g)>
In the present invention, a carbon nanotube containing component of the conductive polymer (a), the solvent (b), the carbon nanotube (c), the polymer compound (d), the basic compound (e), and the surfactant (f) is contained. A silane coupling agent (g) can be used in combination with the composition. The water resistance of the coating film obtained from the carbon nanotube-containing polymer combined with the silane coupling agent (g) is remarkably improved. As the silane coupling agent (g), a silane coupling agent (g) represented by the following 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.

Wherein l 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.

<Colloidal silica (h)>
In the present invention, conductive polymer (a), solvent (b), carbon nanotube (c), polymer compound (d), basic compound (e), surfactant (f), silane coupling agent (g The colloidal silica (h) can be used in combination with the crosslinkable carbon nanotube-containing composition containing the component (1). The surface hardness and weather resistance of the coating film obtained from the carbon nanotube-containing polymer combined with colloidal silica (h) are remarkably improved.

  Although colloidal silica (h) in this invention is not specifically limited, What is disperse | distributed to the mixed solvent of water, an organic solvent, or water and an organic solvent is used preferably. 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. .

  Further, as the colloidal silica (h), those having a particle diameter of 1 nm to 300 nm are used, preferably those having a particle diameter of 1 nm to 150 nm, more preferably 1 nm to 50 nm. If the particle size is too large, the hardness is insufficient and the solution stability of the colloidal silica itself is also lowered.

<Carbon nanotube-containing composition>
The use ratio of the conductive polymer (a), the polymerizable monomer (i), and the solvent (b) is conductive with respect to a total of 100 parts by mass of the polymerizable monomer (i) and the solvent (b). It is preferable that a polymer (a) is 0.001-50 mass parts, More preferably, it is 0.01-30 mass parts. When the conductive polymer (a) is less than 0.001 part by mass, the conductivity is inferior, and the carbon nanotube (c) 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 (c) is lowered.

  In addition, the use ratio of the carbon nanotube (c), the polymerizable monomer (i), and the solvent (b) is such that the total amount of the polymerizable monomer (i) and the solvent (b) is 100 parts by mass. It is preferable that a nanotube (c) is 0.0001-20 mass parts, More preferably, it is 0.001-10 mass parts. When the carbon nanotube (c) is less than 0.0001 part by mass, the performance due to the carbon nanotube (c) 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 (c) is lowered.

  The use ratio of the polymer compound (d), the polymerizable monomer (i), and the solvent (b) is high relative to 100 parts by mass of the total of the polymerizable monomer (i) and the solvent (b). It is preferable that a compound (d) is 0.1-400 mass parts, More preferably, it is 0.5-300 mass parts. When the polymer compound (d) 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 (d) is 400 parts by mass or less, the conductive polymer (a) and the carbon nanotube (c) There is little decrease in solubility, and high conductivity is maintained.

The use ratio of the basic compound (e), the polymerizable monomer (i) and the solvent (b) is basic with respect to a total of 100 parts by mass of the polymerizable monomer (i) and the solvent (b). It is preferable that a compound (e) is 0.1-10 mass parts, More preferably, it is 0.1-5 mass parts.
When the basic compound (e) is in this range, the solubility of the water-soluble conductive polymer is improved, solubilization or dispersion of the carbon nanotube (c) in the solvent (b) is promoted, and the conductivity is improved. To do.

  The use ratio of the surfactant (f), the polymerizable monomer (i) and the solvent (b) is such that the surfactant is active with respect to a total of 100 parts by mass of the polymerizable monomer (i) and the solvent (b). It is preferable that an agent (f) is 0.0001-10 mass parts, More preferably, it is 0.01-5 mass parts. When the surfactant (f) exceeds 10 parts by mass, the coatability is improved, but a phenomenon such as inferior conductivity occurs, and the efficiency of solubilization or dispersion of the carbon nanotube (c) decreases.

  The use ratio of the silane coupling agent (g), the polymerizable monomer (i), and the solvent (b) is silane with respect to 100 parts by mass of the total of the polymerizable monomer (i) and the solvent (b). It is preferable that a coupling agent (g) is 0.001-20 mass parts, More preferably, it is 0.01-15 mass parts. When the silane coupling agent (g) 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 improved. Sexuality may worsen.

  The use ratio of the colloidal silica (h), the polymerizable monomer (i), and the solvent (b) is colloidal with respect to 100 parts by mass of the total of the polymerizable monomer (i) and the solvent (b). It is preferable that silica (h) is 0.001-100 mass parts, More preferably, it is 0.01-50 mass parts. If colloidal silica (h) is 0.001 mass part or more, the improvement width of water resistance, weather resistance, and hardness will become large. On the other hand, if it exceeds 100 parts by mass, the solubility, flatness, transparency, and conductivity may be deteriorated.

  The use ratio of the solvent (b) and the polymerizable monomer (i) is preferably 0 to 2000 parts by mass, more preferably 1 to 2000 parts by mass of the solvent (b) with respect to 100 parts by mass of the polymerizable monomer (i). 1000 parts by mass. By adding the solvent (b), the solubilization or dispersion efficiency of the carbon nanotube (c) is improved, and the polymerizability of the polymerizable monomer (i) is improved. On the other hand, when it exceeds 2000 parts by mass, the production rate of the carbon nanotube-containing polymer is lowered.

  Furthermore, the carbon nanotube-containing composition and the carbon nanotube-containing polymer of the present invention include a plasticizer, a dispersant, a coating surface adjuster, a fluidity adjuster, an ultraviolet absorber, an antioxidant, and a storage stabilizer as necessary. In addition, various known substances such as adhesion assistants and thickeners can be added and used.

  In addition, the carbon nanotube-containing composition and the carbon nanotube-containing polymer of the present invention can contain a conductive substance in order to further improve the conductivity. Examples of the conductive material include carbon-based materials such as carbon fiber, conductive carbon black, and graphite, metal oxides such as tin oxide and zinc oxide, and metals such as silver, nickel, and copper.

<Method for producing carbon nanotube-containing composition>
When mixing these components, stirring or kneading devices such as ultrasonic waves, homogenizers, spiral mixers, planetary mixers, dispersers, and hybrid mixers are used. In particular, the conductive polymer (a) having a sulfonic acid group ammonium salt and / or a carboxylic acid group ammonium salt, a solvent (b), a carbon nanotube (c), and other components are mixed and subjected to ultrasonic waves. Irradiation is preferable, and in this case, it is preferable to perform treatment by using ultrasonic irradiation and a homogenizer 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 processing time are sufficient to uniformly disperse or dissolve the carbon nanotube (c) in the solvent (b). . 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, and 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. Moreover, the time of ultrasonic irradiation treatment is preferably 1 minute to 48 hours, more preferably 5 minutes to 48 hours. Thereafter, it is desirable to thoroughly disperse or dissolve using a ball-type kneader such as a ball mill, a vibration mill, a sand mill, or a roll mill.

<Polymerization reaction>
In the polymerization using a polymerization initiator, a radical form of the polymerization initiator is generated in the reaction solution, and sequential polymerization of the polymerizable monomer (i) proceeds from this radical form as a starting point. The polymerization initiator used for producing the carbon nanotube-containing polymer of the present invention is preferably one that generates radicals efficiently by heat. Examples of such a polymerization initiator include 2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (2,4-dimethylvaleronitrile). Azo compounds such as 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, benzoyl peroxide, organic peroxides such as di-t-butyl peroxide, potassium persulfate, ammonium persulfate, etc. Is mentioned.

  A chain transfer agent may be used when producing the carbon nanotube-containing polymer. When a chain transfer agent is used, there are advantages such that the amount of the polymerization initiator can be reduced when the low molecular weight copolymer is produced, and the molecular weight distribution of the copolymer can be reduced. Suitable chain transfer agents include, for example, 1-butanethiol, 2-butanethiol, 1-octanethiol, 1-decanethiol, 1-tetradecanethiol, cyclohexanethiol, 2-methyl-1-propanethiol, n-dodecyl. A mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan, etc. are mentioned.

  As a method for producing the carbon nanotube-containing polymer of the present invention, a polymerization method generally referred to as solution polymerization is preferable. In solution polymerization, a polymerizable monomer, an initiator, and in some cases a chain transfer agent may be charged all at once into the polymerization reaction vessel to carry out the polymerization reaction, or the copolymerization reactivity ratio of each polymerizable monomer, each polymerization In consideration of the polymerization rate constant in the case of homopolymerization and copolymerization of the polymerizable monomer, there is also a method in which each polymerizable monomer and initiator, and in some cases, the chain transfer agent are dropped independently at an individual speed and / or concentration. Can be used. The polymerization temperature in the solution polymerization method is not particularly limited, but is preferably in the range of 50 to 150 ° C.

  The solvent used in the solution polymerization method is preferably a solvent that can dissolve both the polymerizable monomer (i), the polymerization initiator, and the chain transfer agent when the chain transfer agent is used in combination.

<Composite>
In the present invention, the base material on which the carbon nanotube-containing polymer 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, polymer compounds, plastics, and films include 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 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 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.

  After coating the carbon nanotube-containing polymer on the surface of the substrate, it can be left at room temperature, but the coating film can also be heat-treated. By the heat treatment, the crosslinking reaction between the carbon nanotube (c), the polymer compound (d), the basic compound (e), and the conductive polymer (a) is further promoted, and water resistance can be imparted in a shorter time. Moreover, since the quantity of the solvent (b) which remains can be reduced more and electroconductivity improves further, it is preferable. 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 composite of the present invention still has excellent conductivity, it is doped with an acid after coating a carbon nanotube-containing polymer 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 polymer of the present invention described above, the carbon nanotube (c) is added to the polymerizable monomer (i) and / or the solvent (b) together with the conductive polymer (a). (C) The carbon nanotube (c) can be dispersed or solubilized in the polymerizable monomer (i) and / or the solvent (b) without impairing the properties of itself, and can be separated and aggregated even during long-term storage. do not do. Although the reason for this is not clearly understood, the carbon nanotube (c) is dispersed or solubilized together with the conductive polymer (a) by adsorbing or spirally wrapping the conductive polymer (a) on the carbon nanotube (c). It is speculated that
Moreover, in the carbon nanotube-containing polymer of the present invention, since the conductive polymer (a) and the carbon nanotube (c) are used in combination, they are excellent in conductivity, film formability, and moldability.

<Method for evaluating properties of carbon nanotube>
The carbon nanotube-containing polymer of the present invention is coated on at least one surface of the substrate, and after standing at room temperature or heat treatment to form a coating film, the conductivity of the coating film is measured by a known method. By doing so, it is possible to easily evaluate the conductivity, the degree of aggregation, and the degree of bundling of the carbon nanotube itself used.
(Example)

  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.

<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 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 dropped into 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 salt of a sulfonic acid group.

<Preparation of carbon nanotube-containing composition>
Carbon nanotube-containing composition 1:
5 parts by mass of the conductive polymer (A-1) of Production Example 1 above, 20 parts by mass of vinylpyrrolidone, 1.0 part by mass of carbon nanotubes (multi-walled carbon nanotubes manufactured by ILJIN, CVD method) 80 parts by mass of water Were mixed at room temperature to prepare a carbon nanotube-containing composition 1.

Carbon nanotube-containing composition 2:
5 parts by mass of the conductive polymer (A-1) of Production Example 1 above, 20 parts by mass of vinyl pyrrolidone, 1.0 part by mass of carbon nanotubes, and 0.1 part by mass of ammonia were mixed with 80 parts by mass of water at room temperature to form carbon. A nanotube-containing composition 2 was prepared.

Carbon nanotube-containing composition 3:
5 parts by mass of the conductive polymer (A-1) of Production Example 1 above, 20 parts by mass of vinyl pyrrolidone, 1.0 part by mass of carbon nanotubes, 0.5 part by mass of γ-glycidoxypropyltrimethoxysilane were added to 80 parts by mass of water. And a carbon nanotube-containing composition 3 was prepared by mixing at room temperature.

Carbon nanotube-containing composition 4:
Carbon nanotubes were prepared by mixing 5 parts by mass of the conductive polymer (A-1) of Production Example 1 above, 10 parts by mass of vinyl pyrrolidone, 1.0 part by mass of carbon nanotubes, and 10 parts by mass of polyvinyl alcohol with 80 parts by mass of water at room temperature. Containing composition 4 was prepared.

Carbon nanotube-containing composition 5:
5 parts by mass of the conductive polymer (A-2) of Production Example 2 above, 25 parts by mass of methyl methacrylate, and 0.4 parts by mass of carbon nanotubes were mixed with 75 parts by mass of dimethylacetamide at room temperature to prepare a carbon nanotube-containing composition 5 Was prepared.

Carbon nanotube-containing composition 6:
5 parts by weight of the conductive polymer (A-2) of Production Example 2, 25 parts by weight of methyl methacrylate, 0.4 parts by weight of carbon nanotubes, and 0.1 parts by weight of sodium dodecylbenzenesulfonate are added to 75 parts by weight of dimethylacetamide at room temperature. To prepare a carbon nanotube-containing composition 6.

Carbon nanotube-containing composition 7:
5 parts by mass of the conductive polymer (A-2) of Production Example 2 above, 25 parts by mass of methyl methacrylate, 0.4 parts by mass of carbon nanotubes, and 5 parts by mass of colloidal silica (particle diameter: 10 nm) are added to 75 parts by mass of dimethylacetamide. A carbon nanotube-containing composition 7 was prepared by mixing at room temperature.

Carbon nanotube-containing composition 8:
20 parts by mass of vinyl pyrrolidone and 1.0 part by mass of carbon nanotubes were mixed with 80 parts by mass of water at room temperature to prepare a carbon nanotube-containing composition 8.

Carbon nanotube-containing composition 9:
A carbon nanotube-containing composition 9 was prepared by mixing 25 parts by mass of methyl methacrylate and 0.4 parts by mass of carbon nanotubes with 75 parts by mass of dimethylacetamide at room temperature.

Conductive composition 1:
The conductive composition 1 was prepared by mixing 5 parts by mass of the conductive polymer (A-2) of Production Example 2 and 25 parts by mass of methyl methacrylate with 100 parts by mass of dimethylacetamide at room temperature.

<Polymerization reaction>
Examples 1-4, Comparative Example 1
(No sonication)
Nitrogen bubbling (200 cc, 1 Hr) was performed on 5 g of the carbon nanotube-containing compositions 1 to 4 and 8, and then a polymerization reaction was performed at 100 ° C. for 10 hours to obtain a carbon nanotube-containing polymer.
(With ultrasonic treatment)
An ultrasonic homogenizer treatment (vibra cell 20 kHz, manufactured by SONICS) was performed on 5 g of the carbon nanotube-containing compositions 1 to 4 and 8 for 1 hour. The composition was subjected to nitrogen bubbling (200 cc, 1 Hr) and then subjected to a polymerization reaction at 100 ° C. for 10 hours to obtain a carbon nanotube-containing polymer.

Examples 5-7, Comparative Example 2
(No sonication)
To 2 g of the above carbon nanotube-containing compositions 5 to 7 and 9, 0.125 g of 2,2′-azobis (isobutyronitrile) was added and dissolved by stirring. Thereafter, nitrogen bubbling (200 cc, 1.5 min) was performed on the composition, and then a polymerization reaction was performed at 80 ° C. for 6 hours to obtain a polymer.
(With ultrasonic treatment)
An ultrasonic homogenizer treatment (vibra cell 20 kHz, manufactured by SONICS) was performed on 5 g of the carbon nanotube-containing compositions 5 to 7 and 9 for 1 hour. To the composition, 2,025 g of 2,2′-azobis (isobutyronitrile) was added and dissolved by stirring. Thereafter, nitrogen bubbling (200 cc, 1.5 min) was performed on the composition, and then a polymerization reaction was performed at 80 ° C. for 6 hours to obtain a carbon nanotube-containing polymer.

Comparative Example 3
(No sonication)
To 2 g of the conductive composition 1, 0.1025 g of 2,2′-azobis (isobutyronitrile) was added and dissolved by stirring. Thereafter, nitrogen bubbling (200 cc, 1.5 min) was performed on the composition, and then a polymerization reaction was performed at 80 ° C. for 6 hours to obtain a carbon nanotube-containing polymer.
(With ultrasonic treatment)
An ultrasonic homogenizer treatment (vibra cell 20 KHz manufactured by SONICS) was performed on 5 g of the conductive composition 1 for 1 hour. To the composition, 2,025 g of 2,2′-azobis (isobutyronitrile) was added and dissolved by stirring. Thereafter, the composition was subjected to nitrogen bubbling (200 cc, 1.5 min) and then subjected to a polymerization reaction at 80 ° C. for 6 hours to obtain a polymer.

<Evaluation method>
After visually observing the state of the solution of the carbon nanotube-containing polymer obtained in Examples 1 to 7 and Comparative Examples 1 and 2, the polymer was applied to a glass substrate by a bar coater method (using bar coat No. 5). And dried at 150 ° C. for 5 minutes to form a coating film, and after observing the appearance, the surface resistance value was measured. The results are shown in Table 1.

  After visually observing the state of the polymer solution obtained in Comparative Example 3, the polymer was applied to a glass substrate by the bar coater method (using bar coat No. 5) and dried at 150 ° C. for 5 minutes. After forming the coating film and observing the appearance, the surface resistance was measured. The results are shown in Table 1.

(Solution state)
After the preparation of the carbon nanotube-containing polymer, the solution state after 24 hours was visually observed.
○: uniformly dispersed or dissolved ×: unevenly dispersed (surface resistance value)
For the measurement of the surface resistance value under the conditions of 25 ° C. and 15% RH, when the surface resistance value is 10 ⁸ Ω or more, the double probe method (distance between electrodes: 20 mm) is used, and the surface resistance value is 10 ⁷ Ω. In the following cases, the 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.

  The carbon nanotube-containing composition of the present invention can be obtained by using various antistatic agents, capacitors, batteries, fuel cells and their polymer electrolyte membranes, electrode layers, catalysts by using simple coating techniques such as coating, spraying, casting, and dipping. Layer, gas diffusion layer, gas diffusion electrode layer, separator, etc., EMI shield, chemical sensor, display element, nonlinear material, anticorrosive, adhesive, fiber, spinning material, antistatic paint, anticorrosion paint, electrodeposition paint It can be applied to applications such as plating primer, conductive primer for electrostatic coating, anticorrosion, and improvement of battery storage capacity. Further, the composite of the present invention is an anti-static film such as an industrial packaging material such as a semiconductor or an electric electronic component, an electrophotographic recording material such as an overhead projector film or a slide film, an audio tape, a video tape, a computer tape, Prevention of electrification of magnetic recording tapes such as floppy disks, LSI wiring of electronic devices, electron guns and electrodes of field emission displays (FEDs), hydrogen storage agents, transparent touch panels, electroluminescence displays, liquid crystal displays, etc. Input and display device surface antistatic and transparent electrodes, light emitting materials forming organic electroluminescent elements, buffer materials, electron transport materials, hole transport materials and fluorescent materials, thermal transfer sheets, transfer sheets, thermal transfer image receiving sheets, receiving It is used as a sheet.

Claims (29)

  A carbon nanotube-containing weight characterized in that a polymerizable monomer (i) is subjected to a polymerization reaction in a carbon nanotube-containing composition containing a conductive polymer (a), a polymerizable monomer (i), and a carbon nanotube (c). Manufacturing method of coalescence.   The method for producing a carbon nanotube-containing polymer according to claim 1, wherein the carbon nanotube-containing composition further contains a solvent (b).   The method for producing a carbon nanotube-containing polymer according to claim 1 or 2, wherein the carbon nanotube-containing composition further contains a polymer compound (d).   The method for producing a carbon nanotube-containing polymer according to any one of claims 1 to 3, wherein the carbon nanotube-containing composition further contains a basic compound (e).   The method for producing a carbon nanotube-containing polymer according to any one of claims 1 to 4, wherein the carbon nanotube-containing composition further contains a surfactant (f). The carbon nanotube-containing polymer according to any one of claims 1 to 5, wherein the carbon nanotube-containing composition further contains a silane coupling agent (g) represented by the following formula (1): Production method.

(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. )   The method for producing a carbon nanotube-containing polymer according to any one of claims 1 to 6, wherein the carbon nanotube-containing composition further contains colloidal silica (h). The conductive polymer (a) is a conductive polymer (a) having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group, and the ammonium ion of the ammonium salt is represented by the following formula (2) The method for producing a carbon nanotube-containing polymer according to any one of claims 1 to 7, wherein the polymer is a carbon nanotube-containing polymer.

(In the formula (2), R ^{48 to} R ⁵¹ 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 ^{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. The conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group contains at least one or more repeating units selected from the following formulas (3) to (11), and the total number of repeating units in the entire polymer. The method for producing a carbon nanotube-containing polymer according to claim 8, wherein the polymer is a conductive polymer contained in an amount of 20 to 100%.

(In the formula ^{(3), R 1, 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 - M +, -R 35}} SO 3 - M + ^{-COO - M +, -R 35 COO} - is a group selected from the group consisting of M ^+).

(In the formula ^{(4), R 3, 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 R ⁴ is _{^{-SO 3 - M +, -R 35}} SO 3 - M + ^{-COO - M +, -R 35 COO} - is a group selected from the group consisting of M ^+).

(In the formula ^(5), R 5 ~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 -SO ₃ of ^{~R 8 - M +, -R 35} SO 3 - M +, ^{COO - M +, -R 35 COO} - is a group selected from the group consisting of M ^+).

(In the formula (6), R ⁹ ~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 ⁹ at least one of to R ¹³ is _{^{-SO 3 - M +, -R 35}} SO 3 - M + ^{, -COO - M +, -R 35} COO - as M ⁺ group selected from the group consisting of).

(In the formula (7), R ^{14 _{is, -SO 3 - M +, -R}} 83 SO 3 - M +, -COO - M + and -R ⁸³ COO ^- selected from the group consisting of M ^+, where M ⁺ represents an ammonium ion, and R ⁸³ represents an alkylene, arylene, or aralkylene group having 1 to 24 carbon atoms.)

(In the formula (8), each independently ^{R 52 ~R 57, 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 - M +, -R} 35 SO 3 - M ^{, -COO - M +, -R 35} COO - a M ⁺ group selected from the group consisting of, Ht is, NR ^82, S, O, heteroaryl atom group selected from the group consisting of Se and Te , R ⁸² represents hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms or a substituted or unsubstituted aryl group, and the hydrocarbon chains of R ^{52 to} R ⁵⁷ are bonded to each other at an arbitrary position; A divalent chain forming a cyclic structure of at least one or more 3 to 7-membered saturated or unsaturated hydrocarbons with carbon atoms substituted by such groups may be formed, and is thus formed. The cyclic bond chain may contain a bond of carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino at any position, and n is sandwiched between a heterocycle and a benzene ring having substituents R ^{53 to} R ^56. Shrinkage It represents the number of rings, an integer of 0 or 1-3.)

(In the formula (9), R ⁵⁸ ~R ⁶⁶ are each ^{_{independently, H, -SO 3 -, -SO}} 3 - M +, -SO 3 H, -R 3
_{^{5 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, alkyl for R ³⁵ having 1 to 24 carbon atoms, aryl or aralkyl group Alternatively alkylene, arylene or aralkylene group, and at least one of -SO ₃ of ^{R 58 ~R 66 - M +,} -R 35 SO 3 - + M, -COO - M +, -R 35 COO - M + A group selected from the group consisting of: n is a substituent R ⁵⁸ And the number of condensed rings sandwiched between the benzene ring having R ⁵⁹ and the benzene ring having substituents R ^{61 to} R ⁶⁴ , and is an integer of 0 or 1 to 3. )

(In the formula (10), each independently ^{R 67 ~R 76, 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 ⁶⁷ to R ⁷⁶ is _{^{-SO 3 - M +, -R 35}} SO 3 - ^{+, -COO - M +, -R} 35 COO - is a group selected from the group consisting of M ^+, n is the number of condensed rings sandwiched benzene ring and a benzoquinone ring having a substituent R ⁶⁷ to R ⁶⁹ Represents 0 or an integer of 1 to 3.)

(In the formula (11), R ⁷⁷ ~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 - M +, -R 35}} SO 3 - ^{+, -COO - M +, -R} 35 COO - a M ⁺ group selected from the group consisting of, X ^a- is chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, sulfate Hydrogen ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluenesulfonate ion, trifluoroacetate ion, and trifluoromethanesulfonate It is at least one kind of anion selected from a group of 1 to 3 anions made of ions, a represents an ionic valence of X, is an integer of 1 to 3, p is a doping rate, and its value Is 0.001-1.) The conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group contains 20 to 100% of a repeating unit represented by the following formula (12) in the total number of repeating units of the whole polymer. The method for producing a carbon nanotube-containing polymer according to claim 8.

(In the formula (12), y is 0 <any number of y <1, the 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 An aralkyl group or an alkylene, arylene or aralkylene group, and at least one of R ^{15 to} R ³² is —SO _{^{3 - M +, -R 35 SO}} 3 - + M, -COO - M +, -R 35 COO - is a group selected from the group consisting of M ^+). 9. The carbon nanotube-containing polymer according to claim 8, wherein the conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group is represented by the following formula (13). Production method.

(In 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 an ammonium salt of a group and an ammonium salt of a carboxylic acid group, wherein R ³⁴ is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group. 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, Selected from the group consisting of octoxy, dodecoxy, tetracosoxy, fluoro, chloro and bromo groups Shows one groups, X is 0 <show any number of X <1, n is 3 or more indicates a polymerization degree.) The conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group comprises an acidic group-substituted aniline represented by the following formula (14), an alkali metal salt thereof, an ammonium salt, and a substituted ammonium salt: 9. The method for producing a carbon nanotube-containing polymer according to claim 8, which is a conductive polymer obtained by polymerizing one selected compound with a oxidizing agent in a solution containing a basic compound. .

(In the formula (14), the 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 or alkylene, arylene or aralkylene group having 1 to 24 carbon atoms, and R ^{36 to} R ⁴¹ out at least one of _{^{-SO 3 - M +, -R 35}} SO 3 - M +, -COO ^- M ^+, -R ³⁵ COO ^- is a group selected from the group consisting of M ^+).   The conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group is selected from the group consisting of an alkoxy group-substituted aminobenzene sulfonic acid, an alkali metal salt thereof, an ammonium salt, and a substituted ammonium salt, of which at least One is a conductive polymer obtained by polymerizing a compound containing an ammonium salt of a sulfonic acid group-substituted aniline or an ammonium salt of a carboxylic acid group-substituted aniline with a oxidizing agent in a solution containing a basic compound. The method for producing a carbon nanotube-containing polymer according to claim 8. The conductive polymer having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group is an ammonium salt represented by the following formula (15) and / or an amine and a sulfonic acid group represented by the following formula (16): 9. The method for producing a carbon nanotube-containing polymer according to claim 8, which is a conductive polymer obtained by reacting a water-soluble conductive polymer having a carboxyl group in a solution.

(In the formula (15), R ^{148 to} R ¹⁵¹ are each independently hydrogen, R ³⁵ OH, alkyl having 1 to 24 carbon atoms (C _{1 to} C ₂₄ ), 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, and X _k ^Z− is water. Oxide ion, 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, boron Fluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion ON, p-toluenesulfonate ion, valerate ion, dodecylbenzenesulfonate ion, camphorsulfonate ion, butyrate ion, formate ion, trimethylacetate ion, bromoacetate ion, lactate ion, citrate ion, succinate ion, Shu Acid ion, tartrate ion, fumarate ion, maleate ion, malonate ion, ascorbate ion, anisate ion, anthranilate ion, benzoate ion, cinnamic acid ion, phenylacetate ion, phthalate ion, aniline sulfonic acid Z represents at least one anion selected from the group of 1 to 3 anions consisting of ions, thiocarboxylate ions, methylsulfinate ions, trifluoroacetate ions, and trifluoromethanesulfonate ions. with ion valence of _k Yes, an integer of 1 to 3 is shown, and j is an integer of 1 to 3.

(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.   9. The conductive polymer (a) having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxylic acid group is polyethylene dioxythiophene polystyrene sulfonate ammonium and / or a substituted ammonium. Method for producing carbon nanotube-containing polymer   The method for producing a carbon nanotube-containing polymer according to any one of claims 1 to 7, wherein the conductive polymer (a) is a water-soluble conductive polymer.   The method for producing a carbon nanotube-containing polymer according to claim 16, wherein the water-soluble conductive polymer is a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group. The water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group contains 20 to 100 of at least one repeating unit selected from the following formulas (17) to (25) in the total number of repeating units of the whole polymer. The method for producing a carbon nanotube-containing polymer according to claim 14 or 17, wherein the carbon nanotube-containing polymer is a water-soluble conductive polymer.

(In Formula (17), R ¹⁰¹ and R ¹⁰² are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ¹⁰¹ and R ¹⁰² is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (18), R ¹⁰³ and R ¹⁰⁴ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ¹⁰³ and R ¹⁰⁴ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (19), R ^{105 to} R ¹⁰⁸ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{105 to} R ¹⁰⁸ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (20), R ^{109 to} R ¹¹³ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ^— , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Or an alkylene, arylene, or aralkylene group, and at least one of R ^{109 to} R ¹¹³ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH, and —R. ³⁵ is a group selected from the group consisting of COOH.)

(In the formula (21), R ¹¹⁴ is selected from the group consisting of —SO ₃ ⁻ , —SO ₃ H, —R ⁴² SO ₃ ⁻ , —R ⁴² SO ₃ H, —COOH and —R ⁴² COOH, R ⁴² is an alkylene, arylene or aralkylene group having 1 to 24 carbon atoms.)

(In the formula (22), R ^{152 to} R ¹⁵⁷ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{152 to} R ¹⁵⁷ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, and Ht is NR ⁸² , a heteroatom group selected from the group consisting of S, O, Se and Te, wherein R ⁸² represents hydrogen and a linear or branched alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted aryl group. And the hydrocarbon chains of R ^{152 to} R ¹⁵⁷ are bonded to each other at any position, and together with carbon atoms substituted by such groups, at least one or more 3 to 7 membered saturated or unsaturated hydrocarbons. A bivalent chain forming a cyclic structure may be formed, and the thus formed cyclic bond chain may contain a bond of carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, imino at any position. Well, n represents the number of condensed rings sandwiched between a heterocycle and a benzene ring having substituents R ^{53 to} R ⁵⁶ and is an integer of 0 or 1 to 3).

(In the formula (23), R ^{158 to} R ¹⁶⁶ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Or an alkylene, arylene or aralkylene group, and at least one of R ^{158 to} R ¹⁶⁶ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, and n is a substituent R ^This represents the number of condensed rings sandwiched between the benzene ring having ¹⁵⁸ and R ¹⁵⁹ and the benzene ring having substituents R ^{161 to} R ¹⁶⁴ and is an integer of 0 or 1-3.

(In the formula (24), R ^{167 to} R ¹⁷⁶ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{167 to} R ¹⁷⁶ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. ³⁵ is a group selected from the group consisting of COOH, and n is a substituent R Represents the number of condensed rings sandwiched between a benzene ring having ^{167 to} R ¹⁶⁹ and a benzoquinone ring, and is an integer of 0 or 1 to 3)

(In the formula (25), R ^{177 to} R ¹⁸¹ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{177 to} R ¹⁸¹ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R. a group selected from the group consisting of ³⁵ COOH, X ^a- is chlorine ON, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion , P-toluenesulfonate ion, trifluoroacetate ion, and trifluoromethanesulfonate ion, at least one kind of anion selected from the group of 1 to 3 anions, and a represents the valence of X , 1-3, p is the doping rate, and the value is 0.001-1.) The water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group contains 20 to 100% of a repeating unit represented by the following formula (26) in the total number of repeating units of the whole polymer. Item 18. A method for producing a carbon nanotube-containing polymer according to Item 14 or Item 17.

(In formula (26), y represents an arbitrary number of 0 <y <1, and R ^{115 to} R ¹³² are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , _{^{-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, -COOH, -R 35 COOH, -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, or an alkylene, arylene or aralkylene group, and at least one of R ^{115 to} R ¹³² is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ^—. , selected from the group consisting of -R ³⁵ SO ₃ H, -COOH and -R ³⁵ COOH The is a group.) The production of a carbon nanotube-containing polymer according to claim 14 or 17, wherein the water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group is represented by the following formula (27): Method.

(In Formula (27), R ¹³³ 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, and R ³⁴ is a methyl group. , Ethyl group, n-propyl group, 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 A group selected from the group consisting of iso-butoxy, sec-butoxy, tert-butoxy, heptoxy, hexoxy, octoxy, dodecoxy, tetracosoxy, fluoro, chloro and bromo X represents an arbitrary number of 0 <X <1, and n represents the degree of polymerization and is 3 or more.) The water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group is an acidic group-substituted aniline represented by the following formula (28), an alkali metal salt thereof, an ammonium salt and / or a substituted ammonium salt, a basic compound: 18. The method for producing a carbon nanotube-containing polymer according to claim 14, wherein the carbon nanotube-containing polymer is a water-soluble conductive polymer obtained by polymerization with an oxidizing agent in a solution containing the carbon nanotube.

(In the formula (28), R ^{136 to} R ¹⁴¹ are each independently H, —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —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, -COOH, -R 35 COOH}} , -COOR 35, -COR 35, selected from the group consisting of -CHO and -CN, wherein, R ³⁵ is alkyl of 1 to 24 carbon atoms, aryl or aralkyl group Alternatively, it is an alkylene, arylene or aralkylene group, and at least one of R ^{136 to} R ¹⁴¹ is —SO ₃ ⁻ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ H, —COOH and —R ^35. A group selected from the group consisting of COOH.)   A water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group contains an alkoxy group-substituted aminobenzene sulfonic acid, its alkali metal salt, ammonium salt and / or substituted ammonium salt in an oxidizer in a solution containing a basic compound. The method for producing a carbon nanotube-containing polymer according to claim 14 or 16, wherein the polymer is a water-soluble conductive polymer obtained by polymerization.   The method for producing a carbon nanotube-containing polymer according to claim 14 or 16, wherein the water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group is polyethylene dioxythiophene polystyrene sulfate.   The method for producing a carbon nanotube-containing polymer according to any one of claims 1 to 23, wherein the carbon nanotube-containing composition is irradiated with ultrasonic waves.   The carbon nanotube containing polymer manufactured by the manufacturing method of the carbon nanotube containing polymer as described in any one of Claims 1 thru | or 24.   A composite comprising the coating film comprising the carbon nanotube-containing polymer according to claim 25 on at least one surface of a substrate.   A method for producing a composite comprising: coating a carbon nanotube-containing polymer according to claim 25 on at least one surface of a substrate; and forming a coating film by standing at room temperature or by performing a heat treatment. .   The method for producing a composite according to claim 27, wherein the heat treatment is performed in a temperature range from room temperature to 250 ° C.   A carbon nanotube-containing polymer according to claim 25 is coated on at least one surface of a substrate, and a coating film is formed by standing or heating treatment at room temperature. Method.