JP4947759B2 - Carbon nanotube-containing curable composition and composite having the cured coating film - Google Patents

Description

The present invention relates to a carbon nanotube-containing curable composition and a composite having the cured coating film.

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

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

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

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

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

  Conventionally, plastic base materials used for home appliances, information electronic devices, automobile parts, and the like have been subjected to various surface coating treatments in order to improve their surface protection and design properties. Among them, surface coating treatment for the purpose of protecting the surface of a plastic substrate is often used in various fields because it can impart high surface hardness and scratch resistance to the plastic substrate. In particular, in recent years, with the increase in demand for optical materials such as image display devices based on plastic lenses, plastic films, etc., the amount of use has also increased.

On the other hand, there is a problem that the surface of an image display device such as a flat display such as a CRT, LCD, or PDP is easily charged, and dust adheres to the surface, resulting in poor visibility of the screen. In order to solve these problems, attempts have been made to add conductivity (antistatic properties) to the coating film by adding various conductive materials to the coating material for surface coating treatment. For example, when a carbon material such as carbon black or a metal filler is used, it is necessary to add several tens of mass% for the expression of conductivity, and the transparency of the coating film is lowered, and the scratch resistance and smoothness of the coating film are low. There is a problem of becoming. In addition, when a surfactant is added, the transparency is excellent, but the addition amount is still required to be several tens of mass%, and the scratch resistance of the coating film is lowered. In addition, the surfactant has humidity dependency due to ionic conduction, and there are problems such as a decrease in conductive performance and a variation in low humidity conditions such as winter.
WO2002 / 016257 JP 2005-35810 A S. Iijima, Nature, 354, 56 (1991) R. E. Smalley et al., Science, 280, 1253 (1998) J. et al. Chen et al., Science, 282, 95 (1998). Nakajima et al., Chem. Lett. 638 (2002)

  The object of the present invention is to disperse or solubilize carbon nanotubes without impairing the characteristics of the carbon nanotubes themselves, and the carbon nanotubes do not separate and aggregate even during long-term storage, and are conductive and film-forming. The carbon nanotube-containing curable composition is excellent in moldability, can be applied and coated on a substrate by a simple method, and the coating film has excellent water resistance, weather resistance, mechanical strength, scratch resistance and hardness, And providing a composite having the cured coating film.

  As a result of intensive studies to solve these problems, the present inventor has obtained a scratch resistance by curing a polyfunctional (meth) acrylate dispersed with carbon nanotubes with a polymerization initiator in the presence of a conductive polymer. The present inventors have found that a cured coating film excellent in the above can be formed, and that by further coexisting a solvent, the dispersion of carbon nanotubes can be promoted and a more effective cured coating film can be formed.

That is, the first of the present invention is a carbon nanotube-containing curable composition containing a conductive polymer (a), a carbon nanotube (b), a polyfunctional (meth) acrylate (c), and a polymerization initiator (d). There,
The group in which the sulfonic acid group and / or carboxyl group in the conductive polymer (a) is composed of halogenated alkyldimethylbenzylammonium halide, alkyldiethylbenzylammonium halide, tetraalkylammonium halide, trimethylbenzylammonium hydroxide, anilines. The conductive polymer (a) is 0.001 to 50 masses with respect to 100 mass parts of the polyfunctional (meth) acrylate (c). Part, the carbon nanotube (b) is 0.0001 to 40 parts by mass, and the polymerization initiator (d) is 0.001 to 20 parts by mass.

The second of the present invention is a carbon nanotube-containing curable composition further containing a solvent (e), and the conductive polymer (a) is 0.001 with respect to 100 parts by mass of the solvent (e). The carbon nanotube-containing curable composition is -50 parts by mass,
  A third aspect of the present invention is a cured coating formed by coating the carbon nanotube-containing curable composition on at least one surface of a substrate, irradiating with active energy rays and / or leaving or heating at room temperature. The present invention relates to a composite having a membrane.

  The carbon nanotube-containing curable composition of the present invention can disperse or solubilize carbon nanotubes without impairing the properties of the carbon nanotubes themselves, and does not separate or aggregate even during long-term storage. Moreover, according to the curable composition containing carbon nanotubes of the present invention, a cured coating film can be formed in a very short time by coating the composition on a substrate and irradiating and / or heat-treating active energy rays. I can do it. The conductive polymer (a), the carbon nanotube (b), and the polyfunctional (meth) acrylate (c) itself are fully exhibited to obtain a coating film that is not dependent on humidity and has excellent conductivity and film formability. be able to. Moreover, the coating film is excellent in water resistance, weather resistance, mechanical strength, scratch resistance and hardness.

  Hereinafter, the present invention will be described in detail.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Among the above conductive polymers having an ammonium salt of a sulfonic acid group and / or an ammonium salt of a carboxyl group, the repeating unit represented by the following general formula (12) is 20 to 100 in the total number of repeating units of the whole polymer. % Is more preferably used.
(In the formula (12), y represents an arbitrary number of 0 <y <1, and R ^{15 to} R ³² are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, _{^{-R 35 SO 3 -, -R 35}} SO 3 - M +, -R 35 SO 3 H, -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, - N (R ³⁵ ) ₂ , —NHCOR ³⁵ , —OH, —O ⁻ , —SR ³⁵ , —OR ³⁵ , —OCOR ³⁵ , —NO ₂ , —COO ⁻ M ⁺ , —COOH, —R ³⁵ COOH, —R ³⁵ COO ⁻ M ⁺ , —COOR ³⁵ , —COR ³⁵ , —CHO and —CN, wherein M ⁺ is an ammonium ion and R ³⁵ is alkyl having 1 to 24 carbon atoms, aryl or aralkyl group or an alkylene, arylene or aralkylene group, at least one of -SO ₃ of R ¹⁵ to R ^{32 -,} -SO _{3 ^{, -R 35 SO 3 -, -R}} 35 SO 3 H, -COOH, -R 35 COOH, and _{^{-SO 3 - M +, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO ^- it is a group selected from the group consisting of M ^+).

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

In addition, the substituent added to the aromatic ring is preferably an alkyl group, an alkoxy group, a halogen group or the like from the viewpoint of conductivity and solubility, and particularly preferably a conductive polymer having an alkoxy group. Among these combinations, the most preferable water-soluble conductive polymer is represented by the following general formula (13).
(In the formula (13), R ³³ is one group selected from the group consisting of a sulfonic acid group, a carboxyl group, and alkali metal salts, ammonium salts and substituted ammonium salts thereof, at least one of which is a sulfonic acid group. R ³⁴ is a group selected from the group consisting of a group, a carboxyl group, an ammonium salt of a sulfonic acid group, and an ammonium salt of a carboxyl group, and R ³⁴ is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, n -Butyl group, iso-butyl group, sec-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group , Heptoxy group, hexoxy group, octoxy group, dodecoxy group, tetracosoxy group, fluoro group, chloro And shows one group selected from the group consisting of bromo group, X is 0 <show any number of X <1, n is 3 or more indicates a polymerization degree.)

As the conductive polymer in the present invention, polymers obtained by various synthetic methods such as chemical polymerization or electrolytic polymerization can be used. For example, the synthesis methods described in Japanese Patent Application Laid-Open Nos. 7-196791 and 7-324132 proposed by the present inventors are applied. That is, one compound selected from the group consisting of an acidic group-substituted aniline represented by the following general formula (14), an alkali metal salt thereof, an ammonium salt, and a substituted ammonium salt is oxidized in a solution containing a basic compound. It is the conductive polymer obtained by making it superpose | polymerize by.
(In the formula (14), R ^{36 to} R ⁴¹ are each independently H, —SO ₃ ⁻ , —SO ₃ ⁻ M ⁺ , —SO ₃ H, —R ³⁵ SO ₃ ⁻ , —R ³⁵ SO ₃ ⁻ M _{^{+, -R 35 SO 3 H,}} -OCH 3, -CH 3, -C 2 H 5, -F, -Cl, -Br, -I, -N (R 35) 2, -NHCOR 35, -OH, ^{-O -, -SR 35, -OR 35} , -OCOR 35, -COO - M +, -COOH, -R 35 COOH, -R 35 COO - M +, -COOR 35, -COR 35, -CHO and - Selected from the group consisting of CN, wherein M ⁺ is an ammonium ion, R ³⁵ is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms or an alkylene, arylene or aralkylene group, and R ^{36 to} R ⁴¹ out at least one of _{^{-SO 3 -, -SO 3 H,}} -R 35 SO 3 -, -R 35 SO 3 H, -CO H, -R ³⁵ COOH, and _{^{-SO 3 - + M, -R 35}} SO 3 - + M, -COO - M +, -R 35 COO - is a group selected from the group consisting of M ^+).

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

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

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

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

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

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

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

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

<Carbon nanotube (b)>
The carbon nanotube (b) that is an essential constituent of the curable composition containing carbon nanotubes of the present invention is not particularly limited, and is a normal carbon nanotube, that is, a single-walled carbon nanotube, and several layers are concentric. Overlapping multi-walled carbon nanotubes, those in which they are coiled, and the like can be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Among these polymer compounds (f), 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 (g)>
By adding the basic compound (g) to the carbon nanotube-containing curable composition of the present invention, the conductive polymer (a), which is a constituent component, is dedoped, and the dissolution into the composition is more effectively improved. . Further, by forming a salt with free sulfonic acid groups and carboxyl groups, dissolution in the composition is particularly improved, and solubilization or dispersion of the carbon nanotube (b) in the composition is promoted.

The basic compound (g) is not particularly limited, and for example, ammonia, fatty amines, cyclic saturated amines, cyclic unsaturated amines and ammonium salts, inorganic bases and the like are preferably used. .
The structural formula of amines used as the basic compound (g) is shown in the following general formula (17).
(In formula (17), R ^{245 to} R ²⁴⁷ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, CH ₂ OH, CH ₂ CH ₂ OH, CONH ₂ or NH _2. )

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

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

Two or more basic compounds (g) 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 (h)>
When the surfactant (h) is added to the carbon nanotube-containing curable composition of the present invention, further solubilization or dispersion is promoted, and flatness, coatability, conductivity and the like are improved.

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

<Silane coupling agent (i)>
In the present invention, the silane coupling agent (i) can be used in combination with the carbon nanotube-containing curable composition. The water resistance of the coating film obtained from the carbon nanotube-containing curable composition combined with the silane coupling agent (i) is significantly improved. As the silane coupling agent (i), a silane coupling agent (i) represented by the following general formula (1) is used.
(In the formula (1), R ⁴² , R ⁴³ and R ⁴⁴ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, X is a group selected from the group consisting of an amino group, an acetyl group, a phenyl group, and a halogen group.
1 and m are numbers from 0 to 6, and Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, an epoxy group, and an epoxycyclohexyl group. )

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

<Colloidal silica (j)>
In the present invention, colloidal silica (j) can be used in combination with the carbon nanotube-containing curable composition. The coating film obtained from the carbon nanotube-containing curable composition used in combination with colloidal silica (j) has significantly improved surface hardness and weather resistance.

  Although colloidal silica (j) used by 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 (j), 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.

<Stabilizers such as antioxidants and light stabilizers (k)>
In the present invention, it is preferable to add a stabilizer (k) such as an antioxidant or a light stabilizer to the carbon nanotube-containing curable composition. The cured coating film obtained from the carbon nanotube-containing curable composition in combination with a stabilizer (k) such as an antioxidant or a light stabilizer can prevent yellowing of the coating film over time. Specific examples of this include, for example, various commercially available Sumitomo Chemical Co., Ltd., Sumitizer BHT, Sumilizer S, Summarizer BP-76, Summarizer MDP-S, Summarizer GM, Summarizer BBM-S, Summarizer WX-R, and Summarizer. NW, Sumilyzer BP-179, Sumilyzer BP-101, Sumilyzer GA-80, Sumilyzer TNP, Sumilyzer TPP-R, Sumilyzer P-16, Adeka Stub AO-20, Adeka Stub AO-30, Adeka Stub AO- 40, ADK STAB AO-50, ADK STAB AO-60 AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP 36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 329K, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, CHIBIN SPECIAL CHEMICALS CO., LTD. , Tinuvin 111, Tinuvin 123, Tinuvin 292 and the like.

<Carbon nanotube-containing curable composition>
The preferable composition ratio of the carbon nanotube-containing curable composition of the present invention is 0.0001 to 40 parts by mass (particularly preferably) of carbon nanotubes (b) with respect to 100 parts by mass of the polyfunctional (meth) acrylate (c). 0.001-20 parts by mass), polymerization initiator (d) 0.001-20 parts by mass (particularly preferably 0.05-10 parts by mass), conductive polymer (a) 0.001-50 parts by mass (particularly Preferably it is 0.01-30 mass parts).

  The carbon nanotube-containing curable composition of the present invention is improved in solubility / dispersibility, applicability, operability, etc. by using the solvent (e) as a constituent component, but the composition ratio when using the solvent (e) is It is as follows.

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

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

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

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

  The use ratio of the polymer compound (f) and the solvent (e) is preferably 0.1 to 400 parts by mass, more preferably 0, with respect to 100 parts by mass of the solvent (e). .5 to 300 parts by mass. When the polymer compound (f) 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 (f) is 400 parts by mass or less, the conductive polymer (a) and the carbon nanotube (b) There is little decrease in solubility, and high conductivity is maintained.

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

  The use ratio of the surfactant (h) and the solvent (e) is preferably 0.0001 to 10 parts by mass of the surfactant (h) with respect to 100 parts by mass of the solvent (e), more preferably 0. 0.01 to 5 parts by mass. When the surfactant (h) exceeds 10 parts by mass, the coatability is improved, but a phenomenon such as poor conductivity occurs, and the efficiency of solubilization or dispersion of the carbon nanotube (b) is lowered.

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

  The use ratio of the colloidal silica (j) and the solvent (e) is preferably such that the colloidal silica (j) is 0.001 to 100 parts by mass, more preferably 0.01 to 100 parts by mass of the solvent (e). -50 mass parts. If colloidal silica (j) is 0.001 mass part or more, the improvement width of water resistance, weather resistance, and hardness will become large. On the other hand, when it exceeds 100 parts by mass, the solubility, flatness, transparency, and conductivity may be deteriorated.

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

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

  In addition, the carbon nanotube-containing curable composition of the present invention may 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 curable composition>
Conductive polymer (a), carbon nanotube (b), polyfunctional (meth) acrylate (c), polymerization initiator (d), and other initiators as necessary, which are essential components of the curable composition containing carbon nanotubes of the present invention When mixing the components, a stirring or kneading apparatus such as an ultrasonic wave, a homogenizer, a spiral mixer, a planetary mixer, a disperser, or a hybrid mixer is used. In particular, when a carbon nanotube-containing curable composition having good dispersibility and coatability is obtained to obtain a high-performance composite, the combined use of the solvent (d) is effective. In this case, it is preferable that the conductive polymer (a), the solvent (e), the carbon nanotube (b), or other components are mixed and irradiated with ultrasonic waves. In this case, the ultrasonic irradiation and the homogenizer are performed. It is particularly preferable to carry out the treatment in combination (ultrasonic homogenizer).

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

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

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

<Composite>
In the present invention, as a base material on which a carbon nanotube-containing curable composition is applied to form a cured coating film, a polymer compound, plastic, wood, paper material, ceramics, fiber, nonwoven fabric, carbon fiber, carbon fiber paper, These films, foams, porous membranes, elastomers, glass plates and the like are used. For example, as polymer compounds, plastics and films, polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyester, polyamide, polyimide, polyaramid, Examples include polyphenylene sulfide, polyether ether ketone, polyphenylene ether, polyether nitrile, polyamide imide, polyether sulfone, polysulfone, polyether imide, polybutylene terephthalate, polyurethane, these films, foams and elastomers. Since these films form a cured coating film on at least one surface thereof, the surface is preferably subjected to corona surface treatment or plasma treatment for the purpose of improving the adhesion of the cured coating film.

  The curable coating film in this invention is formed in the surface of a base material by the method used for a general coating. For example, gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, phanten coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, screen coater, etc. Spraying methods such as spray coating such as air spray and airless spray, and dipping methods such as dipping are used.

<Method for producing composite>
After the carbon nanotube-containing curable composition is applied to the surface of the substrate, it may be irradiated with active energy rays, or left at room temperature or subjected to heat treatment to form a curable coating film. Since it can be cured in a short time without heating, it is preferable to cure using active energy rays.

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

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

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

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

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

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

  The composite of the present invention still has excellent conductivity, but after forming a coating film by coating the carbon nanotube-containing curable composition on at least one surface of the substrate, the acid Conductivity can be further improved by performing a doping treatment by the above, 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 curable composition using the conductive polymer (a) of the present invention and the solvent (e) described above, the carbon nanotube (b) is converted into the conductive polymer (a) and the siloxane compound (c). In addition to the solvent (e), the carbon nanotube (b) is dispersed or solubilized in the solvent (e) without impairing the properties of the carbon nanotube (b) and the polyfunctional (meth) acrylate (c) itself. It can be separated, and does not separate or aggregate even during long-term storage. The reason for this is not clearly understood, but the carbon nanotube (b) is dispersed or solubilized together with the conductive polymer (a) by adsorbing or helically wrapping the conductive polymer (a) on the carbon nanotube (b). Presumed to be. In the carbon nanotube-containing curable composition of the present invention, the conductive polymer (a) and the carbon nanotube (b) are used in combination with the cured coating film formed from the polyfunctional (meth) acrylate (c). Therefore, it is excellent in conductivity, film formability and moldability, and its coating film is excellent in water resistance, weather resistance, mechanical strength and hardness.

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

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

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

<Carbon nanotube-containing composition>
Carbon nanotube-containing composition 1:
1 part by mass of the conductive polymer (A-1) of Production Example 1 and 1.0 part by mass of carbon nanotubes are mixed with 100 parts by mass of water at room temperature, and 1 ultrasonic homogenizer treatment (vibra cell 20 kHz, manufactured by SONIC) is performed. Carried out for a while, a carbon nanotube-containing composition 1 was prepared.

Carbon nanotube-containing composition 2:
1 part by mass of the conductive polymer (A-2) of Production Example 1 and 0.5 part by mass of the carbon nanotube are mixed with 100 parts by mass of dimethylacetamide at room temperature, and subjected to ultrasonic homogenizer treatment (vibra cell 20 kHz, manufactured by SONIC). Carried out for 1 hour, a carbon nanotube-containing composition 2 was prepared.

Carbon nanotube-containing composition 3:
A carbon nanotube-containing composition 3 was prepared by mixing 1.0 part by mass of carbon nanotubes with 100 parts by mass of water at room temperature and performing ultrasonic homogenizer treatment (vibra cell 20 kHz, manufactured by SONIC) for 1 hour.

<Carbon nanotube-containing curable composition>
(Reference Example 1) : Curable composition 1 containing carbon nanotubes
Carbon nanotube-containing curable composition 1 was prepared by mixing and stirring 5 parts by mass of carbon nanotube-containing composition 1 and 20.5 parts by mass of curable composition 1.

<Carbon nanotube-containing curable composition>
(Reference Example 2) : Curable composition 2 containing carbon nanotubes
A carbon nanotube-containing curable composition 2 was prepared by mixing and stirring 0.5 mass parts of the carbon nanotube-containing composition 1 and 20.5 parts by mass of the curable composition 1.

(Example 3): Carbon nanotube-containing curable composition 3
5 parts by mass of the carbon nanotube-containing composition 2 and 20.5 parts by mass of the curable composition 1 were mixed and stirred to prepare a carbon nanotube-containing curable composition 3.

(Comparative Example 1): Carbon nanotube-containing curable composition 4
Carbon nanotube-containing curable composition 4 was prepared by mixing and stirring 5 parts by mass of carbon nanotube-containing composition 3 and 20.5 parts by mass of curable composition 1.

<Evaluation method>
An appropriate amount of the carbon nanotube-containing curable compositions obtained in Examples and Comparative Examples was dropped on a PET film (product name: A-4100, manufactured by Toyobo Co., Ltd.) and applied by a bar coating method (bar coater # 10). It dried at 100 degreeC with the dryer for about 1 minute. Then a high pressure mercury lamp (Co. Oak Seisakusho, ultraviolet irradiation apparatus, handy UV-1200, QRU-2161 type) for about 30 seconds with ultraviolet light at about 1000 mJ / cm ² was irradiated to form a cured coating film, appearance observation Thereafter, the surface resistance value and the total light transmittance were measured. The results are shown in Table 1.

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

The carbon nanotube-containing curable composition of the present invention is obtained by using various antistatic agents, capacitors, batteries, fuel cells, polymer electrolyte membranes thereof, and electrode layers by using a simple coating method such as coating, spraying, casting, and dipping. , Members such as catalyst layers, gas diffusion layers, gas diffusion electrode layers, separators, EMI shields, chemical sensors, display elements, nonlinear materials, anticorrosives, adhesives, fibers, spinning materials, antistatic paints, anticorrosion paints, electric It can be applied to applications such as coating paint, plating primer, conductive primer for electrostatic coating, cathodic protection, 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 (sources) 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, transparent electrode, light emitting material forming organic electroluminescence element, buffer material, electron transport material, hole transport material and fluorescent material, thermal transfer sheet, transfer sheet, thermal transfer image receiving sheet, image receiving sheet It is used as a.

Claims (3)

A carbon nanotube-containing curable composition comprising a conductive polymer (a), a carbon nanotube (b), a polyfunctional (meth) acrylate (c), and a polymerization initiator (d) ,
The group in which the sulfonic acid group and / or carboxyl group in the conductive polymer (a) is composed of halogenated alkyldimethylbenzylammonium halide, alkyldiethylbenzylammonium halide, tetraalkylammonium halide, trimethylbenzylammonium hydroxide, anilines. The conductive polymer (a) is 0.001 to 50 masses with respect to 100 mass parts of the polyfunctional (meth) acrylate (c). The carbon nanotube-containing curable composition, wherein the carbon nanotube (b) is 0.0001 to 40 parts by mass, and the polymerization initiator (d) is 0.001 to 20 parts by mass. Furthermore, it is a carbon nanotube-containing curable composition containing a solvent (e) , and the conductive polymer (a) is 0.001 to 50 parts by mass with respect to 100 parts by mass of the solvent (e). The carbon nanotube-containing curable composition according to claim 1.   Curing formed by applying the carbon nanotube-containing curable composition according to claim 1 or 2 on at least one surface of a substrate and irradiating with active energy rays and / or leaving or heating at room temperature. A composite having a coating film.