JP2007056125A - Curing composition comprising carbon nano-tube and composite having cured coated film thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing composition comprising carbon nano-tubes, dispersing or solubilizing the carbon nano-tubes without deteriorating characteristics of the carbon nano-tubes themselves, having excellent electroconductivity, film-forming properties and moldability without separating and aggregating the carbon nano-tubes even during long-term preservation, applicable and coverable on a substrate according to a simple method and affording a coated film thereof having excellent water resistance, weather resistance and scuff resistance and hardness and to provide a composite having a cured coated film composed of the composition. <P>SOLUTION: The curing composition comprising the carbon nano-tubes comprises the carbon nano-tubes (A), a siloxane compound (B), an active energy ray-sensitive cationic polymerization initiator (C) and, as necessary, further an electroconductive polymer (D), a solvent (E), a high polymer (F), a basic compound (G), a surfactant (H), a silane coupling agent (I) and colloidal silica (J). The composite has the cured coated film composed of the composition on at least one surface of the substrate. <P>COPYRIGHT: (C)2007,JPO&INPIT

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.

  In addition, a composition comprising a carbon nanotube, a conductive polymer and a solvent, and a composite produced therefrom have been proposed (Patent Document 3). The composition and composite can coexist with a conductive polymer to disperse or solubilize carbon nanotubes in a solvent such as water, organic solvent, water-containing organic solvent, etc. without damaging the properties of the carbon nanotube itself, and stable for long-term storage It is reported to be excellent. A carbon nanotube composition in which a conductive polymer coexists is excellent in conductivity, film formability, and moldability, and can be applied and coated on a substrate by a simple method. There was a problem that the sex was not enough.

On the other hand, in recent years, transparent plastic materials such as acrylic resin and polycarbonate resin, which are excellent in crush resistance and light weight, have been widely used as an alternative to transparent glass. However, since the transparent plastic material has a lower surface hardness than glass, it has a problem that the surface is easily damaged.

  Therefore, many attempts have been made to improve the scratch resistance of plastic materials. In these attempts, in order to impart particularly high scratch resistance to the plastic material, a silica-based composition comprising an alkoxysilane compound is applied to the surface of the plastic material and cured by heat to form a protective coating film. There are methods (Patent Document 4, Patent Document 5). However, such a method requires a heating time of several tens of minutes to several hours in order to form a protective coating film, which is problematic in terms of productivity.

  In order to solve these problems, a composition containing a linear inorganic oligomer having a siloxane skeleton and a cationic polymerization initiator as essential components is cured by irradiation with active energy rays to form an inorganic protective coating film. A method has been proposed (Patent Document 6). However, in the formation of such an inorganic coating film, a composition composed of a linear inorganic oligomer (alkyl silicate) and a cationic polymerization initiator is coated on the substrate and further irradiated with active energy rays. Thus, a crosslinked structure is formed for the first time, resulting in a cured coating film. Therefore, there is a problem that a sufficient crosslinked structure is not formed only by irradiation with an active energy ray for a short time, and the physical properties of the coating film are hardly exhibited. In particular, sufficient performance is hardly exhibited in terms of scratch resistance. Further, there is a problem that a rapid polycondensation reaction occurs in a short time during curing, and cracks are generated in the cured coating film due to the stress generated by the shrinkage, and adhesion to the substrate is lowered.

Furthermore, in order to improve such points, in addition to alkyl silicates and an active energy ray-sensitive cationic polymerization initiator, a cationic polymerizable epoxy compound having excellent polymerizability and flexibility, and an active energy ray-sensitive property. There has been proposed a method for reducing cracks and imparting adhesion to a coating film by blending a radical polymerization initiator and a radical polymerizable acrylic compound. However, depending on the blending amount of these organic compounds, there is a problem that the high hardness and high scratch resistance, which are the characteristics of the inorganic protective coating film, are likely to be lowered.
WO2002 / 016257 JP 2005-35810 A WO2004 / 039873 JP 48-26822 A JP 55-94971 A JP 2001-348515 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 found that a cured coating film having excellent scratch resistance can be formed by curing a siloxane compound in which carbon nanotubes are dispersed with a cationic polymerization initiator. The present inventors have found that the coexistence of the conductive polymer promotes the dispersion of the carbon nanotubes and can form a more effective cured coating film.

  That is, the first of the present invention relates to a curable composition containing carbon nanotubes, which contains a carbon nanotube (A), a siloxane compound (B), and an active energy ray-sensitive cationic polymerization initiator (C). The carbon nanotube-containing curable composition of the present invention can further improve dispersibility, conductivity and the like by further containing a conductive polymer (D).

  In a second aspect of the present invention, the carbon nanotube-containing curable composition according to claim 1 or 2 is applied onto at least one surface of a substrate, and the active energy ray is irradiated and / or left at room temperature. The present invention relates to a composite having a cured coating film formed by heat treatment.

  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 carbon nanotube containing curable composition of this invention, a cured coating film can be formed in a very short time by apply | coating this composition to a base material and irradiating an active energy ray. The carbon nanotube (A), the siloxane compound (B), and the conductive polymer (D) itself can be fully used to obtain a coating film that is not dependent on humidity and has excellent conductivity and film formability. it can. 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.
<Carbon nanotube (A)>
The carbon nanotube (A) 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 (A) will be described in more detail. A cylinder with rounded graphite-like carbon atoms with 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.

  Further, 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 (A), can also be used.

  The method for producing the carbon nanotube (A) 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 (A) obtained by these production methods are preferably single-walled carbon nanotubes and multi-walled carbon nanotubes, and various purification methods 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 (A), 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 also used. be able to.

<Siloxane compound (B)>
The siloxane compound used in the present invention is a general term for compounds having a structure of —O—Si—O— in the molecule. The siloxane compound used in the present invention is not particularly limited, and for example, alkyl silicates, organosilanes, or condensates thereof are preferably used.

（式中Ｒ^４５、Ｒ^４６、Ｒ^４７、およびＲ^４８はそれぞれ炭素原子数１〜５のアルキル基を示し、ｎは１〜２０の整数、好ましくは４〜１０の整数を示す） Alkyl silicate is a general term for tetraalkoxysilane and compounds obtained by linear polycondensation thereof, and is represented by the following general formula (1).

(In the formula, R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each represent an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 20, preferably an integer of 4 to 10).

Alkyl silicate is hydrolyzed and condensed in advance to form a cross-linked structure between the alkyl silicate molecules to increase the molecular weight, thereby improving the curability of the composition and dramatically improving the physical properties of the resulting cured coating film. Can be improved. Further, by using a high molecular weight oligomer, shrinkage due to polycondensation during curing and the stress generated therewith can be reduced, and as a result, cracks can be reduced and coating film adhesion can be improved.

When the number of repeating units n of the alkyl silicate is larger than 20, gelation tends to occur during hydrolysis / condensation. From the viewpoint of obtaining good curability and physical properties of the coating film and being difficult to gel, n is preferably an integer of 4 to 10 (concentration equivalent to silica: equivalent to about 51 to 54% by mass). Here, the silica equivalent concentration means the mass of SiO ₂ obtained when the alkylsilicate is completely hydrolyzed and condensed.

Specific examples of the alkyl silicate represented by the general formula (1) include methyl silicate in which R ^{45 to} R ⁴⁸ are methyl groups, ethyl silicate in which R ^{45 to} R ⁴⁸ are ethyl groups, and R ^{45 to} R ⁴⁸ are isopropyl groups. isopropyl silicate ^{is, R} 45 to R ⁴⁸ is a n- propyl group n- propyl ^{silicate, R} 45 to R ⁴⁸ is a n- butyl group n- butyl ^silicate, in ^R 45 to R ⁴⁸ is n- pentyl group A certain n-pentyl group silicate etc. are mentioned. Of these, methyl silicate and ethyl silicate are preferred because they are easy to produce and have a high hydrolysis rate.

  Alkyl silicate can be hydrolyzed / condensed using a known method. For example, an alkyl silicate is mixed with an alcohol, and water (for example, 1 to 1000 mol of water with respect to 1 mol of the alkyl silicate) and an acid such as hydrochloric acid or acetic acid are added to make the solution acidic (for example, pH 2 to 5). There is a method of stirring. In addition, there is a method in which an alkyl silicate is mixed with an alcohol, and water (for example, 1 to 1000 mol with respect to 1 mol of the alkyl silicate) is added and heated (for example, 30 to 100 ° C.). The alcohol generated during the hydrolysis may be distilled out of the system. Condensation following hydrolysis can proceed by leaving the alkyl silicate in the hydrolyzed state. At that time, the progress of the condensation can be accelerated by controlling the pH to be near neutral (for example, pH 6 to 7). The water generated during the condensation may be distilled out of the system.

The organosilane used in the present invention is a general term for compounds in which 1 to 3 organic groups and 1 to 3 alkoxy groups are bonded directly to Si atoms. Specific examples of the organosilane include methyltriethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyl Oxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, p-styryltriethoxysilane, p-styryltrimethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, Examples include, but are not limited to, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, trimethylethoxysilane, and triethylethoxysilane. It is not something. The hydrolysis / condensation of the organosilane can be performed in the same manner as the hydrolysis / condensation of the alkyl silicate. In the hydrolysis / condensation of the alkyl silicate, organosilane may be present in the coexistence so long as the effects of the present invention are not impaired.

（式（３１）中、Ｒ⁴²、Ｒ⁴³、Ｒ⁴⁴は各々独立に、水素、炭素数１〜６の直鎖または分岐のアルキル基、炭素数１〜６の直鎖または分岐のアルコキシ基、アミノ基、アセチル基、フェニル基、ハロゲン基よりなる群から選ばれた基であり、Ｘは、

を示し、ｌ及びｍは０〜６までの数であり、Ｙは、水酸基、チオール基、アミノ基、エポキシ基及びエポキシシクロヘキシル基よりなる群から選ばれた基である。） <Silane coupling agent (I)>
Moreover, in this invention, a silane coupling agent (I) can be used together as 1 type of a siloxane compound (B). The water resistance of the coating film obtained from the carbon nanotube-containing curable composition combined with the silane coupling agent (I) is remarkably improved. As the silane coupling agent (I), a silane coupling agent (I) represented by the following general formula (31) is preferably used.

(In the formula (31), 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.

<Active energy ray-sensitive cationic polymerization initiator (C)>
The active energy ray-sensitive cationic polymerization initiator (C) used in the present invention is an initiator that causes a cationic polymerization initiation reaction by active energy rays such as visible light, ultraviolet rays, heat rays, and electron beams. Photosensitive cationic polymerization initiators that generate acid by visible light and ultraviolet light, and heat sensitive cationic polymerization initiators that generate acid by heat rays are preferred. Among these, a photosensitive cationic polymerization initiator is more preferable because it has high activity and does not cause thermal deterioration of the plastic material.

  Examples of the photosensitive cationic polymerization initiator include diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salt compounds, etc., preferably iodonium salts, sulfonium salts and the like are used. Specific examples include Irgacure 250 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.), Adekaoptomer SP-150, SP-170 (above, trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), Syracure UVI- 6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-6990, Cyracure UVI-6950 (above, trade name, manufactured by Dow Chemical Japan Co., Ltd.), DAICATII (trade name, manufactured by Daicel Chemical Industries), UVAC1591 (Daicel USB Co., Ltd., trade name), CI-2734, CI-2855, CI-2823, CI-2758 (above, Nippon Soda Co., Ltd., trade name) and the like.

<Conductive polymer (D)>
In the present invention, by using a conductive polymer in combination, the solubility and dispersibility of 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 conductive polymer (D) 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

（式（１５）中、Ｒ^１４８〜Ｒ^１５１は各々独立に水素、Ｒ³⁵ＯＨ、炭素数１〜２４（Ｃ_１〜Ｃ_２４）のアルキル、アリールまたはアラルキル基あるいはフェニル基、ベンジル基、ＣＯＮＨ_２またはＮＨ_２であり、かつＲ^１４８〜Ｒ^１５１のうち少なくとも一つが炭素数５以上の基であり、Ｒ³⁵は炭素数１〜２４のアルキレン、アリーレンまたはアラルキレン基であり、Ｘ_ｋ ^Ｚ- は水酸化物イオン、塩素イオン、臭素イオン、ヨウ素イオン、フッ素イオン、硝酸イオン、硫酸イオン、硫酸水素イオン、アミド硫酸イオン、亜硫酸イオン、ホスフィン酸イオン、リン酸イオン、ピロリン酸イオン、トリポリリン酸イオン、ほうフッ化イオン、過塩素酸イオン、チオシアン酸イオン、酢酸イオン、プロピオン酸イオン、メタンスルホン酸イオン、ｐ−トルエンスルホン酸イオン、吉草酸イオン、ドデシルベンゼンスルホン酸イオン、カンファースルホン酸イオン、酪酸イオン、蟻酸イオン、トリメチル酢酸イオン、ブロモ酢酸イオン、乳酸イオン、クエン酸イオン、コハク酸イオン、シュウ酸イオン、酒石酸イオン、フマル酸イオン、マレイン酸イオン、マロン酸イオン、アスコルビン酸イオン、アニス酸イオン、アントラニル酸イオン、安息香酸イオン、ケイ皮酸イオン、フェニル酢酸イオン、フタル酸イオン、アニリンスルホン酸イオン、チオカルボン酸イオン、メチルスルフィン酸イオン、トリフルオロ酢酸イオン、及びトリフルオロメタンスルホン酸イオンよりなる１〜３価の陰イオン群より選ばれた少なくとも１種の陰イオンを示す。また、ＺはＸ_ｋのイオン価数であり、１〜３の整数を示し、ｊは１〜３の整数を示す。）

(In the formula (15), R ^{148 to} R ¹⁵¹ are each independently hydrogen, R ³⁵ OH, alkyl having 1 to 24 carbon atoms (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, methanesulfonic acid Ion, 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 X 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, represents an integer of 1 to 3, and j represents an integer of 1 to 3.)

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

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

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

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

  As the conductive polymer (D) 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. Further, those having a mass average molecular weight of 3,000 or more and 1,000,000 or less are more preferable, and those having a mass average molecular weight of 5,000 or more and 500,000 or less are most preferable.

  The conductive polymer (D) can be used as it is, but a conductive polymer (D) can be used which has been subjected to a doping treatment method using an acid by a known method to which an external dopant is added. For example, the doping treatment can be performed by a treatment such as immersing a conductor containing the conductive polymer (D) 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.

<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 (A) is further improved, and the applicability and operability are also improved. The solvent (E) is not particularly limited as long as it dissolves or disperses the carbon nanotube (A), the siloxane compound (B), and the active energy ray-sensitive cationic polymerization initiator (C). It is more preferable if it can dissolve or disperse the conductive polymer (D).

Examples of the solvent (E) include water, alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, and butanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone; 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 (E) when 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 (D), is a solubility, a dispersibility of the carbon nanotube (A). In this respect, an organic solvent or a water-containing organic solvent is preferably used.

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

  The carbon nanotube-containing curable composition of the present invention may further include a polymer compound (F), a basic compound (G), a surfactant (H), colloidal silica (J), and the silane coupling described above, if desired. Agent (I) and the like can be used in combination. These concomitant agents can be used alone or in combination of plural or all kinds depending on the purpose.

<Polymer compound (F)>
In the carbon nanotube-containing curable composition of the present invention, by adding the polymer compound (F), the substrate adhesion and strength of the coating film are further improved. 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, polystyrene sulfonic 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 (D), 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)>
When the carbon nanotube-containing curable composition of the present invention contains a conductive polymer, the basic compound (G) has an effect of dedoping the conductive polymer and further improving the dissolution in the composition. Further, by forming a salt with free sulfonic acid groups and carboxyl groups, the solubility in the composition and the solvent is particularly improved, and the solubilization or dispersion of the carbon nanotube (A) is promoted.

（式（１７）中、Ｒ^２４５〜Ｒ^２４７は各々互いに独立に、水素、炭素数１〜４（Ｃ₁ 〜Ｃ₄ ）のアルキル基、ＣＨ₂ＯＨ 、ＣＨ₂ＣＨ₂ＯＨ、ＣＯＮＨ₂ またはＮＨ₂ を表す。） The basic compound (G) is not particularly limited, and 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 (G) is shown in the following general formula (17).

(In the formula (17), R ^{245 to} R ²⁴⁷ 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 )

（式（１８）中、Ｒ^２４８〜Ｒ^２５１は各々互いに独立に、水素、炭素数１〜４（Ｃ₁ 〜Ｃ₄ ）のアルキル基、ＣＨ₂ＯＨ 、ＣＨ₂ＣＨ₂ＯＨ、ＣＯＮＨ₂ またはＮＨ₂ を表し、Ｘ^- はＯＨ^- 、１／２・ＳＯ₄ ^2-、ＮＯ₃ ^-、１／２ＣＯ₃ ^2-、ＨＣＯ₃ ^-、１／２・（ＣＯＯ）₂ ^2-、またはＲ’ＣＯＯ^- を表し、Ｒ’は炭素数１〜３（Ｃ₁ 〜Ｃ₃ ）のアルキル基である。） The structural formula of ammonium salts used as the basic compound (G) is shown in the following general formula (18).

(In the formula (18), 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 (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, the solubilization or dispersion is further promoted, and the flatness, coatability and conductivity 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.

<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 colloidal silica (J), those having a particle size of 1 nm to 300 nm are used, preferably those having a particle size 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 curable composition>
The component ratio of the carbon nanotube-containing curable composition of the present invention is 0.0001 to 40 parts by mass (preferably 0.001 to 20 parts by mass) of the carbon nanotube (A) with respect to 100 parts by mass of the siloxane compound (B). Part), 0.01 to 10 parts by mass (preferably 0.05 to 5 parts by mass) of the active energy ray-sensitive cationic polymerization initiator (C). When using together a conductive polymer (D), 0.001-50 mass parts (preferably 0.01-30 mass parts) are used with respect to 100 mass parts of siloxane compounds (B).

  The carbon nanotube-containing curable composition of the present invention can use a solvent (E) as a constituent component, and the use of the solvent improves solubility / dispersibility, coatability, operability, etc. The composition ratio when used is as follows.

  The use ratio of the carbon nanotube (A) 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 (A) is less than 0.0001 parts by mass, the performance of the carbon nanotube (A) 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 (A) is lowered.

  The proportion of the siloxane compound (B) and the solvent (E) used is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the solvent (E). It is. When the siloxane compound (B) is less than 1 part by mass, the scratch resistance tends to be inferior.

  The blending amount of the active energy ray-sensitive cationic polymerization initiator (C) is not particularly limited, but is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the siloxane compound (B). If it is 0.01 mass part or more, it will fully harden | cure by irradiation of an active energy ray, and there exists a tendency for a favorable protective coating film to be obtained. Moreover, if it is 10 mass parts or less, about the physical property of the protective coating film obtained by hardening, there is no coloring in particular, and it exists in the tendency for surface hardness and abrasion resistance to become favorable. Furthermore, the compounding amount is more preferably in the range of 0.05 to 5 parts by mass from the viewpoint of good curability and a protective coating film having good performance.

The proportion of the conductive polymer (D) and the solvent (E) used is preferably 0.001 to 50 parts by mass of the conductive polymer (D) 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 (D) is less than 0.001 part by mass, the conductivity is inferior, and the carbon nanotube (A) 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 is increased, so that the solubilization or dispersion efficiency of the carbon nanotube (A) is lowered.

  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 (D) and the carbon nanotube (A) 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 in this range, the solubility of the water-soluble conductive polymer is improved, solubilization or dispersion of the carbon nanotube (A) in the solvent (E) is promoted, and the conductivity is improved. To do.

  It is preferable that surfactant (H) is 0.0001-10 mass parts with respect to 100 mass parts of solvent (E), and, as for the usage-amount of surfactant (H) and a solvent (E), More preferably, it is 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 inferior conductivity occurs and the efficiency of solubilization or dispersion of the carbon nanotube (A) 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. If 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, if it exceeds 20 parts by mass, solubility, flatness, transparency, and conductivity are improved. Sexuality may worsen.

  The use ratio of the colloidal silica (j) and the solvent (E) is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 100 parts by mass of the colloidal silica (J) with respect 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.

  Further, the carbon nanotube-containing curable composition of the present invention may include a plasticizer, a dispersing agent, a coating surface adjusting agent, a fluidity adjusting agent, an ultraviolet absorber, an antioxidant, a storage stabilizer, and an adhesion assistant as necessary. Further, various known substances such as thickeners 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>
When mixing the carbon nanotube (A), the siloxane compound (B), the active energy ray-sensitive cation initiator (C), and other components as necessary, which are essential components of the carbon nanotube-containing curable composition of the present invention. 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 with good dispersibility and coating properties is obtained to obtain a high-performance composite, a combination of a conductive polymer (D) and a solvent (E) in addition to the essential components Is effective. In this case, it is preferable to mix the conductive polymer (D), the solvent (E), the carbon nanotube (A), or other components, and irradiate this with ultrasonic waves. In this case, the ultrasonic irradiation and the homogenizer 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 (A) 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 components, 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 concentrated 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 mixed and used, 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. Moreover, as a preferable preparation method, the carbon nanotube-containing composition and the siloxane compound (B) in which the carbon nanotubes are dispersed by subjecting the conductive polymer (D), the carbon nanotube (A), and the solvent (E) to an ultrasonic homogenizer treatment, A method of preparing a carbon nanotube-containing curable composition by mixing an active energy ray-sensitive cationic polymerization initiator (C) and a curable composition comprising a solvent (E) is used.

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

<Method for 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 it can be left at room temperature or subjected to heat treatment to form a cured coating film.

Examples of active energy rays for curing the carbon nanotube-containing curable composition include vacuum ultraviolet rays, ultraviolet rays, visible rays, near infrared rays, infrared rays, far infrared rays, microwaves, electron beams, β rays, and γ rays. It is done. Among them, it is preferable to use ultraviolet rays and visible rays in combination with an active energy ray-sensitive acid generator from the viewpoint of a high polymerization rate and relatively little deterioration of the substrate. Specific examples of active energy ray light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, incandescent bulbs, xenon lamps, halogen lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, gallium lamps, Excimer laser, the sun, etc. are mentioned. Regarding irradiation energy, it is preferable to irradiate so that the integrated energy of a wavelength of 200 to 600 nm is 0.05 to 10 J / cm ² . The irradiation atmosphere of active energy rays may be air or an inert gas such as nitrogen or argon. One kind of active energy rays may be used alone, or a plurality of kinds of different kinds may be used. When different types of active energy rays are used, they may be irradiated simultaneously or sequentially.

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 the siloxane compound (B), the polymer compound (F), the basic compound (G), and the conductive polymer (D) are contained by the heat treatment, the crosslinking reaction with them is further promoted and the water resistance Can be applied in a shorter time, the amount of the remaining solvent (E) can be further reduced, and the conductivity is further improved, which 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. If the temperature is higher than 250 ° C., the conductive polymer (D) itself may be decomposed and the conductivity may be significantly 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 has excellent electrical conductivity as it is, but when the conductive polymer (D) is contained, the carbon nanotube-containing curable composition is formed on at least one surface of the substrate. After forming a coating film by coating the film, the conductivity can be further improved by performing a doping treatment with an acid 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 (D) and the solvent (E) of the present invention described above, the carbon nanotube (A) is converted into the conductive polymer (D) and the siloxane compound (B). In addition to the solvent (E), the carbon nanotube (A) can be dispersed or solubilized in the solvent (E) without impairing the properties of the carbon nanotube (A) and the siloxane compound (B) itself. And does not separate or aggregate even during long-term storage. Although the reason for this is not clearly understood, the carbon nanotube (A) is dispersed or solubilized together with the conductive polymer (D) by adsorbing or spirally wrapping the conductive polymer (D) on the carbon nanotube (A). It is speculated that Further, in the curable composition containing carbon nanotubes using the conductive polymer (D) of the present invention, the conductive polymer (a) and the carbon nanotube (A) are used in combination, so Excellent film and moldability. Further, by using the siloxane compound (B), a cured coating film excellent in film formability and scratch resistance can be formed.

  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 (D-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 (D-2) obtained by reaction of water-soluble conductive polymer (D-1) and benzalkonium chloride)
5 g of water-soluble conductive polymer (D-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 (D-2) having an ammonium sulfonate group.

<Manufacture of siloxane compound solution>
(Production Example 3, Siloxane Compound Solution (B-1))
Methyl silicate with a silica equivalent concentration of 53% (manufactured by Colcoat Co., Ltd., average molecular weight of about 789,
Trade name Methyl silicate 53A) 100 g (solid content 53.0 g), methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 136, trade name KBM-13) 172 g (solid content 84)
0.7 g) and 100 g of isopropyl alcohol were mixed and stirred to obtain a uniform solution. further,
21.0 g of water was added, and the mixture was heated at 80 ° C. for 3 hours with stirring to conduct hydrolysis and condensation.

Thereafter, the temperature was cooled to 25 ° C., and the mixture was stirred for 24 hours to allow condensation to proceed. Furthermore, isopropyl alcohol was added to make a total of 690 g, and a solution of silicon compound A having a solid content concentration of 20% was obtained. Here, the solid content concentration means the mass fraction (%) of the solid content in the silicon compound solution. The solid content means the mass of the compound obtained when the silicon compound is completely hydrolyzed and condensed.

<Carbon nanotube-containing composition>
Carbon nanotube-containing composition 1:
1 part by mass of the conductive polymer (D-1) of Production Example 1 and 1.0 part by mass of carbon nanotubes were mixed with 100 parts by mass of water at room temperature, and 1 ultrasonic homogenizer treatment (vibra cell 20 kHz, manufactured by SONIC) was 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 (D-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 composition 4 (Comparative Example 3):
Carbon nanotube-containing composition 1 5 parts by mass, acrylic resin “Dianal MX-1845” (Mitsubishi Rayon Co., Ltd., resin content 40% by mass) 47.5 parts by mass and water 47.5 parts by mass, which is an aqueous emulsion, are mixed. Stirring to prepare a carbon nanotube-containing composition 5.

<Curable composition>
Curable composition 1 (Comparative Example 1):
A curable composition 1 was prepared by mixing and stirring 95 parts by mass of a siloxane compound solution and 0.4 parts by mass of Syracure UVI-6992 (trade name, manufactured by Dow Chemical Japan Co., Ltd.).

Curable composition 2 (Comparative Example 2):
90 parts by mass of a siloxane compound solution and 0.4 parts by mass of Cyracure UVI-6992 (manufactured by Dow Chemical Japan Co., Ltd., trade name) were mixed and stirred to prepare curable composition 2.

<Carbon nanotube-containing curable composition>
Carbon nanotube-containing curable composition 1 (Example 1):
5 parts by mass of the carbon nanotube-containing composition 1, 95 parts by mass of the siloxane compound solution, and 0.4 parts by mass of Cyracure UVI-6992 (trade name, manufactured by Union Carbide, USA) are mixed and stirred, and the carbon nanotube-containing curable composition 1 is mixed. Was prepared.

Carbon nanotube-containing curable composition 2 (Example 2):
10 parts by mass of the carbon nanotube-containing composition 2, 90 parts by mass of the siloxane compound solution, and 0.4 parts by mass of Cyracure UVI-6992 (trade name, manufactured by Union Carbide, USA) are mixed and stirred, and the carbon nanotube-containing curable composition 2 is mixed. Was prepared.

<Evaluation method>
An appropriate amount of the carbon nanotube-containing curable compositions 1-2, curable compositions 1-2, and carbon nanotube-containing composition 4 obtained in Examples 1-2 and Comparative Examples 1-3 are dropped on a glass substrate, and the bar It was applied by a coating method (bar coater # 12) and dried with a dryer at 60 ° C. for about 10 minutes. 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 2000 mJ / cm ² was irradiated to form a cured coating film, after external observation The surface resistance value and scratch resistance 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)
For the measurement of the surface resistance value under the conditions of 25 ° C. and 50% RH, when the surface resistance value is 10 ⁸ Ω or more, the two-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.
(Abrasion resistance)
The surface of the obtained cured coating film was rubbed 10 times with # 000 steel wool at a pressure of 9.8 × 10 ⁴ Pa, and the degree of scratches generated in the range of 1 cm × 3 cm was observed. It was evaluated with.
“A”: 1 to 9 scratches. There is a glossy surface.
“B”: Countless scratches. There is a glossy surface.

  The carbon nanotube-containing composition of the present invention comprises various antistatic agents, capacitors, electric double layer capacitors, batteries, fuel cells, and polymer electrolyte membranes thereof by using a simple coating method such as coating, spraying, casting, and dipping. , Electrode layers, 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 It can be applied to applications such as paint, electrodeposition paint, plating primer, conductive primer for electrostatic coating, cathodic protection, and improvement of battery storage capacity. In addition, the composite of the present invention includes industrial packaging materials such as semiconductors and electronic parts, transparent conductive resin plates used in semiconductor manufacturing clean rooms, etc., electrophotographic recording materials such as overhead projector films and slide films, etc. Anti-static films, transparent conductive films, audio tapes, video tapes, computer tapes, floppy disks, and other magnetic recording tapes, electronic device LSI wiring, field emission display (FED) electron guns ( Source) and electrode, hydrogen storage agent, transparent touch panel, electroluminescence display, liquid crystal display and other flat panel display input and display device surface display protective plate, front plate, antistatic and transparent electrode, transparent electrode film, organic sensor Luminescent materials, buffer materials for forming the click Toro EL device, an electron-transporting material, a hole-transporting material and a fluorescent material, a thermal transfer sheet, the transfer sheet is used a thermal transfer image-receiving sheet, as the image-receiving sheet.

Claims (3)

  A carbon nanotube-containing curable composition comprising a carbon nanotube (A), a siloxane compound (B), and an active energy ray-sensitive cationic polymerization initiator (C). The carbon nanotube-containing curable composition according to claim 1, further comprising a conductive polymer (D).   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 comprising a coating film.