JP2009040021A - Carbon nanotube-containing structure, carbon nanotube-containing composition, and manufacturing process of carbon nanotube-containing structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing process of a carbon nanotube-containing structure capable of being formed into a coating film which is excellent in the formability and film-forming property, can be applied onto a base material by a simple method, by spoiling no characteristic of the carbon nanotube, and which can maintain conductivity, transparency, a water resistance, a mechanical strength, thermal conductivity, and an abrasive resistance, together with excellent durability of such properties long run. <P>SOLUTION: The carbon nanotube-containing structure comprises the carbon nanotube (a), an urethane compound (b), and a granular substance (c). The manufacturing process of the carbon nanotube-containing structure comprises the step of applying, on at least one surface of the base material, the carbon nanotube-containing composition containing the carbon nanotube (a), the urethane compound (b), and the granular substance (c), and a step of irradiating with an active energy beam and/or leaving at an ordinary temperature or heat processing. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a carbon nanotube-containing structure, a carbon nanotube-containing composition, and a method for producing a carbon nanotube-containing structure.

In recent years, nanotechnology that handles so-called nanomaterials having a nanometer size has attracted attention in various industrial fields. By combining nanomaterials with other materials at the nanometer level, materials with superior functions that have never been seen before have been developed.
Nanomaterials exhibit different properties from the bulk state by being uniformly dispersed in the material. Therefore, it is indispensable to have a technique in which nanomaterials are dispersed in a composition that is combined with other materials. However, in general, since the surface state of nanomaterials is unstable, there is a problem that the nanomaterials aggregate when combined with other materials and cannot exhibit the functions specific to nanomaterials.

By the way, since carbon nanotubes were discovered in 1991 among nanomaterials, their physical properties have been evaluated and their functions have been elucidated, and research and development relating to their applications are also active.
However, carbon nanotubes tend to become entangled and aggregated in the production stage, and when they are combined with other materials such as resin or solvent, the entanglement of carbon nanotubes further aggregates, There has been a problem that the carbon nanotubes cannot exhibit their inherent properties.

In order to solve this problem, attempts have been made to uniformly disperse or dissolve the carbon nanotubes in a resin or solvent by physically treating or chemically modifying the carbon nanotubes.
For example, a method has been proposed in which carbon nanotubes are sonicated in a strong acid to be cut shortly and dispersed (Non-patent Document 1).
However, in the method according to this proposal, since the carbon nanotubes are treated in a strong acid, the operation becomes complicated, and the method is not industrially suitable and the dispersibility is not sufficient.

Also, for example, carbon nanotubes are cut short, both ends of the cut carbon nanotubes are terminated with oxygen-containing functional groups such as carboxylic acid groups, and the carboxylic acid groups are converted into acid chlorides, which are then reacted with amine compounds. Thus, a method for improving dispersibility in a solvent by introducing a long-chain alkyl group has been proposed (Non-patent Document 2).
However, in this proposed method, since a covalent bond is used to introduce a long-chain alkyl group into the carbon nanotube, damage to the graphene sheet structure of the carbon nanotube (hexagon network sheet structure composed of a plurality of carbon atoms), Alternatively, there remain problems such as affecting various characteristics of the carbon nanotube itself.

As another attempt, by utilizing the fact that pyrene molecules adsorb on the surface of carbon nanotubes by strong interaction, a substituent containing ammonium ions is introduced into pyrene molecules, and these pyrene molecules are superposed with carbon nanotubes in water. A method for sonication has been proposed (Non-Patent Document 3). If the method by this proposal is used, a water-soluble carbon nanotube can be manufactured by adsorb | sucking a pyrene molecule to a carbon nanotube non-covalently. In addition, the graphene sheet is hardly damaged due to non-covalent chemical modification.
However, in the method according to this proposal, there is a problem that the conductivity of the carbon nanotube is lowered because non-conductive pyrene molecules exist on the surface of the carbon nanotube.

In addition, a method for obtaining a dispersion by dispersing or dissolving carbon nanotubes in a solvent such as water or an organic solvent by using a general-purpose surfactant or a polymer-based dispersant without impairing the characteristics of the carbon nanotubes themselves. Has been proposed (Patent Document 1, Patent Document 2). There is a description that the carbon nanotubes are stably dispersed in the dispersion.
However, the method according to this proposal does not describe the coating film formed from the dispersion, the dispersion state of the carbon nanotubes in the composite, and the application to a conductive material or the like.

In addition, a carbon nanotube-containing composition comprising carbon nanotubes, a conductive polymer and a solvent, and a structure produced therefrom have been proposed (Patent Document 3). In the method based on this proposal, it has been reported that a structure that does not impair the characteristics of the carbon nanotube itself can be obtained by the coexistence of the conductive polymer. In addition, it has been reported that long-term storage stability of carbon nanotubes in carbon nanotube-containing compositions can be improved by uniformly dispersing or dissolving carbon nanotubes in water, organic solvents, water-containing organic solvents, and other solvents. Yes. The carbon nanotube-containing composition in which the conductive polymer coexists is excellent in conductivity, film formability, and moldability, and can be applied to the substrate by a simple method.
However, in the method according to this proposal, coloring derived from the conductive polymer to be used occurs, so that it is difficult to apply to a material that is required to be colorless and transparent. In general, conductive polymers have low solubility in various solvents, and thus there is a problem that the limit of usable solvents is large.

In addition, a composition comprising a nanomaterial, a (meth) acrylic polymer, a solvent, and a structure produced therefrom have been proposed (Patent Document 4). In the method according to this proposal, the composition and the structure are made to coexist with a (meth) acrylic polymer so that the nanomaterial can be dissolved in a solvent such as water, an organic solvent, or a water-containing organic solvent without impairing the characteristics of the nanomaterial. It is reported that the nanomaterials are excellent in long-term storage stability. A nanomaterial-containing composition in which a (meth) acrylic polymer coexists is excellent in film formability and moldability, and can be applied to a substrate by a simple method.
However, in the method according to this proposal, in order to improve dispersibility, it is necessary to use an amine compound in combination, and there is a problem that a solvent that can be used is limited. Furthermore, since the composition according to this proposal contains a compound containing a sulfonic acid group or the like, when the composition is added to a polymerizable monomer and used as a coating film (cured film), There was no crosslinking point with other materials forming the coating film, and there was a problem that the water resistance and scratch resistance of the coating film were lowered.

In addition, a photosensitive composition for a black matrix has been proposed in which a black pigment such as carbon black or carbon nanotube is added to a binder resin containing a urethane acrylate compound that is a reaction product of an isocyanate compound and a polyhydroxy compound. (Patent Document 5). In the method according to this proposal, the photosensitive composition containing the urethane acrylate compound can easily form a pattern having a high light-shielding property with a thin film, and has a high sensitivity and a high curing speed, so that a black matrix can be produced at a low cost. It is reported that it can be done.
However, in this proposed method, a dispersant for black pigment is added, but the dispersibility of the carbon nanotubes has not been sufficiently studied. In addition, the black matrix is intended to develop light-shielding properties by a coating film obtained from a photosensitive composition containing a black pigment. Since the dispersibility of the carbon nanotubes in the photosensitive composition is low, a sufficiently transparent coating film cannot be obtained. Further, this proposal does not describe improvement in conductivity by carbon nanotubes.

On the other hand, regarding the prior art in which a particulate material is added to a composite (a cured product obtained by combining a plurality of materials), a conductive composition in which conductive particles and carbon nanotubes are dispersed in a thermoplastic resin. Has been proposed (Patent Document 6). In the method according to this proposal, it is reported that the carbon nanotubes contained in the electrically conductive composition assist the conduction between the electrically conductive particles, so that high conductivity can be expressed with a small amount of electrically conductive particles.
However, in the method according to this proposal, no measures for improving the dispersibility of the carbon nanotubes are taken, and the melt is simply kneaded with other materials in a mill. For this reason, the dispersibility of the carbon nanotubes is insufficient, and it cannot be said that the conductivity can be sufficiently improved. In addition, the conductive composition relies on conductive fine particles for the development of conductivity, and the carbon nanotubes themselves are merely used to assist the conduction of the conductive particles. Therefore, it cannot be said that the excellent conductivity of the carbon nanotube is sufficiently exhibited.

Moreover, the radiation-curable composition containing the silica particle which consists of hydrolysis of the oligomer of an alkoxysilane, the monomer which has a urethane bond, and / or its oligomer is proposed (patent document 7). In this proposal, a carbon nanotube is exemplified as an example of the auxiliary material.
However, this proposal does not consider improvement in dispersibility when carbon nanotubes are added to the radiation curable composition, and the characteristics and dispersibility of carbon nanotubes are insufficient.

Further, in the composite mainly composed of the polymer and the particulate matter, the carbon nanotubes are further joined between the polymer / particulate matter in which the polymer and the particulate matter are joined, and the polymer particles A composite of a conductive carbon nanotube and a polymer capable of forming an interconnected network between at least some has been proposed (Patent Document 8). In the method according to this proposal, a surface active agent such as sodium dodecyl sulfate is exemplified as a carbon nanotube stabilizer when forming a composite.
International Publication No. 2002/016257 Pamphlet JP 2005-35810 A International Publication No. 2004/039893 Pamphlet International Publication No. 2006/028200 Pamphlet JP 2005-331938 A JP 2003-34751 A JP 2004-169028 A JP-T-2006-525220 R. E. Smalley et al., “Fullerene Pipes”, Science, 280, p. 1253 (1998) J. et al. Chen et al., “Solution Properties Single-Walled Carbon Nanotube”, Science, 282, p. 95 (1998) Nakajima et al., “Water-Solution Single-Walled Carbon Nanotube Via Noncovalent Side-Functionalization with Pyrene Ammonium Ion”, Chem. Lett. , P. 638 (2002)

However, the proposal of Patent Document 8 describes that although a homogeneous dispersion can be obtained as a whole at the macroscopic level, the carbon nanotubes are dispersed non-uniformly at the microscopic level. There is a problem that is not fully exhibited.
The present invention has been made in view of the above circumstances, and has a carbon nanotube-containing structure having a coating film capable of maintaining excellent conductivity, transparency, water resistance, mechanical strength, thermal conductivity, and scratch resistance in the long term. An object is to provide a body and a carbon nanotube-containing composition for use in the body. Furthermore, it is excellent in film formability and film formability, and can be applied to a substrate by a simple method without impairing the properties of the carbon nanotubes, and the resulting film has excellent long-term conductivity. Another object of the present invention is to provide a carbon nanotube-containing structure that can maintain transparency, water resistance, mechanical strength, thermal conductivity, and scratch resistance.

As a result of intensive studies to solve these problems, the present inventor has reached the present invention. That is, in order to achieve the above object, the present invention employs the following configuration.
[1] A carbon nanotube-containing structure in which a film containing the carbon nanotube (a), the urethane compound (b), and the particulate material (c) is formed on at least one surface of the substrate.
[2] A carbon nanotube-containing composition containing a carbon nanotube (a), a urethane compound (b), and a granular material (c).
[3] A carbon nanotube-containing composition containing the carbon nanotube (a), the urethane compound (b), and the particulate material (c) is applied on at least one surface of the substrate, and active energy rays are applied. A method for producing a carbon nanotube-containing structure, which is irradiated and / or left at room temperature or heat-treated.

The carbon nanotube-containing structure of the present invention maintains excellent conductivity, transparency, water resistance, mechanical strength, thermal conductivity, and scratch resistance in the long term because the carbon nanotubes are uniformly dispersed in the coating. it can.
In addition, by using the carbon nanotube-containing composition of the present invention, a carbon nanotube-containing structure having a film capable of maintaining excellent electrical conductivity, transparency, water resistance, mechanical strength, thermal conductivity, and scratch resistance over the long term. Can provide the body.
In addition, according to the method for producing a carbon nanotube-containing structure of the present invention, it is excellent in film formability and film formability, and can be applied to a substrate by a simple method without impairing the characteristics of the carbon nanotube. Moreover, it is possible to obtain a carbon nanotube-containing structure in which the formed film can maintain long-term excellent conductivity, transparency, water resistance, mechanical strength, thermal conductivity, and scratch resistance.

  Hereinafter, the present invention will be described in detail. In the present invention, “(meth) acrylate” means “acrylate and / or methacrylate”. In addition, “(meth) acryl” means “acryl and / or methacryl”, and “(meth) acryloyl” means “acryloyl and / or methacryloyl”.

<< Carbon nanotube-containing structure >>
The carbon nanotube-containing structure of the present invention has a film containing a carbon nanotube (a), a urethane compound (b), and a granular material (c). By allowing the urethane compound (b) and the particulate material (c) to coexist with the carbon nanotube (a), a carbon nanotube-containing structure having a coating capable of maintaining excellent conductivity and transparency over the long term can be obtained. .

<Carbon nanotube (a)>
The carbon nanotube (a) is, for example, a graphite-like cylinder with several atomic layers rounded, or a cylinder in which a plurality of cylinders are nested, and the outer diameter is extremely small with an order of nm. It is a serious substance.
Examples of the carbon nanotube (a) include ordinary carbon nanotubes, that is, single-walled carbon nanotubes, multi-walled carbon nanotubes in which several layers are concentrically overlapped, coiled carbon nanotubes in which these are coiled, and carbon nanotubes Carbon nanohorns with a closed shape on one side, cup-stacked carbon nanotubes that are shaped like stacked cups, or fullerenes that are analogs of carbon nanotubes (carbon clusters in which carbon atoms are bonded in a hollow spherical shape) ), Carbon nanofibers and the like. Further, those obtained by performing chemical and physical treatments on these carbon nanotubes (a) to introduce functional groups may be used.

Examples of the method for producing the carbon nanotube (a) include a catalytic hydrogen reduction method using carbon dioxide, an arc discharge method, a laser evaporation method, a chemical vapor deposition method (CVD-1 method), and a vapor deposition method. Furthermore, there is a HiPco method in which carbon monoxide is reacted with an iron catalyst at high temperature and pressure to form carbon nanotubes in the gas phase. Examples of the carbon nanotube (a) preferably used in the present invention include single-walled carbon nanotubes and multi-walled carbon nanotubes because various characteristics of the carbon nanotubes are easily expressed.
Moreover, it is preferable that the carbon nanotube (a) is further purified by various purification methods such as a washing method, a centrifugal separation method, a filtration method, an oxidation method, and a chromatographic method.
Furthermore, the carbon nanotube (a) may be pulverized using a ball-type kneading apparatus such as a ball mill, a vibration mill, a sand mill, or a roll mill, or may be cut short by chemical or physical treatment.

<Urethane compound (b)>
The urethane compound (b) is not particularly limited as long as it is a compound having a urethane bond, but is a urethane which is a reaction product by a polymerization reaction of a hydroxyl group-containing (meth) acrylate compound (b-1) and an isocyanate compound (b-2). It is preferable to contain the polymer (b-3) having a bond. When the urethane compound (b) contains the polymer (b-3), the conductivity is further improved.
The urethane compound (b) may be a compound having one or more urethane bonds in one molecule. When two or more urethane bonds are present in the urethane compound (b), the functional groups bonded to each urethane bond may be the same or different. As such a urethane compound (b), for example, a cationic, anionic, nonionic or amphoteric compound can be used. Further, it may be a silicone-based urethane compound having a silicon atom or a fluorine atom in its structure, or a urethane compound having a fluorine-based urethane bond.

(Hydroxyl-containing (meth) acrylate compound (b-1))
The hydroxyl group-containing (meth) acrylate compound (b-1) that can be used in the present invention is not particularly limited as long as it is a compound containing one or more hydroxyl groups and one or more (meth) acrylate groups in the molecule. However, for example, compounds represented by the following general formulas (1) and (2) can be preferably exemplified.

（式中、Ｒ^１１は水素原子またはメチル基を示し、Ｒ^１２はエーテル結合を好ましく含む炭素数２〜２４の炭化水素基であり、ｍ及びｎはそれぞれ１以上、かつ（ｍ＋ｎ）がＲ^１２の炭素数以下である整数を表す。）

(Wherein R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a hydrocarbon group having 2 to 24 carbon atoms preferably containing an ether bond, m and n are each 1 or more, and (m + n) is R ^12. Represents an integer that is less than or equal to the carbon number of

（式中、Ｒ^２１は水素原子またはメチル基を示し、Ｒ^２２は炭素数２〜２４のアルキレン基、炭素数１〜２４のアリーレン基、または炭素数１〜２４のアラルキレン基を、ｎは１〜１００の整数を表す。）

(In the formula, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents an alkylene group having 2 to 24 carbon atoms, an arylene group having 1 to 24 carbon atoms, or an aralkylene group having 1 to 24 carbon atoms; Represents an integer of ~ 100.)

  Examples of the hydroxyl group-containing (meth) acrylate compound (b-1) having one (meth) acrylate group and one hydroxyl group include 1-hydroxyethyl (meth) acrylate and 2-hydroxy (meth) acrylate. Ethyl, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-1,1-dimethylethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-1-methyl (meth) acrylate Ethyl, 3-hydroxy-2-methylpropyl (meth) acrylate, 2-hydroxy-2-methylpropyl (meth) acrylate, 1- (hydroxymethyl) propyl (meth) acrylate, hydroxybutyl (meth) acrylate , (Meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 2-hydroxy-1- Tylpropyl, 3-hydroxy-1-methylpropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (meth) acryl 2-hydroxyhexyl acid, 2-hydroxyheptyl (meth) acrylate, 2-hydroxyoctyl (meth) acrylate, 2-[(6-hydroxyhexanoyl) oxy] ethyl (meth) acrylate, (meth) acrylic acid 2-hydroxy-3-methoxypropyl, 3-butoxy-2-hydroxypropyl (meth) acrylate, 9-hydroxy-10-methoxydecyl (meth) acrylate, 2,2-dimethyl-3- (meth) acrylate Hydroxypropyl, 3-hydroxybutyl (meth) acrylate, (meth) 3-methyl-3-hydroxybutyl crylate, 1-methyl-3-hydroxypropyl (meth) acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, 2- [2- (2-hydroxyethoxy) ethoxy]) ethyl, 2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} ethyl (meth) acrylate, decaethylene glycol (meth) acrylate, tridecaethylene glyco -(Meth) acrylate, (meth) acrylic acid 17-hydroxy-3,6,9,12,15-pentaoxaheptadecan-1-yl, (meth) acrylic acid 20-hydroxy-3,6,9,12 , 15,18-hexaoxaicosan-1-yl, 2-methyl-2- (3-hydroxy-2,2-dimethylpropyl) (meth) acrylate (Ropoxycarbonyl) propyl, (meth) acrylic acid 3- [3- (3-hydroxypropyl) -3-oxopropoxy] -3-oxopropyl, (meth) acrylic acid 2-hydroxy-3-allyloxypropyl, 1-phenyl-2-hydroxyethyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (4-hydroxyphenyl) ethyl (meth) acrylate 2-((2-hydroxybenzyl) oxy] ethyl (meth) acrylate, 2- (4-hydroxyphenoxy) ethyl (meth) acrylate, 3-hydroxy-4-acetylphenyl (meth) acrylate, (meta ) Acrylic acid 4- (hydroxymethyl) cyclohexylmethyl, (meth) acrylic acid 3-hydroxy Proxy-4-benzoylphenyl, and (meth) acrylic acid 1- (hydroxymethyl) tridecyl, (meth) acrylate, 12-hydroxydecyl, 2-hydroxyethyl (meth) tetradecyl acrylic acid.

  Examples of the hydroxyl group-containing (meth) acrylate compound (b-1) having one (meth) acrylate group and two or more hydroxyl groups include 3,4-dihydroxybutyl (meth) acrylate and (meth) acrylic. 2,2-bis (hydroxymethyl) butyl acid, 2-hydroxy-1-hydroxymethyl ethyl (meth) acrylate, 1,1-bis (hydroxymethyl) ethyl (meth) acrylate, 2, (meth) acrylic acid 2, 3-dihydroxypropyl, 2,3-dihydroxybutyl (meth) acrylate, 2-hydroxy-1-hydroxymethylpropyl (meth) acrylate, 3-hydroxy-2- (hydroxymethyl) propyl (meth) acrylate, ( 2,3-dihydroxy-1-methylpropyl (meth) acrylate, 2,4-dihydro (meth) acrylate Sibutyl, 2-methyl-3-hydroxy-2- (hydroxymethyl) propyl (meth) acrylate, 2,3-dihydroxy-2-methylpropyl (meth) acrylate, 3-hydroxy-1- (meth) acrylate (Hydroxymethyl) propyl, (meth) acrylic acid 9,10-dihydroxydecyl, (meth) acrylic acid 2,3-dihydroxy-2- (hydroxymethyl) propyl, (meth) acrylic acid 2-hydroxy-1,1- Bis (hydroxymethyl) ethyl, pentaerythritol mono (meth) acrylate, 2,3,4-trihydroxybutyl (meth) acrylate, 1- (hydroxymethyl) -2,3-dihydroxypropyl (meth) acrylate, etc. Can be mentioned.

  Examples of the hydroxyl group-containing (meth) acrylate compound (b-1) having two or more (meth) acrylate groups and one hydroxyl group include di (meth) acrylate 2-hydroxytrimethylene and di (meth). 2-hydroxy-2-methyltrimethylene acrylate, 2-hydroxymethyl-2-methyl-1,3-propanediyl bis (meth) acrylate, 2-ethyl-2- (hydroxymethyl) di (meth) acrylate Trimethylene, di (meth) acrylic acid 2- (hydroxymethyl) -1,3-propanediyl, bis (meth) acrylic acid 2-hydroxy-1-methyl-1,3-propanediyl, bis (meth) acrylic acid 1 -(2-hydroxyethyl) -1,2-ethanediyl, bis (meth) acrylate 1-hydroxymethyl-1,2-ethanediyl, bi 1- (1-hydroxyethyl) -1,2-ethanediyl (meth) acrylate, 1-hydroxymethyl-2-methyl-1,2-ethanediyl bis (meth) acrylate, 1- (bis (meth) acrylic acid Hydroxymethyl) -1-methylethylene, bis (meth) acrylic acid 2-hydroxy-1,4-butanediyl, bis (meth) acrylic acid 1- (hydroxymethyl) -1,3-propanediyl, bis (meth) acrylic Acid 2-hydroxy-1,6-hexanediyl, bis (meth) acrylic acid 1- (2-hydroxypropoxymethyl) ethylenebis [oxy (1-methyl-2,1-ethanediyl)], bis (meth) acrylic acid 2- (2-hydroxypropoxy) -1,3-propanediylbis [oxy (1-methyl-2,1-ethanediyl)], (meth ) 8- (2-hydroxypropoxy) acrylic acid-1,4,12-trimethyl-14-oxo-3,6,10,13-tetraoxa-15-hexadecen-1-yl, 2-hydroxy (meth) acrylic acid 3-[(2-methyl-1-oxo-2-propenyl) oxy] propyl, pentaerythritol tri (meth) acrylate, tris (meth) acrylic acid 2- (hydroxymethyl) propane-1,2,3- Triyl, bis (meth) acrylic acid 2- (acryloyloxymethyl) -2-hydroxypropane-1,3-diyl, tris (meth) acrylic acid 3- (hydroxymethyl) propane-1,2,3-triyl, Tris (Meth) acrylic acid 3-hydroxybutane-1,2,4-triyl, (meth) acrylic acid 3- [2,2-bis [((meth) [Acryloyloxy) methyl] -3-hydroxypropoxy] -2,2-bis [((meth) acryloyloxy) methyl] propyldipentaerythritol penta (meth) acrylate, bis (meth) acrylic acid 2-({[ 2- (Hydroxymethyl) -2-[((meth) acryloyloxy) methyl] -3-(((meth) acryloyloxy) propyl] oxy} methyl) -2-[((meth) acryloyloxy) methoxy] propane- 1,3-diyl and the like can be mentioned.

Examples of the hydroxyl group-containing (meth) acrylate compound (b-1) having two or more (meth) acrylate groups and two or more hydroxyl groups include bis (meth) acrylic acid 2,3-dihydroxybutane-1, 4-diyl, bis (meth) acrylic acid 2-hydroxy-2- (hydroxymethyl) propane-1,3-diyl, di (meth) acrylic acid 2,2-bis (hydroxymethyl) -1,3-propanediyl Bis (meth) acrylic acid 2-hydroxy-3- (hydroxymethyl) propane-1,3-diyl, bis (meth) acrylic acid 1,1-bis (hydroxymethyl) ethylene, bis (meth) acrylic acid 1- (1,2-dihydroxyethyl) ethane-1,2-diyl, bis (meth) acrylic acid 1,2-bis (hydroxymethyl) ethylene, bis (meth) a 1,6-Hexanediylbis (oxy) bis (2-hydroxy-3,1-propanediyl) yllate, bis (meth) acrylic acid (2,11-dihydroxy-4,9-dioxadodecane) -1, 12-diyl, bis (meth) acrylic acid 2,9-dihydroxy-4,7-dioxadecane-1,10-diyl, di (meth) acrylic acid 3,3 ′-(1,3-phenylenebisoxy) bis ( 2-hydroxypropyl) and the like.
These compounds may be used alone or in combination of two or more.

(Isocyanate compound (b-2))
The isocyanate compound (b-2) that can be used in the present invention is not particularly limited as long as it is an isocyanate, diisocyanate, triisocyanate, or polyisocyanate, but is preferably a diisocyanate compound and / or a triisocyanate compound.

  Examples of the isocyanates include phenyl isocyanate, tolyl isocyanate, naphthyl isocyanate, vinyl isocyanate, and the like.

  Examples of the diisocyanates include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate. Diisocyanates; cycloaliphatic diisocyanates such as isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω'-diisocyanate dimethylcyclohexane; xylylene diisocyanate, α, α, α ', α'-tetra Aliphatic diisocyanates having an aromatic ring such as methylxylylene diisocyanate; benzene-1,3-diiso Benzene diisocyanates such as anate and benzene-1,4-diisocyanate; toluene diisocyanates such as toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, toluene-3,5-diisocyanate 1,2-xylene-3,5-diisocyanate, 1,2-xylene-3,6-diisocyanate, 1,2-xylene-4,6-diisocyanate, 1,3-xylene-2,4-diisocyanate, 1,3-xylene-2,5-diisocyanate, 1,3-xylene-2,6-diisocyanate, 1,3-xylene-4,6-diisocyanate, 1,4-xylene-2,5-diisocyanate, 1, Xylene diisocyanates such as 4-xylene-2,6-diisocyanate And aromatic diisocyanates such as sulphonates.

  Examples of the triisocyanates include benzene triisocyanates such as benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate, and benzene-1,3,5-triisocyanate; 2,3,5-triisocyanate, toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate, toluene-2,4,6-triisocyanate, toluene-3,4,6- Tolocyanate such as triisocyanate, toluene-3,5,6-triisocyanate; 1,2-xylene-3,4,6-triisocyanate, 1,2-xylene-3,5,6-triisocyanate, 1,3-xylene-2,4,5-triisocyanate, 1,3-xylene-2,4,6-to Xylene tris such as isocyanate, 1,3-xylene-3,4,5-triisocyanate, 1,4-xylene-2,3,5-triisocyanate, 1,4-xylene-2,3,6-triisocyanate Aromatic triisocyanates such as isocyanate; lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptanetri Mention may be made of aliphatic, alicyclic or heteroatom-containing triisocyanates such as isocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate.

  Examples of the polyisocyanates include the diisocyanates, trimers of triisocyanates, and polyol adducts thereof.

  The diisocyanates are represented by the following general formula (3), the triisocyanates are the following general formula (4), and the diisocyanates or the aromatic isocyanates in the triisocyanates are represented by the following general formula (5). A compound can be mentioned as a preferred example.

（式中、Ｒ^３１は水素、または炭素数１〜８のアルキル基、ｎは１〜２５の整数を表す。また、ｎが２以上の場合には、各（置換）メチレン基に置換するＲ^３１は同一であっても、異なってもよい。）

(In the formula, R ³¹ represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 25. When n is 2 or more, each (substituted) methylene group is substituted with R. ³¹ may be the same or different.)

（式中、Ｒ^４１〜Ｒ^４３はそれぞれ独立に炭素数１〜２４のアルキレン基、アリーレン基、またはアラルキレン基から選ばれた２価の基を表す。）

(Wherein, R ^{41 to} R ⁴³ each independently represents a divalent group selected from an alkylene group having 1 to 24 carbon atoms, an arylene group, or an aralkylene group.)

（式中、Ｒ^５１は炭素数１〜８のアルキル基、アリール基、アラルキル基から選ばれた基であり、ｍは０〜４の整数であり、ｍが２以上の時には同一であってもよいし、異なっていてもよい。ｎは２〜６の整数であり、（ｍ＋ｎ）は６以下の整数である。）

(In the formula, R ⁵¹ is a group selected from an alkyl group having 1 to 8 carbon atoms, an aryl group, and an aralkyl group, m is an integer of 0 to 4, and when m is 2 or more, they may be the same. (N may be an integer of 2 to 6, and (m + n) is an integer of 6 or less.)

  Preferred examples of the diisocyanates represented by the general formula (3) include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and octamethylene diisocyanate. .

  As triisocyanate represented by the said General formula (4), what consists of a trimer of the said diisocyanate is preferable.

  As aromatic isocyanates represented by the general formula (5), benzene-1,3-diisocyanate, benzene-1,4-diisocyanate, toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene -2,6-diisocyanate, toluene-3,5-diisocyanate, 1,2-xylene-3,5-diisocyanate, 1,2-xylene-3,6-diisocyanate, 1,2-xylene-4,6-diisocyanate 1,3-xylene-2,4-diisocyanate, 1,3-xylene-2,5-diisocyanate, 1,3-xylene-2,6-diisocyanate, 1,3-xylene-4,6-diisocyanate, , 4-xylene-2,5-diisocyanate, 1,4-xylene-2,6-diisocyanate And the like preferably.

Of these isocyanate compounds (b-2), hexamethylene diisocyanate, hexamethylene diisocyanate trimer, toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, Toluene-3,5-diisocyanate, 1,2-xylene-3,5-diisocyanate, 1,2-xylene-3,6-diisocyanate, 1,2-xylene-4,6-diisocyanate, 1,3-xylene- 2,4-diisocyanate, 1,3-xylene-2,5-diisocyanate, 1,3-xylene-2,6-diisocyanate, 1,3-xylene-4,6-diisocyanate, 1,4-xylene-2, 5-diisocyanate, 1,4-xylene-2,6-diisocyanate It is used.
In addition, these isocyanate compounds (b-2) may be used independently and can also be used together 2 or more types.

  As a urethane compound (b) used by this invention, the hydroxyl-containing (meth) acrylate compound (b-1) represented by the said General formula (1) and the said General formula (2), and the said General formula (3) A reaction product with the isocyanate compound (b-2) represented by formulas (4) and (5) is particularly preferable. The reactant in the urethane compound (b) also has a function as a polymerizable monomer, and the carbon nanotube (a) is uniformly dispersed in the polymerizable monomer (d-1) described later. It works particularly effectively.

  The urethane compound (b) may be used alone or in combination of two or more. The urethane compound (b) may contain a urethane compound other than those exemplified above.

<Particulate matter (c)>
The particulate material (c) used in the present invention is not particularly limited as long as it has a particulate form in the obtained coating film. For example, organic particles, inorganic particles, ceramic particles are used. , Metal oxide particles, metal particles, dyes, pigments and the like. Specifically, resin particles such as acrylic, silica, colloidal silica, plate-like alumina, fibrous alumina, zirconia, spinel, talc, mullite, cordierite, silicon carbide, yttrium oxide, cerium oxide, samarium oxide, lanthanum oxide, Terbium oxide, europium oxide, neodymium oxide, zinc oxide, titanium oxide, gnesium fluoride, tin oxide, indium oxide, antimony-containing tin oxide (ATO), tin-containing indium oxide (ITO), zinc antimonate, antimony pentoxide, gold And metal particles such as silver, copper and nickel, hematite, cobalt blue, cobalt violet, cobalt green, magnetite, Mn-Zn ferrite, Ni-Zn ferrite and barium titanate.
Among these particulate materials, for example, yttrium oxide, cerium oxide, samarium oxide, lanthanum oxide, terbium oxide, europium oxide, neodymium oxide, zinc oxide, titanium oxide, gnesium fluoride, tin oxide, indium oxide, antimony-containing tin oxide, Use of metal particles such as tin-containing indium oxide, zinc antimonate, antimony pentoxide, gold, silver, copper, nickel, etc. is preferred because it can provide better conductivity. Moreover, you may use the metal salt double oxide which is a higher order compound which consists of 2 or more types of metal oxides. Examples of the metal salt double oxide include antimony double oxide composed of zinc antimonate and the like.

The particulate material (c) is preferably used in the form of a colloid obtained by dispersing in a solvent such as water, an organic solvent, or a mixed solvent of water and an organic solvent. 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. .
The particle diameter of the granular material (c) is preferably 1 nm to 50000 nm, more preferably 1 nm to 10000 nm, and further preferably 1 nm to 1000 nm. When the particle diameter exceeds the above range, the transparency is insufficient, and the dispersibility and stability of the particulate material (c) in the solvent are lowered.

  In the carbon nanotube-containing structure of the present invention, a dense conductive network can be formed between the carbon nanotube (a) and the granular material (c) because the coating contains the granular material (c). The conductivity can be further improved. In addition, since the portion where the carbon nanotube (a) exists in the coating and the portion where the carbon nanotube (a) does not exist due to the granular material (c) are uniformly distributed, the light absorption, scattering, Reflection is suppressed, and the transparency, mechanical strength, thermal conductivity, etc. of the carbon nanotube-containing structure are improved. In addition, a granular material (c) may be used independently and can also be used together 2 or more types.

<Polymer (e) having unit of polymerizable monomer (d-1)>
It is preferable that the carbon nanotube-containing structure contains a polymer (e) having a coating monomer (d-1) unit. By containing the polymer (e), the scratch resistance of the coating film of the carbon nanotube-containing structure can be improved. In addition, it is preferable to use a polymer (e) that is compatible with the urethane compound (b).
As the polymerizable monomer (d-1) forming the polymer (e), (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic compound having two or more polymerizable groups, styrene , Methylstyrene, bromostyrene, vinyltoluene, divinylbenzene, vinyl acetate, N-vinylcaprolactam, N-vinylpyrrolidone and the like. Among these, from the viewpoint of transparency, impact resistance, scratch resistance, and easy moldability of the resulting cured film, it has (meth) acrylic acid, (meth) acrylic acid ester, and two or more polymerizable groups (meta ) Acrylic compounds are preferred.

  (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic. I-butyl acid, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) Dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate , Ethyl trimethylammonium chloride (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) acrylic acid 1,4-butanediol and the like can be mentioned.

  As the (meth) acrylic compound having two or more polymerizable groups, (A) esterified product obtained by reacting 2 mol or more of (meth) acrylic acid or a derivative thereof with 1 mol of polyhydric alcohol; B) Linear ester having two or more (meth) acryloyloxy groups in one molecule obtained from polyvalent carboxylic acid or its anhydride, polyhydric alcohol, and (meth) acrylic acid or derivatives thereof (C) poly [(meth) acryloyloxyethyl] isocyanurate; (D) epoxy polyacrylate and the like.

  Examples of the esterified product (A) include polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri ( (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol te La (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate.

In the esterified product (B), preferred combinations of polycarboxylic acid or anhydride / polyhydric alcohol / (meth) acrylic acid include malonic acid / trimethylolethane / (meth) acrylic acid, malonic acid / trimethylol. Propane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, succinic acid / trimethylolpropane / (Meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meth) acrylic acid, adipic acid / trimethylolethane / (meth) acrylic acid, adipic acid / trimethylolpropane / (Meth) acrylic acid, adipic acid / glycerin / (meta Acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid, glutaric acid / trimethylolethane / (meth) acrylic acid, glutaric acid / trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic Acid, glutaric acid / pentaerythritol / (meth) acrylic acid, sebacic acid / trimethylolethane / (meth) acrylic acid, sebacic acid / trimethylolpropane / (meth) acrylic acid, sebacic acid / glycerin / (meth) acrylic acid , Sebacic acid / pentaerythritol / (meth) acrylic acid, fumaric acid / trimethylolethane / (meth) acrylic acid, fumaric acid / trimethylolpropane / (meth) acrylic acid, fumaric acid / glycerin / (meth) acrylic acid, Fumaric acid / pentaerythritol / ( TA) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic acid / glycerin / (meth) acrylic acid, itaconic acid / pentaerythritol / (meta) ) Acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid, maleic anhydride / trimethylolpropane / (meth) acrylic acid, maleic anhydride / glycerin / (meth) acrylic acid, maleic anhydride / pentaerythritol / (Meth) acrylic acid and the like.
Examples of (C) poly [(meth) acryloyloxyethyl] isocyanurate include di- or tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid. These polymerizable monomers (d-1) may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The polymer (e) having a polymerizable monomer unit contained in the film is a polymer or copolymer containing one or more of the polymerizable monomers (d-1), or the above-mentioned one type. It is a copolymer of the above polymerizable monomer (d-1) and another vinyl monomer.

The carbon nanotube-containing structure of the present invention has a coating containing the carbon nanotube (a), the urethane compound (b), and the granular material (c) as described above on at least one surface of the substrate. Is formed.
Base materials include synthetic resin films, sheets, foams, porous membranes, elastomers, various molded products; wood, paper materials, ceramics, fibers, non-woven fabrics, carbon fibers, carbon fiber paper, glass plates, stainless steel plates, etc. Can be mentioned.

The preferred composition ratio of the carbon nanotube (a), the urethane compound (b), and the granular material (c) contained in the carbon nanotube-containing structure of the present invention is 0.0001 to 40 parts by mass of the carbon nanotube (a), the urethane compound ( b) 0.001 to 50 parts by mass, granular material (c) 0.0001 to 40 parts by mass. Further preferable composition ratios are 0.001 to 20 parts by mass of the carbon nanotube (a), 0.01 to 30 parts by mass of the urethane compound (b), and 0.001 to 20 parts by mass of the granular substance (c) (a, b , C is 100 parts by mass).
When the carbon nanotube-containing composition contains the polymer (e) having a unit of the polymerizable monomer (d-1), a preferable composition ratio of each material included in the carbon nanotube-containing structure of the present invention is: Carbon nanotube (a) 0.0001-40 mass parts, urethane compound (b) 0.001-50 mass with respect to 100 mass parts of polymer (e) which has a unit of polymerizable monomer (d-1). Part, granular material (c) 0.0001-40 parts by mass.

The thickness of the coating containing the carbon nanotube (a), the urethane compound (b), the granular material (c) and the polymer (e) having a unit of the polymerizable monomer (d-1) is sufficient. In order to achieve good conductivity, 0.5 to 100 μm is preferable, and 1 to 50 μm is more preferable. When the thickness of the coating is within the above range, sufficient transparency can be obtained, and cracking of the coating can be suppressed, and chipping of the coating at the time of cutting the laminate can be suppressed.
Moreover, the thickness of the film obtained by preparing the carbon nanotube (a), the urethane compound (b), and the granular material (c) using the solvent (d-2) described later is in the range of 0.01 to 100 μm. Is more preferable, and it is 0.1-50 micrometers. When the thickness of the coating is within the above range, the transparency of the coating can be sufficiently maintained and sufficient conductivity can be exhibited.
In the carbon nanotube-containing structure of the present invention, an antireflection film may be further laminated on the coating, if necessary. Further, a carbon nanotube-containing film may be provided on one surface of the substrate, and another functional thin film such as an antireflection film, a diffusion layer, or an adhesive layer may be provided on the other surface.

  In the carbon nanotube-containing structure of the present invention, since the urethane compound (b), the particulate substance (c), and the carbon nanotube (a) coexist in the film, the carbon nanotube (a) is extremely aggregated and unevenly distributed. Few. The reason is not clear, but it is assumed that the urethane compound (b) adsorbs the carbon nanotubes (a) or wraps them in a spiral shape to obtain a film in which the carbon nanotubes (a) are uniformly dispersed. The In addition, the coating in which the carbon nanotubes (a) are uniformly dispersed is less likely to cause the carbon nanotubes (a) to be detached or damaged even when an external stimulus such as friction is applied. Therefore, the carbon nanotube-containing structure of the present invention can maintain excellent conductivity, transparency, water resistance, mechanical strength, thermal conductivity, and scratch resistance in the coating film for a long period of time.

  For example, the transparency of the coating formed on the carbon nanotube-containing structure of the present invention depends on the physical properties of other components, but its total light transmittance is approximately 50% or more, and in some cases 70% or more. Can be maintained. Therefore, the carbon nanotube-containing structure of the present invention can be widely applied to various uses requiring transparency, such as a transparent conductive film, a transparent conductive sheet, and a transparent conductive molded body.

<< Method for producing carbon nanotube-containing structure >>
In the method for producing a carbon nanotube-containing structure, a carbon nanotube-containing composition containing a carbon nanotube (a), a urethane compound (b), and a granular material (c) is applied on at least one surface of a substrate. It is characterized in that it is irradiated with active energy rays and / or left at room temperature, or is heat-treated.

<Constituent material of base material>
Base materials include synthetic resin films, sheets, foams, porous membranes, elastomers, and other various molded articles; wood, paper, ceramics, fibers, nonwoven fabrics, carbon fibers, carbon fiber paper, glass plates, stainless steel A board etc. are mentioned.
Examples of the synthetic resin include polyethylene, polyvinyl chloride, polypropylene, polystyrene, acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-styrene resin (AS resin), acrylic resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, Polyvinylidene fluoride, polyester, polyamide, polyimide, polyaramid, polyphenylene sulfide, polyether ether ketone, polyphenylene ether, polyether nitrile, polyamide imide, polyether sulfone, polysulfone, polyether imide, polybutylene terephthalate, polyurethane, etc. . These synthetic resins may be used alone or as a mixture of two or more.

The polymerizable raw material for forming the base material is appropriately selected depending on its use. For example, in order to obtain a carbon nanotube-containing structure that requires excellent transparency such as a transparent conductive film, a transparent conductive resin plate, a transparent electrode film, a transparent touch panel, etc., a polymer having excellent transparency can be obtained. A monomer mixture containing (meth) acrylic acid or (meth) acrylic acid ester as a main component or a monomer mixture containing a polymer obtained by polymerizing a part of this monomer mixture is preferably used. The polymer content in the monomer mixture containing the polymer is preferably 35% by mass or less in the monomer mixture.
(Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic Cyclohexyl acid, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acryldimethylaminoethyl, diethylaminoethyl (meth) acrylate, ethyl trimethylammonium (meth) acrylate Examples include chloride.

  The monomer mixture may contain other polymerizable monomers such as styrene, methylstyrene, bromostyrene, vinyltoluene, divinylbenzene, vinyl acetate, N-vinylcaprolactam, N-vinylpyrrolidone and the like. Another polymerizable monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  When the polymerizable raw material is subjected to a polymerization reaction, a chain transfer agent may be added. The chain transfer agent is preferably a mercaptan chain transfer agent such as an alkyl mercaptan having 2 to 20 carbon atoms, mercapto acid, thiophenol, or a mixture thereof, and a mercaptan having a short alkyl chain such as n-octyl mercaptan or n-dodecyl mercaptan. Is particularly preferred. By adding a chain transfer agent, the molecular weight of the resulting polymer can be more preferably adjusted.

  When the polymerizable raw material is polymerized by heat treatment, a radical polymerization initiator such as an azo compound, an organic peroxide, or a redox polymerization initiator may be added. Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvalero). Nitrile) and the like. Examples of the organic peroxide include benzoyl peroxide and lauroyl peroxide. Examples of redox polymerization initiators include combinations of organic peroxides and amines.

  When polymerizing a polymerizable raw material by ultraviolet irradiation, a photopolymerization initiator such as a phenyl ketone compound or a benzophenone compound may be added. Commercially available photopolymerization initiators include “Irgacure 184” (manufactured by Ciba Geigy Japan), “Irgacure 907” (manufactured by Ciba Geigy Japan), “Darocure 1173” (manufactured by Merck Japan), “Ezacure KIP100F” (Nihon Siebel) Hegner) and the like.

  Further, when the polymerizable raw material is polymerized by ultraviolet irradiation, a photosensitizer may be added. Examples of photosensitizers include benzoin, benzoin ethyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, azobisisobutyronitrile, benzoyl peroxide, and the like. Is mentioned. Further, for example, benzoin isobutyl ether, benzoin isopropyl ether, or 4,4′-bis (diethylamino) -benzophenone may be added as a photosensitizer having a sensitizing action in a wavelength region of 400 nm or less.

<Constituent material of carbon nanotube-containing composition>
The carbon nanotube-containing composition contains the carbon nanotube (a), the urethane compound (b), and the particulate material (c) as essential constituent materials. Furthermore, a polymerizable monomer (d-1) and a polymerization initiator (f) may be added to the carbon nanotube-containing composition in order to improve scratch resistance. Further, in order to improve dispersibility, conductivity, etc., a solvent (d-2) may be added, and in order to improve mechanical strength and adhesion to a substrate, it contains a polymer compound (g). May be. In order to further improve the solubility or dispersibility of the carbon nanotube (a), a surfactant (h) may be added. In order to improve water resistance, a silane coupling agent (i) or the like may be added. Constituent materials may be added.
The constituent materials that are preferably added will be described below. Since the polymerizable monomer (d-1) has been described above, the description thereof is omitted.

(Solvent (d-2))
By adding the solvent (d-2), the carbon nanotubes (a) can be more uniformly dispersed, and the conductivity of the resulting coating can be further improved.
The solvent (d-2) is not particularly limited as long as it can dissolve the urethane compound (b). Specifically, water; alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone, diacetone alcohol; ethyl acetate, n-butyl acetate , Esters such as 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, pro Propylene glycols such as lenglycol monomethyl ether acetate; amides such as N, N-dimethylformamide and dimethylacetamide; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; dimethylsulfoxide, γ-butyrolactone, methyl lactate, Hydroxyesters such as ethyl lactate, 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 Chlorinated solvents such as tetrahydrofuran, 1,4-dioxane, ethyl cellosolve, butyl cellosolve, methoxypropanol, chloroform, carbon tetrachloride and ethylene dichloride are preferably used.

(Polymerization initiator (f))
By adding the polymerization initiator (f), the polymerization reaction of the polymerizable monomer and / or polymerizable monomer (d-1) contained in the urethane compound (b) can be smoothly advanced and cured. The scratch resistance of the film can be improved.
Examples of the polymerization initiator (f) preferably used in the present invention include a photopolymerization initiator and a thermal polymerization initiator. In the present invention, either a photopolymerization initiator or a thermal polymerization initiator is appropriately selected according to the constituent material and application of the carbon nanotube-containing composition.
The photopolymerization initiator is a material that imparts a polymerization promoting effect by active energy rays to the urethane compound (b) or the polymerizable monomer (d-1). As photopolymerization initiators, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. Carbonyl compounds; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoy Examples include rudiethoxyphosphine oxide. A photoinitiator may be used individually by 1 type and may use 2 or more types together.

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. Moreover, you may use a thermal-polymerization initiator and a photoinitiator together as needed.

(Polymer compound (g))
By adding the polymer compound (g), the adhesion of the coating to the substrate and the mechanical strength of the coating can be further improved.
The polymer compound (g) does not include the urethane compound (b) and the particulate material (c) described above.
The polymer compound (g) is not particularly limited as long as it can be dissolved in the urethane compound (b), the polymerizable monomer (d-1), the solvent (d-2), etc. For example, polyvinyl alcohol, Polyvinyl alcohols such as polyvinyl formal and polyvinyl butyral; poly (meth) acrylates such as polymethyl methacrylate, polybutyl methacrylate and polymethyl acrylate; polyacrylic acid, polymethacrylic acid, polyacrylate and polymethacrylate Poly (meth) acrylic acids such as polyacrylamides, polyacrylamides such as poly (Nt-butylacrylamide); polyvinylpyrrolidones, polystyrene sulfonic acid and its soda salts, cellulose, alkyd resins, melamine resins, Urea resin, phenolic resin, epoxy Resin, polybutadiene resin, acrylic 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, acetic acid Vinyl / acrylic copolymer resin, polyester resin, styrene / maleic acid copolymer resin, fluororesin, and copolymers thereof are used. Moreover, these polymer compounds (g) may be used individually by 1 type, and may mix 2 or more types in arbitrary ratios.

(Surfactant (h))
By adding the surfactant (h), the solubility or dispersibility of the carbon nanotube (a) in the carbon nanotube-containing composition can be further improved. In addition, by using the surfactant (h), the formability and film formability of the carbon nanotube-containing composition on the base material are improved, and the flatness and conductivity of the resulting film are also 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, tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridiniums Salts, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium salts, N, N-dialkylmorpholinium salts, polyethylene polyamine fatty acid amides and salts thereof, urea condensates of polyethylene polyamine fatty acid amides and salts thereof, Cationic surfactants such as quaternary ammonium salts of urea condensates of polyethylene polyamine fatty acid amides; N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N, N, N-trialkyl-N- Betaines such as sulfoalkylene ammonium betaine, N, N-dialkyl-N, N-bispolyoxyethylene ammonium sulfate betaine, 2-alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine; N, N— Dialkylaminoalkylene Amphoteric surfactants such as aminocarboxylic acids such as borate; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-poly Oxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylenated castor oil, fatty acid diethanolamide, polyoxyethylene alkylamine, Nonionic surfactants such as triethanolamine fatty acid partial esters and trialkylamine oxides; and fluoroalkylcarboxylic acids, perfluoro Alkyl carboxylic acids, perfluoro benzene sulfonic acid, 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, these surfactant (h) may be used individually by 1 type, and may be used together 2 or more types.

(Silane coupling agent (i))
By adding the silane coupling agent (i), the water resistance of the resulting film can be improved.
Although it does not specifically limit as a silane coupling agent (i), For example, the silane coupling agent represented by following General formula (6) is mentioned.

（式（６）中、Ｒ^６１〜Ｒ^６３は、それぞれ独立に水素原子、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、ハロゲン原子を表し、Ｘ^６１は、下記式（７）を表し、Ｙ^６1は、エポキシ基、アミノ基、チオール基、水酸基、エポキシシクロヘキシル基を表す。）

(In the formula (6), R ^{61 to} R ⁶³ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, or an amino group. , An acetyl group, a phenyl group, and a halogen atom, X ⁶¹ represents the following formula (7), and Y ⁶¹ represents an epoxy group, an amino group, a thiol group, a hydroxyl group, and an epoxycyclohexyl group.

（式（７）中、ｐ、ｑ、ｒは、それぞれ１〜６の整数を表す。）

(In the formula (7), p, q and r each represent an integer of 1 to 6.)

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

(Other additives)
Further, the carbon nanotube-containing composition may include a plasticizer, a dispersant, a coating surface modifier, a fluidity modifier, an ultraviolet absorber, an antioxidant, a storage stabilizer, an adhesion aid, and a thickener as necessary. Various known substances such as these may be added. In addition, a conductive substance may be added to the carbon nanotube-containing composition in order to improve conductivity. Examples of the conductive material include carbon materials such as carbon fiber, conductive carbon black, and graphite; metal oxides such as tin oxide and zinc oxide; metals such as silver, nickel, and copper; phenylene vinylene, vinylene, thienylene, Π-conjugated polymers containing repeating units such as pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene, carbazolylene; symmetric or asymmetric indole derivative trimers and the like. Among these conductive substances, a π-conjugated polymer, an indole derivative trimer or a doped product thereof is more preferable, and a water-soluble π-conjugated polymer having a sulfonic acid group and / or a carboxylic acid group, Indole derivative trimers or their doped products are particularly preferred.

<Addition amount of constituent material in carbon nanotube-containing composition>
Next, the preferable addition amount of each constituent material to the carbon nanotube-containing composition will be described.
The amount of carbon nanotube (a) added is a constituent material other than carbon nanotube (a) in the carbon nanotube-containing composition (urethane compound (b) and granular substance (c), urethane compound (b) and granular substance (c). And polymerizable monomer (d-1), urethane compound (b), particulate material (c) and solvent (d-2), urethane compound (b), particulate material (c) and polymerizable monomer (d -1) and any combination of solvent (d-2).) The total amount of carbon nanotubes (a) is preferably 0.0001 to 40 parts by mass, more preferably 100 parts by mass. 0.001 to 20 parts by mass. When the carbon nanotube (a) is within the above range, the solubility or dispersibility in the carbon nanotube-containing composition is particularly good, and various properties such as conductivity of the resulting film are also good. In addition, even if content of a carbon nanotube (a) exceeds the said range, the effect acquired is not improved significantly. When content of a carbon nanotube (a) is less than the said range, it will become difficult to exhibit the various characteristics of a carbon nanotube (a).

  When the polymerizable monomer (d-1) and / or the solvent (d-2) are used in combination, the addition amount of the urethane compound (b) is the polymerizable monomer (d-1) and / or the solvent (d -2) It is preferable that a urethane compound (b) is 0.001-99.9 mass parts with respect to 100 mass parts, More preferably, it is 0.01-99.9 mass parts. If it is in the said range, the solubility or dispersibility of the carbon nanotube (a) in the carbon nanotube-containing composition is particularly good, and various properties such as conductivity of the resulting film are also good. In addition, even if content of a compound (b) exceeds the said range, the effect acquired is not improved significantly. When the content of the compound (b) is less than the above range, the solubility or dispersibility of the carbon nanotube (a) is deteriorated.

  The amount of the particulate material (c) added is a constituent material other than the particulate material (c) in the carbon nanotube-containing composition (carbon nanotube (a), urethane compound (b), particulate material (c), carbon nanotube (a). , Urethane compound (b), particulate material (c), polymerizable monomer (d-1), carbon nanotube (a), urethane compound (b), particulate material (c), solvent (d-2), carbon For a total of 100 parts by mass of the nanotube (a), the urethane compound (b), the particulate material (c), the polymerizable monomer (d-1), and the solvent (d-2). The granular material (c) is preferably 0.0001 to 50 parts by mass, and more preferably 0.001 to 20 parts by mass. When the particulate material (c) is less than 0.0001 parts by mass, it is difficult to form an efficient conduction path with the carbon nanotube (a). For this reason, conductivity, transparency, and mechanical strength are not lowered, but are not improved. On the other hand, when the content of the particulate material (c) exceeds 50 parts by mass, the solubility or dispersibility of the carbon nanotube (a) is lowered.

  When the polymerizable monomer (d-1) and the solvent (d-2) are used in combination, the polymerizable monomer (d-1) and the solvent (d-2) contained in the carbon nanotube-containing composition. ), The polymerizable monomer (d-1) / solvent (d-2) is 100/0 to 0/100, and can be mixed at an arbitrary ratio.

  The amount of the polymerization initiator (f) added is a constituent material other than the carbon nanotube (a) in the carbon nanotube-containing composition (urethane compound (b) and granular substance (c), urethane compound (b) and granular substance (c). ) And a polymerizable monomer (d-1), a urethane compound (b), a granular material (c) and a solvent (d-2), a urethane compound (b), a granular material (c) and a polymerizable monomer ( The combination of d-1) and solvent (d-2) is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass in total. When the polymerization initiator (f) is within the above range, the carbon nanotube-containing composition can be sufficiently cured, and a polymer excellent in transparency can be obtained without coloring the cured film.

  The amount of the polymer compound (g) added is a constituent material other than the carbon nanotube (a) in the carbon nanotube-containing composition (urethane compound (b) and granular substance (c), urethane compound (b) and granular substance (c). ) And a polymerizable monomer (d-1), a urethane compound (b), a granular material (c) and a solvent (d-2), a urethane compound (b), a granular material (c) and a polymerizable monomer ( It is preferable that the polymer compound (g) is 0.1 to 400 parts by mass with respect to 100 parts by mass in total of d-1) and any combination of the solvent (d-2). Preferably it is 0.5-300 mass parts. If the polymer compound (g) is within the above range, the urethane compound (b) and the carbon nanotube (a) in the carbon nanotube-containing composition are better dissolved, and a film using the carbon nanotube-containing composition is formed. The film formability and moldability at the time of formation are further improved, and the conductivity and mechanical strength of the resulting film can be maintained in a particularly good state.

  The amount of the surfactant (h) added is a constituent material other than the carbon nanotube (a) in the carbon nanotube-containing composition (urethane compound (b) and granular substance (c), urethane compound (b) and granular substance (c). ) And a polymerizable monomer (d-1), a urethane compound (b), a granular material (c) and a solvent (d-2), a urethane compound (b), a granular material (c) and a polymerizable monomer ( It is preferable that the surfactant (h) is 0.0001 to 10 parts by mass with respect to a total of 100 parts by mass of any combination of d-1) and the solvent (d-2). Preferably it is 0.01-5 mass parts. When the surfactant (h) is within the above range, the solubility or dispersibility of the carbon nanotube (a) in the carbon nanotube-containing composition and the long-term storage stability are particularly good. In addition, even if surfactant (h) exceeds the said range, the effect acquired is not improved significantly. When surfactant (h) is less than the said range, the effect of surfactant will become difficult to be exhibited.

  The amount of the silane coupling agent (i) added is a constituent material other than the carbon nanotube (a) in the carbon nanotube-containing composition (urethane compound (b) and granular substance (c), urethane compound (b) and granular substance ( c), polymerizable monomer (d-1), urethane compound (b), particulate material (c), solvent (d-2), urethane compound (b), particulate material (c), and polymerizable monomer. It is preferable that silane coupling agent (i) is 0.001-20 mass parts with respect to a total of 100 mass parts of (d-1) and solvent (d-2)), More preferably, 0.01- 15 parts by mass. When the silane coupling agent (i) is within the above range, the water resistance of the coating is particularly good. In addition, even if a silane coupling agent (i) exceeds the said range, the effect acquired is not improved significantly. When the silane coupling agent (i) is less than the above range, it is difficult to obtain the effect of the silane coupling agent (i).

<Method for preparing carbon nanotube-containing composition>
In order to mix the constituent materials of the carbon nanotube-containing composition, a stirring or kneading apparatus such as ultrasonic irradiation, a homogenizer, a spiral mixer, a planetary mixer, a disperser, or a hybrid mixer is used. Among these, ultrasonic irradiation is preferably used. Particularly preferably, a combination of ultrasonic irradiation and a homogenizer (ultrasonic homogenizer) is used.
In particular, carbon nanotube (a), urethane compound (b) and particulate material (c), or carbon nanotube (a), urethane compound (b), particulate material (c) polymerizable monomer (d-1) and In the case of mixing the solvent (d-2) and other materials, ultrasonic irradiation is preferably used, and ultrasonic irradiation and a homogenizer (ultrasonic homogenizer) are particularly preferably used in combination.
The treatment intensity and treatment time of ultrasonic irradiation are not particularly limited as long as the ultrasonic wave intensity and treatment time are sufficient to uniformly disperse or dissolve the carbon nanotube (a) in the carbon nanotube-containing composition. . For example, the rated output of the ultrasonic oscillator is preferably 0.1 to 2.0 watt / cm ² per unit bottom area of the ultrasonic oscillator, and more preferably 0.3 to 1.5 watt / cm ² . . As for the oscillation frequency of the ultrasonic wave by an ultrasonic oscillator, 10-200 kHz is preferable, More preferably, it is the range of 20-100 kHz. The time of ultrasonic irradiation is preferably 1 minute to 48 hours, more preferably 5 minutes to 48 hours. After ultrasonic irradiation, dispersion or dissolution may be thoroughly performed using a ball-type kneader such as a ball mill, a vibration mill, a sand mill, or a roll mill.

When mixing predetermined constituent materials, all the materials may be added at once, or various constituent materials may be mixed in a desired order. For example, a small amount of the polymerizable monomer (d-1) and / or solvent (d-2) to be used is weighed and the carbon nanotube (a) and the urethane compound (b) are dissolved therein. After preparing a thick carbon nanotube-containing composition, the remaining polymerizable monomer (d-1) and / or solvent (d-2) may be mixed to obtain a predetermined concentration.
In the case of using a mixture of two or more kinds of the polymerizable monomer (d-1) or the solvent (d-2), for example, the polymerizable monomer (d-1) or the solvent (d-2) The carbon nanotube (a) and the urethane compound (b) are dissolved in one or more materials among them to prepare a dense carbon nanotube-containing composition, and then the remaining carbon nanotube-containing composition The polymerizable monomer (d-1) or the solvent (d-2) may be mixed to obtain a predetermined concentration.
The temperature of the carbon nanotube-containing composition when performing ultrasonic irradiation is preferably 60 ° C. or lower, more preferably 40 ° C. or lower, from the viewpoint of improving dispersibility. In particular, when the urethane compound (b) is a polymerizable monomer and / or when preparing a carbon nanotube-containing composition using the polymerizable monomer (d-1), also from the viewpoint of polymerization prevention. 40 degrees C or less is more preferable.

<Method of coating carbon nanotube-containing composition on substrate>
As a method for coating the carbon nanotube-containing composition on the surface of the substrate, methods used for general coating such as coating, spraying and dipping can be used. Specifically, gravure coaters, roll coaters, curtain flow coaters, spin coaters, bar coaters, reverse coaters, kiss coaters, fan ten coaters, rod coaters, air doctor coaters, knife coaters, blade coaters, cast coaters, screen coaters, etc. The coating method used, spraying methods such as spray coating such as air spray and airless spray, and dipping methods such as dip can be used.

  When the carbon nanotube-containing composition prepared using the solvent (d-2) is applied to the surface of the substrate, it may be cured at room temperature, but heat treatment is preferred. By heat-treating the coating film, the residual amount of the remaining solvent (d-2) can be further reduced, and the conductivity can be further improved. In addition, although the heat processing temperature of a coating film is influenced by the material etc. of the base material to be used, 20-250 degreeC is preferable in general, and 40 degreeC-200 degreeC is especially preferable. When the above range is exceeded, the urethane compound (b) itself may be decomposed, and the transparency and appearance may be deteriorated. When the heat treatment temperature is below the above range, the volatilization of the solvent (d-2) may be insufficient.

As a method for coating the carbon nanotube-containing composition prepared using the polymerizable monomer (d-1), the following three types can be mainly mentioned.
(I) A method in which a carbon nanotube-containing composition is applied to a substrate and cured.
(II) After coating a carbon nanotube-containing composition on the inner surface of a mold having a predetermined shape and curing it to form a cured film, a polymerizable monomer for forming a substrate in the mold ( Hereinafter, it is abbreviated as a polymerizable raw material.) Or a molten resin is poured and cured to form a base material, and the cured film is peeled off from the mold together with the base material.
(III) A carbon nanotube-containing composition is poured between a mold having a predetermined shape and a substrate disposed in the mold and cured to form a cured film, and then the cured film is removed from the mold together with the substrate. How to peel.

In the case of obtaining a film by using the photopolymerization initiator (f) as the polymerization initiator (f) for curing the urethane compound (b) or the polymerizable monomer (d-1) by the method (I), ultraviolet rays, etc. A film can be formed by irradiating the active energy ray.
Moreover, when obtaining a cured film using the thermal polymerization initiator which is a polymerization initiator (f) for hardening of a urethane compound (b) and a polymerizable monomer (d-1), a film is formed by heat treatment. Can be formed.
As a method of coating the surface of the substrate, a method of coating the carbon nanotube-containing composition prepared using the solvent (d-2) described above on the substrate surface can be used.

  Among the methods (I) to (III), the method (II) is preferably used because a coating film having a good surface state can be obtained without deteriorating the appearance due to the influence of dust or the like. Examples of the mold used in the method (II) include casting polymerization molds and molding molds. For example, when the mold is composed of two plate-like products having a smooth surface, a carbon nanotube-containing structure in the form of a plate-like laminate having a smooth surface can be obtained. In this case, a cured film made of the carbon nanotube-containing composition may be formed on one mold or both molds.

  The forming method (II) is a so-called cast polymerization method. Specifically, the cast polymerization method is performed as follows. First, insert a gasket made of soft polyvinyl chloride, ethylene-vinyl acetate copolymer, polyethylene, ethylene-methyl methacrylate copolymer, etc. between two glass plates, and fix them with clamps, etc. Assemble the glass mold for mold polymerization. Next, a carbon nanotube-containing composition prepared using a polymerizable monomer (d-1) and a polymerization initiator (f) is applied to the inner surface of the glass mold and photocured. A carbon nanotube-containing structure can be obtained by removing a glass mold after pouring a polymerizable raw material into the polymer.

Moreover, in the manufacturing method of the carbon nanotube containing structure of this invention, you may use the continuous cast polymerization method which can perform cast polymerization method continuously. Examples of the continuous cast polymerization method include a method using a polymerization apparatus capable of continuously producing a plate-like polymer described in JP-B-46-41602. When using this continuous cast polymerization method, first, a carbon nanotube-containing composition prepared using a polymerizable monomer (d-1) and a polymerization initiator (f) is applied to the steel belt surface of the polymerization apparatus. Then, a cured film is formed by curing, and then a polymerizable raw material serving as a base material is introduced and polymerized on the cured film, thereby forming a plate-like carbon nanotube-containing structure in which a film is formed on the base material You can get a body.
In addition to this, for example, a film that does not dissolve or swell in the carbon nanotube-containing composition is attached to the steel belt of the polymerization apparatus, and then prepared by the polymerizable monomer (d-1) and the polymerization initiator (f). The carbon nanotube-containing composition thus prepared may be applied on a film and cured. In addition, if the design of unevenness etc. is previously given to the steel belt surface of this superposition | polymerization apparatus, the carbon nanotube containing structure which has the designability on the surface can also be manufactured.

In the carbon nanotube-containing composition used for producing the carbon nanotube-containing structure of the present invention, the carbon nanotube (a) is uniformly dispersed or dissolved without impairing various properties. Moreover, the carbon nanotube (a) does not separate and aggregate over a long period in the carbon nanotube-containing composition, and is excellent in long-term storage stability.
The reason why the carbon nanotube (a) can be uniformly dispersed or dissolved in the carbon nanotube-containing composition has not been clearly clarified, but the urethane compound (b) adsorbs or wraps the carbon nanotube (a) in a spiral shape. By doing so, it is presumed that the carbon nanotubes (a) are easily dispersed or dissolved easily in the carbon nanotube-containing composition.
In the method for producing a carbon nanotube-containing structure of the present invention, the carbon nanotube (a) is uniformly dispersed or dissolved in the carbon nanotube-containing composition as described above. In addition, the carbon nanotubes can be coated on the substrate by a simple method without impairing the properties of the carbon nanotubes. Moreover, since the carbon nanotubes (a) are uniformly dispersed in the obtained coating film, excellent electrical conductivity, transparency, water resistance, mechanical strength, thermal conductivity, and scratch resistance can be maintained over the long term.

The carbon nanotube-containing structure of the present invention thus produced includes industrial packaging materials such as semiconductors and electrical and electronic parts, transparent conductive resin plates used in clean rooms for semiconductor production, overhead projector films, and slide films. It is widely used as an antistatic film such as an electrophotographic recording material such as an electrophotographic recording material, a transparent conductive film, a magnetic recording tape such as an audio tape, a video tape, and a computer tape, a magnetic disk, and an optical disk. Furthermore, LSI wiring of electronic devices, electron guns (sources) of field emission displays (FEDs) and their electrodes, hydrogen storage agents, transparent touch panels, electroluminescent displays, liquid crystal displays and other flat panel display inputs and display device surfaces Display protective plate, front plate, transparent electrode, transparent electrode film, light emitting material forming organic electroluminescence element, buffer material, electron transport material, hole transport material, fluorescent material, thermal transfer sheet, transfer sheet, thermal transfer image receiving sheet, Widely used as an image receiving sheet.
Furthermore, since the carbon nanotube-containing composition is excellent in moldability and film formability, it can be applied to various substrates using a simple coating method such as coating, spraying, casting, and dipping. It is. Examples of the carbon nanotube-containing structure of the present invention obtained by these methods include various antistatic agents, capacitors, electric double layer capacitors, batteries, fuel cells and their polymer electrolyte membranes, electrode layers, catalyst layers, gas diffusions. Layer, gas diffusion electrode layer, separator, etc., EMI shield, chemical sensor, display element, nonlinear material, anticorrosive, adhesive, fiber, spinning material, antistatic paint, anticorrosion paint, electrodeposition paint, plating primer, Examples thereof include a conductive primer for electrostatic coating, an anticorrosive material, and a battery.

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.
<Material of carbon nanotube-containing composition>
In order to prepare a carbon nanotube-containing composition, the following carbon nanotube (a), urethane compound (b), granular material (c), polymerizable monomer (d-1), and photopolymerization initiator (f) It was used.
(Carbon nanotube (a))
A multi-walled carbon nanotube (manufactured by ILJIN) manufactured by the CVD-1 method was used.
(Urethane compound (b))
A urethane compound was obtained by reacting 3 mol of 2-hydroxytrimethylene dimethacrylate with 1 mol of triisocyanate composed of a trimer of hexamethylene diisocyanate, and this was used as urethane compound 1.
(Particulate matter (c))
Acrylic resin particle “Finesphere E-MG-151” (manufactured by Nippon Paint Co., Ltd., particle size 100 nm) or colloid liquid “cellnax CX-Z610M-F2” (manufactured by Nissan Chemical Co., Ltd.) in which antimony double oxide is dispersed in methanol Solid content 60% by weight, particle size 15 nm) was used.
(Polymerizable monomer (d-1))
58 parts by mass of 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 4 parts by mass of pentaerythritol tetraacrylate, and 6 parts by mass of pentaerythritol triacrylate were used.
(Photopolymerization initiator (f))
Benzoin ethyl ether was used.

<Preparation of carbon nanotube-containing composition>
(Preparation Example 1)
Carbon nanotube-containing composition 1:
A polymerizable monomer obtained by mixing 32 parts by mass of urethane compound 1, 58 parts by mass of 1,6-hexanediol diacrylate, 4 parts by mass of pentaerythritol tetraacrylate, and 6 parts by mass of pentaerythritol triacrylate was added to a multi-walled carbon nanotube 0. 1 part by mass and 0.1 part by mass of acrylic resin particles were mixed at room temperature, and subjected to ultrasonic homogenizer treatment (Vibra cell 20 kHz, manufactured by SONIC) for 1 hour under ice cooling, followed by 1.5 mass of benzoin ethyl ether. Carbon nanotube-containing composition 1 was prepared by adding parts.

(Preparation Example 2)
Carbon nanotube-containing composition 2:
A carbon nanotube-containing composition 2 was prepared in the same manner as in Preparation Example 1, except that the acrylic resin particles were changed to 0.5 part by mass.

(Preparation Example 3)
Carbon nanotube-containing composition 3:
A carbon nanotube-containing composition 3 was prepared in the same manner as Preparation Example 1 except that the acrylic resin particles were changed to 2 parts by mass.

(Preparation Example 4)
Carbon nanotube-containing composition 4:
A carbon nanotube-containing composition 4 was prepared in the same manner as in Preparation Example 1, except that 1 part by mass of a colloidal solution in which antimony double oxide was dispersed in methanol was used instead of the acrylic resin particles.

(Preparation Example 5)
Carbon nanotube-containing composition 5:
A carbon nanotube-containing composition 5 was prepared in the same manner as in Preparation Example 1 except that the acrylic resin particles were not added.

<Production of carbon nanotube-containing structure>
(Examples 1-4)
Each of the carbon nanotube-containing compositions 1 to 4 is dropped on an acrylic resin plate (thickness 3 mm), a 50 μm-thick PET film (manufactured by Teijin Ltd.) is placed thereon, and has a JIS hardness of 30 °. Ironing with a rubber loom, the thickness of the carbon nanotube-containing composition was set to 15 μm. After that, 10 cm below the 40 W fluorescent ultraviolet lamp (Toshiba Corp., FL40BL) was passed at a speed of 0.8 m / min with the PET film surface facing up, and the carbon nanotube-containing composition was After curing, the PET film was peeled off. Next, the surface of the acrylic resin plate is passed by passing a position 20 cm away from the high-pressure mercury lamp with an output of 30 W / h at a speed of 0.8 m / cm with the coating film facing upward to cure the carbon nanotube-containing composition. The carbon nanotube-containing structures of Examples 1 to 4 having a cured film were prepared.

(Comparative Example 1)
The carbon nanotube-containing composition 5 of Comparative Example 1 having a cured film on the surface of the acrylic resin plate was produced by curing the carbon nanotube-containing composition 5 by the same method as in Examples 1 to 4.

<Method for evaluating carbon nanotube-containing structure>
The dispersion state of the carbon nanotube (a) in the cured film of each produced carbon nanotube-containing structure was evaluated by performing the following observations and calculations.
(Observation of carbon nanotube-containing structures)
The observation of the cured film in the carbon nanotube-containing structure was performed using a confocal laser microscope (LSM5 PASCAL Axioplan2 imaging: manufactured by Carl Zeiss) using a 100-times oil immersion lens (numerical aperture 1.4, Plan-APOCHROMAT). A 1000 × image was acquired. Note that an adjustment liquid having a refractive index of 1.518 (Immersol 518F: manufactured by Carl Zeiss) was used for observation, and an argon laser having a wavelength of 458 nm was used as a laser for image acquisition.
In the vertical scanning, 100 μm square images were taken at a pitch of 0.1 μm for a thickness of about 11 μm from the surface of the cured film to the interface with the substrate. Note that the optical thickness per image under these conditions was about 300 nm.
(Calculation of the area ratio of aggregates with a pixel area of 1000 or more in the cured film)
An extended focus image is created from the image photographed by the above method, and carbon nanotubes in the image are extracted by binarization processing using image processing software (Image-Pro PLUS ver 4.5.0: manufactured by Media Cybernetics). Then, the area ratio of aggregates having a pixel area of 1000 or more formed by carbon nanotubes in the image was measured, and the smaller the aggregate area ratio value, the higher the dispersibility of the carbon nanotubes in the cured film. The results are shown in Table 1.

<Evaluation>
As shown in Table 1, it was confirmed that each example was superior in dispersibility of carbon nanotubes in the cured film as compared with Comparative Example 1. Based on these evaluations, the carbon nanotube-containing structure used in each example has a cured film capable of maintaining excellent conductivity, transparency, water resistance, mechanical strength, thermal conductivity, and scratch resistance in the long term. Can do.

Claims (3)

  A carbon nanotube-containing structure in which a coating containing a carbon nanotube (a), a urethane compound (b), and a particulate material (c) is formed on at least one surface of a substrate.   The carbon nanotube containing composition containing a carbon nanotube (a), a urethane compound (b), and a granular material (c).   A carbon nanotube-containing composition containing the carbon nanotube (a), the urethane compound (b), and the particulate material (c) is applied onto at least one surface of the substrate, and irradiated with active energy rays and / or Alternatively, a method for producing a carbon nanotube-containing structure that is left at room temperature or heat-treated.