WO2011004864A1 - Carbon nanotube dispersant - Google Patents

Abstract

Provided is a carbon nanotube (CNT) dispersant capable of dispersing CNTs to the size of individual CNTs in a medium such as an organic solvent. The carbon nanotube dispersant is characterized by comprising a highly branched polymer which has a weight average molecular weight of 1,000 to 2,000,000 when measured in terms of polystyrene obtained by means of gel permeation chromatography, and has an amino functional group or an imino functional group in the terminals thereof.

Description

Carbon nanotube dispersant

The present invention relates to a carbon nanotube dispersant. More specifically, the present invention relates to a carbon nanotube dispersant composed of a highly branched polymer containing an amino functional group or an imino functional group at the terminal, and a composition containing the dispersant and the carbon nanotube.

Carbon nanotubes (hereinafter also abbreviated as CNT) are considered as potential materials for nanotechnology, and their applicability in a wide range of fields has been studied. The applications include the use of a single CNT itself, such as a transistor or a probe for a microscope, and a large number of CNTs, such as an electron emission electrode, a fuel cell electrode, or a conductive composite in which CNTs are dispersed. It is roughly divided into the method of using as a bulk.
When using single CNT, after adding CNT in a solvent and irradiating this with an ultrasonic wave, the method of taking out only the CNT which is disperse | distributing single by electrophoresis etc. is used.
On the other hand, in a conductive composite used in bulk, it is necessary to disperse CNTs well in a polymer serving as a matrix material. However, in general, there is a problem that CNTs are difficult to disperse, and normal composites are used with incomplete CNT dispersion. For this reason, it is difficult to say that carbon nanotubes are used with sufficient performance, and this problem also makes it difficult to apply carbon nanotubes to various applications. For this reason, various methods for improving dispersibility by modifying the CNT surface, chemical modification, and the like have been studied.

As a method of dispersing such CNTs, for example, a method of adding CNTs to an aqueous solution containing a low molecular surfactant such as sodium dodecyl sulfate (see Patent Document 1) has been proposed. However, when these low molecular surfactants are used, the ability to form a thin film in a solution in which CNTs are dispersed is low, and it is necessary to further add a polymerizable monomer or polymer in order to facilitate thinning. For this reason, there exists a problem that these nonelectroconductive organic substances exist in a thin film and electroconductivity is impaired. In this method, the mass of CNTs on the order of several millimeters is reduced to a size of several μm, and dispersion to the size of CNTs alone (diameter 0.8 to 100 nm) has not been achieved. Met.

On the other hand, as a method of dispersing CNTs using a polymer, a method of attaching poly (m-phenylene vinylene-co-dioctoxy-p-phenylene vinylene) having a coiled structure to the CNT surface is also proposed (see, for example, Patent Document 2). Has been. Here, a TEM image in which CNTs can be dispersed in an organic solvent and a polymer is attached to one CNT is also shown (see FIGS. 1 to 4). However, an object of the present invention is to disperse CNTs to a certain extent and then precipitate them, and to purify and collect them without damaging the CNT structure. However, since this method is not intended to keep the CNT dispersed in the long term, the CNT could not be stored in the dispersed state for a long time.

Furthermore, a material that has been subjected to chemical modification by adding a functional group to CNTs to impart dispersibility (for example, see Non-Patent Document 1) has been reported. However, when the CNTs are chemically modified, the π-conjugated system constituting the CNTs is easily broken, and there is a problem that the original characteristics of the CNTs such as high conductivity are impaired.

As a method for solving the above problems, a method of dispersing CNTs with a polymer such as polyvinyl pyrrolidone which is a water-soluble polymer (for example, see Non-Patent Document 2) is also known. However, since the polymer is a water-soluble polymer, its application range is limited.

On the other hand, as a method using an organic solvent, a method of using a compound having a basic functional group and dispersing it in a ketone-based organic solvent has been proposed (for example, see Patent Document 3). However, this method has no detailed provisions regarding basic functional groups, and the diameter of CNTs that can be stably dispersed is limited.
Further, a polyoxyethylene compound that is a nonionic surfactant is used and dispersed in an amide polar organic solvent (see, for example, Patent Document 4) or dispersed in an amide polar organic solvent using the polyvinylpyrrolidone. And a method of dispersing in an alcoholic organic solvent (see, for example, Patent Document 6) have also been proposed. However, the polymer used as the dispersant is characterized by being a linear polymer, and no knowledge about the hyperbranched polymer has been clarified.

A method focusing on a highly branched polymer as a dispersant for CNT (see, for example, Non-Patent Document 3) has also been proposed. The hyperbranched polymer is a polymer having a branch in the skeleton, such as a star polymer, a dendrimer classified as a dendritic (dendritic) polymer, or a hyperbranched polymer. These hyperbranched polymers are unique in that they have a relatively sparse internal space and particle characteristics in that the conventional polymers generally have a string-like shape but actively introduce branches. It has a large number of ends that can be modified by introducing various functional groups, and has the possibility of highly dispersing CNTs compared to linear polymers by utilizing these characteristics. .
However, in the example of non-patent literature using the above-mentioned hyperbranched polymer as a dispersant, heat treatment is required in addition to mechanical treatment in order to maintain the isolated dispersion state of CNT in the long term. Noh was not so high.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a CNT dispersant capable of dispersing CNTs to their single size in a medium such as an organic solvent.

As a result of intensive studies to achieve the above object, the present inventors have found that a highly branched polymer having an amino functional group or an imino functional group introduced at its terminal has excellent CNT dispersibility, and this highly branched polymer. The present inventors have found that CNT (at least a part thereof) can be isolated and dispersed up to its single size when used as a CNT dispersant.

That is, the present invention provides, as a first aspect, a high molecular weight having an amino functional group or an imino functional group at the end and having a weight average molecular weight of 1,000 to 2,000,000 as measured by gel permeation chromatography in terms of polystyrene. The present invention relates to a carbon nanotube dispersant characterized by comprising a branched polymer.
As a second aspect, the hyperbranched polymer has a monomer A having two or more radical polymerizable double bonds in the molecule, and 5 to 200 mol% of amino functional group or imino functional group with respect to the monomer A. The present invention relates to the carbon nanotube dispersant according to the first aspect, which is a hyperbranched polymer obtained by polymerization in the presence of the polymerization initiator B it has.
As a third aspect, the present invention relates to the carbon nanotube dispersant according to the first aspect or the second aspect, wherein the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator having a heterocyclic amine structure.
As a fourth aspect, the carbon according to the first aspect or the second aspect, wherein the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator having a functional group represented by the formula [1]. The present invention relates to a nanotube dispersant.

(In the formula [1], R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, or R ^1. , R ² and R ³ may be combined with the nitrogen atom to which they are bonded to form a ring.)
As a fifth aspect, the present invention relates to the carbon nanotube dispersant according to the second aspect, wherein the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator represented by the formula [2].

(In the formula [2], R ¹ , R ² and R ³ represent those defined in the formula [1], and R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 6 carbon atoms. To express.)
As a sixth aspect, the hyperbranched polymer includes a monomer A having two or more radical polymerizable double bonds in the molecule and a monomer C having at least one radical polymerizable double bond in the molecule. Hyperbranching obtained by polymerizing in the presence of a polymerization initiator B having an amino functional group or imino functional group in an amount of 5 mol% or more and 200 mol% or less with respect to the total mol of the monomer A and the monomer C The carbon nanotube dispersant according to the first aspect, which is a polymer.
As a seventh aspect, the present invention relates to the carbon nanotube dispersant according to the sixth aspect, wherein the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator having a heterocyclic amine structure.
As an eighth aspect, the carbon nanotube dispersant according to the sixth aspect, wherein the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator having a functional group represented by the formula [1]. .

(In the formula [1], R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, or R ^1. , R ² and R ³ may be combined with the nitrogen atom to which they are bonded to form a ring.)
As a ninth aspect, the present invention relates to the carbon nanotube dispersant according to the eighth aspect, wherein the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator represented by the formula [2].

(In the formula [2], R ¹ , R ² and R ³ represent those defined in the formula [1], and R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 6 carbon atoms. To express.)
As a tenth aspect, the present invention relates to the carbon nanotube dispersant according to any one of the first aspect to the ninth aspect, and a composition containing carbon nanotubes.
An eleventh aspect relates to the composition according to the tenth aspect, wherein the carbon nanotube is at least one selected from single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
As a twelfth aspect, the present invention relates to the composition according to the tenth aspect or the eleventh aspect, wherein the carbon nanotube dispersant adheres to or coordinates with the surface of the carbon nanotube to form a composite.
As a thirteenth aspect, the present invention relates to the composition according to any one of the tenth aspect to the twelfth aspect, further including an organic solvent.
As a fourteenth aspect, the present invention relates to the composition according to the thirteenth aspect, in which the carbon nanotube is dispersed in the organic solvent.
As a fifteenth aspect, the present invention relates to the composition according to the thirteenth aspect, in which the complex is dispersed in the organic solvent.
As a sixteenth aspect, the present invention relates to the composition according to any one of the tenth aspect to the fifteenth aspect, further including a thermosetting compound soluble in an organic solvent.
As a seventeenth aspect, the present invention relates to the composition according to the sixteenth aspect, in which the thermosetting compound is a polyfunctional epoxy compound.
As an eighteenth aspect, the present invention relates to a thin film obtained from the composition according to any one of the tenth aspect to the seventeenth aspect.
As a 19th viewpoint, it is related with the cured film obtained by heat-processing to the thin film obtained from the composition as described in a 16th viewpoint or a 17th viewpoint.
As a twentieth aspect, a step of preparing a mixture by mixing the carbon nanotube dispersant according to any one of the first aspect to the ninth aspect, a carbon nanotube, and an organic solvent, and mechanically treating the mixture And a process for producing the composition.
As a twenty-first aspect, the present invention relates to the manufacturing method according to the twentieth aspect, wherein the mechanical treatment is ultrasonic treatment.
A twenty-second aspect includes a step of preparing the mixture by adding the carbon nanotubes to a solution obtained by dissolving the carbon nanotube dispersant in the organic solvent, and a step of ultrasonicating the mixture. And the manufacturing method according to the twenty-first aspect.

The dispersant of the present invention is composed of a highly branched polymer having an amino functional group or an imino functional group introduced at its terminal, has excellent dispersibility of carbon nanotubes, and at least a part of the carbon nanotubes has a single size (diameter 0.8 to 0.8). 100 nm) and can be stably dispersed (without aggregation) in an organic solvent in a so-called “isolated dissolution” state. In the present invention, “isolated dissolution” means that the carbon nanotubes are dispersed into the medium in such a way that the carbon nanotubes are not separated into a lump, bundle, or rope due to mutual cohesive force. Refers to the state.
Moreover, carbon nanotubes can be dispersed by a mechanical treatment such as ultrasonic treatment of a solution containing a dispersant, carbon nanotubes, and an organic solvent, eliminating the need for further heating and other processing steps and shortening the treatment time. can do.
Therefore, by using the carbon nanotube dispersant of the present invention, it is possible to easily obtain a carbon nanotube-containing composition in which carbon nanotubes (at least a part thereof) are dispersed in an isolated dissolved state.

The carbon nanotube-containing composition obtained by the present invention can be easily formed into a thin film by simply applying it to a substrate, and a highly conductive thin film can be obtained.
And in the said composition, since it is easy to adjust the quantity of a carbon nanotube according to the use, it can use suitably for a wide use as various semiconductor materials, conductor materials, etc.

1 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 1 synthesized in Example 1. FIG. 2 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 1 synthesized in Example 1. FIG. 3 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 2 synthesized in Example 2. FIG. 4 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 2 synthesized in Example 2. FIG. FIG. 5 is a diagram showing the ¹ H NMR spectrum of the hyperbranched polymer 3 synthesized in Example 3. 6 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 3 synthesized in Example 3. FIG. FIG. 7 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 4 synthesized in Example 4. FIG. 8 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 4 synthesized in Example 4. FIG. 9 is a diagram showing a ¹ H NMR spectrum of hyperbranched polymer 5 synthesized in Reference Production Example 1. FIG. 10 is a diagram showing a ¹³ C NMR spectrum of hyperbranched polymer 5 synthesized in Reference Production Example 1. FIG. 11 is a diagram showing a chiral vector of a carbon nanotube. FIG. 12 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 6 synthesized in Example 15. 13 is a diagram showing a ¹³ C NMR spectrum of hyperbranched polymer 6 synthesized in Example 15. FIG. 14 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer 7 synthesized in Example 16. FIG. FIG. 15 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 7 synthesized in Example 16.

<Carbon nanotube (CNT) dispersant>
The CNT dispersant according to the present invention comprises a highly branched polymer having an amino functional group or an imino functional group at its end, more specifically, a monomer A having two or more radical polymerizable double bonds in the molecule. It is obtained by polymerizing in the presence of a polymerization initiator B having an amino functional group or imino functional group in an amount of 5 mol% to 200 mol% with respect to A, and has a weight average molecular weight of 1,000 to 2, It consists of a hyperbranched polymer that is 1,000,000.
This hyperbranched polymer has many basic functional groups (amino functional groups or imino functional groups) that are considered to have high affinity for CNTs and carboxyl groups present at CNT defects. Therefore, high dispersibility of CNT can be expected. Moreover, this hyperbranched polymer can perform various skeleton designs, introduction of functional groups, control of molecular weight and distribution, and further functionalization depending on the combination and conditions of the monomer A and the initiator B. Has characteristics. Moreover, by having a branched structure, it also has a high solubility that cannot be seen in a straight chain.

In the present invention, if the weight average molecular weight of the polymer is less than 1,000, the dispersibility of CNTs may be remarkably lowered or the dispersibility may not be exhibited. If it exceeds 2,000,000, a dispersion treatment is performed. There is a possibility that the handling in the case becomes extremely difficult. A highly branched polymer having a weight average molecular weight of 2,000 to 1,000,000 is more preferred.
In addition, the weight average molecular weight in this invention is a measured value (polystyrene conversion) by gel permeation chromatography.

In the present invention, the monomer A having two or more radically polymerizable double bonds in the molecule preferably has one or both of a vinyl group and a (meth) acryl group, and particularly a divinyl compound or di ( A meth) acrylate compound is preferred. In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

Examples of such a monomer A include organic compounds shown in the following (A1) to (A7).
(A1) Vinyl hydrocarbon:
(A1-1) Aliphatic vinyl hydrocarbons; isoprene, butadiene, 3-methyl-1,2-butadiene, 2,3-dimethyl-1,3-butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octadiene etc.
(A1-2) Alicyclic vinyl hydrocarbon; cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, etc.
(A1-3) Aromatic vinyl hydrocarbons: divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine and the like.
(A2) Vinyl ester, allyl ester, vinyl ether, allyl ether, vinyl ketone:
(A2-1) Vinyl ester; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itaconate, vinyl (meth) acrylate and the like.
(A2-2) Allyl ester: diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl adipate, allyl (meth) acrylate, etc.
(A2-3) Vinyl ether; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether and the like.
(A2-4) Allyl ether; diallyl ether, diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane and the like.
(A2-5) Vinyl ketone; divinyl ketone, diallyl ketone and the like.
(A3) (Meth) acrylic acid ester:
Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, alkoxy titanium tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy 1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, un Decylenoxyethylene glycol di (meth) acrylate, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantanediol di (meth) acrylate, 1 , 3-adamantane dimethanol di (meth) acrylate, bisphenol A diethoxydi (meth) acrylate, etc.
(A4) Vinyl compound having a polyalkylene glycol chain:
Polyethylene glycol (molecular weight 300) di (meth) acrylate, polypropylene glycol (molecular weight 500) di (meth) acrylate, and the like.
(A5) Nitrogen-containing vinyl compound:
Diallylamine, diallyl isocyanurate, diallyl cyanurate, methylenebis (meth) acrylamide, bismaleimide and the like.
(A6) Silicon-containing vinyl compound:
Dimethyldivinylsilane, divinylmethylphenylsilane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetraphenyldisilazane , Dietodivinylsilane and the like.
(A7) Fluorine-containing vinyl compound:
1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, 1,8-divinylperfluorooctane and the like.

Of these, preferred are the aromatic vinyl hydrocarbon compounds of group (A1-3), vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones of group (A2), and (meth) acrylic of group (A3). An acid ester, a vinyl compound having a polyalkylene glycol chain of (A4) group, and a nitrogen-containing vinyl compound of (A5) group. Particularly preferred are divinylbenzene belonging to group (A1-3), diallyl phthalate belonging to group (A2), ethylene glycol di (meth) acrylate belonging to group (A3), 1,3-adamantane dimethanol di (meta). ) Acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A diethoxydi (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene and (A5) group Methylenebis (meth) acrylamide. Among these, divinylbenzene, ethylene glycol di (meth) acrylate and bisphenol A diethoxydi (meth) acrylate are preferable, and divinylbenzene is more preferable.

In the present invention, the polymerization initiator B having an amino functional group or an imino functional group includes an amino group and an amine or imine compound in which a hydrogen atom of ammonia is substituted with a monovalent or divalent hydrocarbon residue, as well as a heterocyclic ring. A polymerization initiator containing an amine.
Examples thereof include primary to tertiary aliphatic amines such as cyclohexylamine, dimethylamine, triethylamine, phenethylamine, and dibenzylamine; primary to tertiary amines such as aniline, dimethylaminopyridine, diphenylamine, and triphenylamine. Tertiary aromatic amines; imines such as methanimine, propane-2-imine, N-methylethanimine; pyrroline, pyrrolidine, pyrazoline, pyrazolidine, imidazoline, imidazolidine, dihydropyridine, tetrahydropyridine, piperidine, dihydropyrimidine, tetrahydropyrimidine, hexa Such as hydropyrimidine, dihydropyrazine, tetrahydropyrazine, piperazine, morpholine, thiomorpholine, quinuclidine, 1,4-diazabicyclo [2.2.2] octane Cyclic heterocyclic amines; polymerization initiators containing structures such as aromatic heterocyclic amines such as pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, carbazole Is mentioned.

Therefore, the polymerization initiator B having an amino functional group or imino functional group is preferably a polymerization initiator having a heterocyclic amine structure, or a polymerization initiator having a functional group represented by the following formula [1], particularly An azo polymerization initiator can be mentioned.

In the formula [1], R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, or R ¹ , Any two or more of R ² and R ³ may be combined with the nitrogen atom to which they are bonded to form a ring.

Examples of the functional group represented by the above formula [1] include groups represented by the following formulas [A] to [M], but are not limited thereto.

Examples of the azo polymerization initiator composed of a compound having a functional group represented by the above formulas [A] to [M] include a polymerization initiator represented by the following formula [2].

In the formula [2], R ¹ , R ² and R ³ represent those defined in the formula [1], and R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 6 carbon atoms. .

Examples of the azo polymerization initiator represented by the above formula [2] include compounds shown in the following (1) to (2);
(1) Cyclic azoamidine compound:
2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] -propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) Propane], 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride and the like.
(2) Azoamidine compound:
2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, and the like.

Among the above azo polymerization initiators, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] or 2,2′-azobis (1-imino-1-containing a heterocyclic amine structure is included. Pyrrolidino-2-methylpropane) dihydrochloride is particularly preferred.

The polymerization initiator B is used in an amount of 5 mol% to 200 mol%, preferably 15 mol% to 200 mol%, more preferably 15 mol% to 170 mol%, more preferably, relative to the monomer A. Used in an amount of 50 mol% to 100 mol%.

The dispersant in the present invention uses a monomer C having at least one radical polymerizable double bond in the molecule in addition to the monomer A having two or more radical polymerizable double bonds in the molecule, It is obtained by polymerizing in the presence of the polymerization initiator B having the above-mentioned amino functional group or imino functional group in an amount of 5 mol% or more and 200 mol% or less with respect to the total mol of the monomer A and the monomer C. Dispersants composed of highly branched polymers are also targeted.

In the present invention, the monomer C having at least one radical polymerizable double bond in the molecule preferably has at least one of either a vinyl group or a (meth) acryl group.
As such a monomer C, the organic compound shown to the following (C1) thru | or (C3) is illustrated, for example.
(C1) (Meth) acrylic compound:
(C1-1) (meth) acrylic acids; (meth) acrylic acid, itaconic acid, 2-trifluoromethyl acrylic acid, 2-ethyl acrylic acid, 2-propyl acrylic acid, 2-bromomethyl acrylic acid, 2-acetamide Acrylic acid, 2-ethylacryloyl chloride, 3,3-dimethyl (meth) acryloyl chloride.
(C1-2) (meth) acrylic acid esters; methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-carboxyethyl (meth) Acrylate, mono-2- (meth) acryloyloxyethyl succinate, bis [2- (meth) acryloyloxyethyl] phosphate, 2- (meth) acryloyloxyethyl acetoacetate, 2-dimethylaminoethyl (meth) acrylate, 2 -Diethylaminoethyl (meth) acrylate, [2- (meth) acryloyloxyethyl] trimethylammonium chloride, 2-isocyanatoethyl (meth) acrylate, 2- [9H-carbazol-9-yl] ethyl (meth) acrylate, vinyl ( (Meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, (R) -α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone, 2-naphthyl (meth) acrylate, ethylene glycol methyl ether (Meth) acrylate, ethylene glycol cyclopentenyl ether (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, ethylene glycol (meth) acrylate phosphate, diethylene glycol ethyl ether (meth) acrylate, diethylene glycol 2-ethylhexyl ether (meth) acrylate , Dipropylene glycol allyl ether (meth) acrylate, neopentyl glycol methyl ether propoxylate (meth) acrylate, polyethylene glycol di (meth) acrylate, polyethylene glycol methyl ether (meth) acrylate, polyethylene glycol phenyl ether (meth) acrylate, polypropylene Glycol di (meth) acrylate, Ripropylene glycol methyl ether (meth) acrylate, polypropylene glycol 4-nonylphenyl ether (meth) acrylate, ethyl 2-ethyl acrylate, benzyl 2-ethyl acrylate, ethyl 2-propyl acrylate, benzyl 2-propyl acrylate, methyl 2-acetamide Acrylate, ethyl cis-2-cyanoacrylate, vinyl crotonate, vinyl cinnamate, isopropyl cinnamate, isobutyl cinnamate, tert-butyl cinnamate, isoamyl cinnamate, ethyl 2-cyano-3,3-diphenyl acrylate, 2- Ethylhexyl 2-cyano-3,3-diphenyl acrylate.
(C1-3) Epoxy group-containing (meth) acrylic acid esters; glycidyl (meth) acrylate.
(C1-4) hydroxy group-containing (meth) acrylic acid esters; 2-hydroxyethyl (meth) acrylate, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl (meth) acrylate, 2-hydroxypropyl 2- ( (Meth) acryloyloxyethyl phthalate, caprolactone 2- (meth) acryloyloxyethyl ester hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-acryloyloxy-2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Methyl 3-hydroxy-2-methylene-butyrate.
(C1-5) Halogen-containing (meth) acrylic acid esters; pentabromobenzyl (meth) acrylate, pentabromophenyl (meth) acrylate, methyl 2-bromoacrylate, tert-butyl 2-bromoacrylate, methyl 2-bromomethyl Acrylate, ethyl 2-bromomethyl acrylate.
(C1-6) silicon-containing (meth) acrylic acid esters; ethyl 2-trimethylsilylmethyl acrylate, 3-trimethoxysilylpropyl (meth) acrylate, 2-trimethylsilyloxyethyl (meth) acrylate, 3- [tris (trimethylsiloxy) ) Silyl] propyl (meth) acrylate, trimethylsilyl (meth) acrylate.
(C1-7) Sulfur-containing (meth) acrylic acid esters; 2-methylthioethyl (meth) acrylate.
(C1-8) (meth) acrylamides; (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-tris (hydroxymethyl) methyl ( (Meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutyloxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- [3-dimethylaminopropyl] (meth) acrylamide, 3-((meta ) Acryloylamino) propyltrimethylammonium chloride, N-tert-butyl (meth) acrylamide, 4- (meth) acryloylmorpholine, N-phenyl (meth) acrylamide, 2-acrylamide glycolic acid, 2-acrylamido 2-methyl-1-propanesulfonic acid.
(C2) (Meth) acrylonitriles:
(Meth) acrylonitrile, 2-chloroacrylonitrile, 1-cyanovinyl acetate.
(C3) Vinyl compound:
(C3-1) styrenes; styrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,4,6-trimethylstyrene, 3,4-dimethoxystyrene, 4-benzyloxy-3-methoxystyrene, 4-ethoxystyrene, 4-tert-butylstyrene, 4-tert-butoxystyrene, 4-acetoxystyrene, 2-trifluoromethylstyrene, 3-trifluoromethylstyrene, 4- Trifluoromethylstyrene, 3,5-bis (trifluoromethyl) styrene, 4-vinylaniline, 4-vinylanisole, N, N-dimethylvinylbenzylamine, 4-vinylbiphenyl, 2-fluorostyrene, 3-fluorostyrene , 4-fluorostyrene, 2,6-difluorostyrene 2,3,4,5,6-pentafluorostyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,6-dichlorostyrene, 2-bromostyrene, 3-bromostyrene, 4- Bromostyrene, 3-nitrostyrene, 3-vinylbenzoic acid, 4-vinylbenzoic acid, tert-butyl 4-vinylphenyl carbonate, 4-styrenesulfonic acid, 4-vinylphenylboronic acid, α-methylstyrene, α, 2 -Dimethylstyrene, 1,3-diisopropenylbenzene, 4-chloro-α-methylstyrene, 2,4-diphenyl-4-methyl-1-pentene, 2-isopropenylaniline, 3-isopropenyl-α, α -Dimethylbenzyl isocyanate, 1-phenyl-1-trimethylsiloxyethylene, α-bromostyrene, 1 Vinyl naphthalene, 2-vinyl naphthalene, 9-vinyl anthracene.
(C3-2) nitrogen-containing heterocyclic vinyl compound; N-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, 9-vinylcarbazole, 1-vinyl-2-pyrrolidone, N-vinylphthalimide, N-vinylcaprolactone.
(C3-3) Vinyl esters; vinyl acetate, vinyl trifluoroacetate, vinyl propionate, vinyl pivalate, vinyl decanoate, vinyl neodecanoate, vinyl stearate, vinyl benzoate.
(C3-4) vinyl ethers; 4-vinyloxymethylcyclohexylmethyl benzoate, ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 4-vinyloxybutyl benzoate, isobutyl vinyl ether, tert-butyl vinyl ether, tert-pentyl Vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl ether, vinyloxytrimethylsilane, 1,4-butanediol vinyl ether, 1,4-cyclohexanedimethanol vinyl ether, ethylene glycol vinyl ether, ethylene glycol butyl vinyl ether, diethylene glycol vinyl ether, Ethyl 1 -Propenyl ether.
(C3-5) Other vinyl compounds; vinylidene chloride, cis-1,3-dichloro-1-propene, 2-methyl-2-vinyloxirane, vinylcyclopentane, vinylcyclohexane, 4-vinyl-1-cyclohexanone, 5- Vinyl-2-norbornene, vinylferrocene, vinyltrimethylsilane, vinyltrimethoxysilane, N-vinylformamide, N-methyl-N-vinylacetamide, vinyl bromide, ethyl vinyl sulfide, methyl vinyl sulfone, vinyl sulfonic acid, vinyl phosphone Acid, trans-4,4′-difluorochalcone.

Among these compounds, preferred are the compounds described in groups (C1), (C2), (C3-1) and (C3-2), and particularly preferred are (C1-2). ) Group (meth) acrylic acid esters, (C1-4) group hydroxy (meth) acrylic acid esters, (C3-1) group styrenes and (C3-2) group nitrogen-containing heterocyclic vinyl compounds More preferred are methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, styrene, 2-vinylnaphthalene, N-vinylimidazole, 2-vinylpyridine, and 1-vinyl-2-pyrrolidone.

The hyperbranched polymer used as the dispersant of the present invention has a weight average molecular weight (hereinafter abbreviated as Mw) measured in terms of polystyrene by gel permeation chromatography, preferably 1,000 to 2,000,000, more preferably 2. , 1,000 to 1,000,000.

The hyperbranched polymer is obtained by polymerizing the monomer A or the monomer A and the monomer C in the presence of a predetermined amount of the polymerization initiator B. Examples of the polymerization method include known methods such as solution polymerization, dispersion polymerization, precipitation polymerization, and bulk polymerization. Among these, solution polymerization or precipitation polymerization is preferable. In particular, it is preferable to carry out the reaction by solution polymerization in an organic solvent from the viewpoint of molecular weight control.

Examples of organic solvents used here include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane Solvent: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate An ester solvent such as ethyl cellosolve acetate or propylene glycol monomethyl ether acetate; an ether solvent such as diethyl ether, tetrahydrofuran or 1,4-dioxane; acetone; Ketone solvents such as tilethylketone, methylisobutylketone, di-n-butylketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, Alcohol solvents such as ethylene glycol, propylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ethyl lactate; N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone Amide solvents such as dimethyl sulfoxide; aliphatic carboxylic acid solvents such as acetic acid and propionic acid, and a mixture of two or more of these solvents. It is.

Among these, preferred are aromatic hydrocarbon solvents, halogen solvents, ester solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, aliphatic carboxylic acid solvents, and the like. Benzene, toluene, xylene, orthodichlorobenzene, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, tetrahydrofuran, dioxane, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol , Tert-butanol, ethylene glycol, propylene glycol monomethyl ether, N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone and the like It is acetic acid, the most preferred are n- propanol, n- butanol, ethylene glycol, N, N'-dimethylformamide, N, N'-dimethylacetamide, N- methyl-2-pyrrolidone and acetic acid.

When the polymerization reaction is performed in the presence of an organic solvent, the content of the organic solvent in the entire polymerization reaction product is preferably 5 to 120 parts by weight, more preferably 10 to 110 parts by weight, with respect to 1 part by weight of the monomer A. Most preferably, it is 30 to 100 parts by mass.

The polymerization reaction is carried out under normal pressure, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Further, preferably carried out in an atmosphere of inert gas such as N _2.
The polymerization temperature is arbitrary as long as it is not higher than the boiling point of the reaction mixture, but from the viewpoint of polymerization efficiency and molecular weight control, it is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 80 ° C. or higher and 150 ° C. or lower, more preferably 80 ° C. It is 120 degrees C or less.
More preferably, the temperature of the polymerization reaction is carried out at a temperature that is 20 ° C. or more higher than the 10-hour half-life temperature of the aforementioned polymerization initiator B, and more specifically, the monomer A (and optionally the monomer C), A polymerization reaction can be performed by dropping a solution containing the polymerization initiator B and the organic solvent into the organic solvent maintained at a temperature 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator B. preferable. It is even more preferable to carry out the polymerization reaction at the reflux temperature of the organic solvent under a reaction pressure.
The reaction time varies depending on the reaction temperature, the types and ratios of the monomer A (and monomer C) and the polymerization initiator B, the organic solvent species, etc., but cannot be defined unconditionally, but preferably 30 minutes or more and 720 minutes Hereinafter, it is more preferably 40 minutes or more and 540 minutes or less.

More preferably, solution polymerization in an organic solvent is preferably performed in the presence of a specific acid. As described above, it is preferable to perform solution polymerization using acetic acid as an organic solvent. However, since it can be said that it is practically difficult to use a large amount of acid as a polymerization solvent from the viewpoint of odor or the like, the amount of the specific acid is actually 100 mol% to 400 mol% with respect to the polymerization initiator B. It is desirable to carry out the polymerization in the presence of

The following can be mentioned as an acid which can be used here.
Inorganic acids: hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, etc.
Aromatic carboxylic acids: benzoic acid, trimellitic acid, trimesic acid, pyromellitic acid, benzenepentacarboxylic acid, merit acid, anisic acid, toluic acid, propylbenzoic acid, propoxybenzoic acid, hydroxybenzoic acid, n-octylbenzoic acid N-octyloxybenzoic acid, hexylbenzoic acid, hexyloxybenzoic acid, heptylbenzoic acid, heptyloxybenzoic acid, ethylbenzoic acid, ethoxybenzoic acid, n-butylbenzoic acid, sec-butylbenzoic acid, tert-butylbenzoic acid Acid, butoxybenzoic acid, bromobenzoic acid, benzyloxybenzoic acid, amylbenzoic acid, amyloxybenzoic acid, aminobenzoic acid, acetylbenzoic acid, acetoxybenzoic acid, naphthalenecarboxylic acid, naphthalenedicarboxylic acid, anthracenecarboxylic acid, anthracenedica Bon acid, anthraquinone carboxylic acid, anthraquinone dicarboxylic acid, pyrene carboxylic acid, Pi dicarboxylic acid, p- toluenesulfonic acid, and trifluoromethanesulfonic acid.
Aliphatic carboxylic acid: acetic acid, trifluoroacetic acid, valeric acid, undecanoic acid, tridecanoic acid, tricosanoic acid, stearic acid, propionic acid, pentadecanoic acid, pentacosanoic acid, palmitic acid, nonanoic acid, nonadecanoic acid, nonacosanoic acid, octanoic acid, Octacosanoic acid, heptacosanoic acid, heneicosanoic acid, myristic acid, melicic acid, ligrinoceric acid, lauric acid, hexanoic acid, heptanoic acid, heptadecanoic acid, decanoic acid, serotic acid, butyric acid, behenic acid, arachidic acid, oleic acid, linolenic acid, Linoleic acid, erucic acid, elaidic acid, arachidonic acid, etc.
Amino acids: L-valine, L-tryptophan, L-serine, L-proline, L-phenylalanine, L-ornithine, L-leucine, L-isoleucine, L-histidine, L-glutamine, L-cysteine, L-asparagine, L-alanine, L-tyrosine, L-threonine, L-lysine, L-arginine, L-glycine and those whose nitrogen atoms are acetyl protected, butoxycarbonyl protected, carbobenzoxy protected, etc., or these D Body, racemic body, etc.

Among the above acids, the aromatic carboxylic acid group is preferable, and benzoic acid is most preferable.

When the polymerization is carried out in the presence of an acid, it is preferable to neutralize with a base after completion of the polymerization reaction. Examples of the base used at this time include alkali metal water such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide. An oxide etc. are mentioned.

After completion of the polymerization reaction, the obtained hyperbranched polymer is collected by an arbitrary method, and post-treatment such as washing is performed as necessary. Examples of a method for recovering the polymer from the reaction solution include a method such as reprecipitation.

The average particle size of the primary particles of the obtained hyperbranched polymer is preferably 1 nm to 100 nm, more preferably 5 nm to 50 nm.

The CNT-containing composition (CNT composition) according to the present invention comprises the CNT dispersant (highly branched polymer) and CNT.
CNTs are usually produced by arc discharge method, chemical vapor deposition method (hereinafter referred to as CVD method), laser ablation method, etc., and CNTs used here can be obtained by any method. Good. In addition, a single-walled CNT (hereinafter referred to as SWCNT) in which a single carbon film (graphene sheet) is wound in a cylindrical shape and a two-layered structure in which two graphene sheets are wound concentrically. There are CNT (hereinafter referred to as DWCNT) and multilayer CNT (hereinafter referred to as MWCNT) in which a plurality of graphene sheets are concentrically wound. In the CNT composition of the present invention, SWCNT, DWCNT, and MWCNT can be used alone or in combination.

When producing SWCNT, DWCNT, and MWCNT by the above method, fullerene, graphite, and amorphous carbon are simultaneously generated as by-products, and catalyst metals such as nickel, iron, cobalt, and yttrium remain. It may be necessary to remove and purify these impurities. In order to remove impurities, ultrasonic treatment is effective together with acid treatment with nitric acid, sulfuric acid and the like. However, acid treatment with nitric acid, sulfuric acid or the like destroys the π-conjugated system constituting CNT and may impair the original properties of CNT. Therefore, it is desirable to purify and use under appropriate conditions.

The electrical characteristics of CNTs vary from metallic to semiconducting depending on how the graphene sheet is wound (helicality, chirality).
The chirality of CNT is defined by the chiral vector shown in FIG. 11 (R = na ₁ + ma ₂ , where m and n are integers). In the case of n = m and nm = 3p (where p is an integer) It is known that the metallic properties and the semiconductor properties are shown in other cases (n ≠ m, nm−3 ≠ 3p). For this reason, particularly when SWCNT is used, it is important to obtain a composition in which a certain kind of chirality is selectively dispersed.
By using the hyperbranched polymer of the present invention as a CNT dispersant, there is a possibility that a composition in which CNTs having a specific chirality are selectively dispersed is obtained.

The CNT composition of the present invention may further contain an organic solvent capable of dissolving the dispersant (highly branched polymer).
Examples of such organic solvents include ether compounds such as tetrahydrofuran (THF), diethyl ether and dimethoxyethane (DME), halogenated hydrocarbons such as methylene chloride and chloroform, N, N′-dimethylformamide (DMF). Amide compounds such as N, N′-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP), ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, methanol, ethanol, isopropanol, propanol Alcohols such as n-heptane, n-hexane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. These organic solvents are used alone. Or it can be used as a mixture of two or more thereof.
In particular, NMP, methanol, and isopropanol are preferable because the ratio of isolated dissolution of CNT can be improved. Furthermore, it is desirable to contain a small amount of a cellosolve solvent such as ethyl cellosolve or butyl cellosolve as an additive for improving the film formability of the composition.

The method for preparing the CNT composition of the present invention is arbitrary. When the dispersant is in a liquid state, the dispersant and CNT are mixed as appropriate, and when the dispersant is a solid, after melting it, It can be prepared by mixing with CNT.
When an organic solvent is used, a composition may be prepared by mixing a dispersant, CNT, and an organic solvent in an arbitrary order. For example, these may be mixed together, or a dispersant may be used. CNTs may be added and mixed in a solution dissolved in an organic solvent.
At this time, it is preferable to disperse a mixture composed of a dispersant, CNTs, and an organic solvent, and this treatment can further improve the ratio of isolated dispersion of CNTs. Examples of dispersion processing include wet processing using a ball mill, bead mill, jet mill, etc. as mechanical processing, and ultrasonic processing using a bath type or probe type sonicator. However, in consideration of processing efficiency, ultrasonic processing is performed. Is preferred.
The time for the dispersion treatment is arbitrary, but is preferably about 5 minutes to 10 hours, more preferably about 10 minutes to 5 hours.

The mixing ratio of the dispersant and the CNT in the CNT composition of the present invention can be about 1,000: 1 to 1: 100 by mass ratio.
Further, the concentration of the dispersant in the composition using the organic solvent is not particularly limited as long as it is a concentration capable of dispersing CNTs in the organic solvent, but in the present invention, 0.001 in the composition. It is preferable to set it as about thru | or 30 mass%, and it is more preferable to set it as about 0.005 thru | or 20 mass%.
Further, the concentration of CNTs in the composition is arbitrary as long as at least a part of the CNTs is isolated and dispersed, but in the present invention, it is preferable to set the concentration to about 0.0001 to 20% by mass in the composition. More preferably, the content is about 0.001 to 10% by mass.
In the CNT composition prepared as described above, it is presumed that the dispersant adheres to the surface of the CNT to form a composite.

The CNT composition of the present invention may be mixed with a general-purpose synthetic resin that is soluble in the organic solvent and combined. Examples of general-purpose synthetic resins include polyolefin resins such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); PS (polystyrene) , Polystyrene resins such as HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer); polycarbonate resin; Polyvinyl resin; Polyamide resin; (Meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate , PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate / adipate and other polyester resins; polyphenylene ether resin; modified polyphenylene ether resin; polyacetal resin; polysulfone resin; Polyvinyl alcohol resin; polyglycolic acid; modified starch; cellulose acetate, cellulose triacetate; chitin, chitosan; thermoplastic resin such as lignin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy Examples thereof include thermosetting resins such as resins.

Further, the CNT composition of the present invention may be mixed with a thermosetting compound that is soluble in the organic solvent and combined.
Preferred examples of the thermosetting compound include polyfunctional epoxy compounds. In addition, the meaning of the thermosetting compound in this specification includes not only a monomer compound (monomer) in a narrow sense but also a dimer, a trimer, an oligomer, and a reactive polymer. .
The polyfunctional epoxy compound is not particularly limited as long as it contains two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type Epoxy resin, dimer acid glycidyl ester type epoxy resin, polyalkylene ether type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthol type epoxy resin, naphthalene type An epoxy resin, an alicyclic epoxy resin, a heterocyclic ring-containing epoxy resin, a diglycidyl epoxy resin, a glycidylamine type epoxy resin, a halogenated bisphenol A type epoxy resin, and the like are preferably used. Mixed and used in.
In addition, the CNT composition of this invention may contain the compound containing one epoxy group in a molecule | numerator as a reactive diluent with a thermosetting compound.
The content of the polyfunctional epoxy compound in the CNT composition of the present invention is preferably 0.1 to 100 parts by mass, more preferably 1 to 10 parts by mass with respect to 1 part by mass of the dispersant.

The CNT composition (solution) of the present invention is applied on an appropriate substrate such as PET, glass, ITO, or the like by an appropriate method such as a casting method, a spin coating method, a bar coating method, a roll coating method, or a dip coating method. Thus, a thin film can be formed.
The obtained thin film can be suitably used for an antistatic film utilizing the metallic properties of CNT, a conductive material such as a transparent electrode, or a photoelectric conversion element and an electroluminescent device utilizing semiconductor properties.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.
(1) GPC (gel permeation chromatography)
Equipment: GPC-101, Showa Denko Co., Ltd.
Column: Showa Denko LF-804 × 3
Column temperature: 60 ° C
Solvent: NMP with 20 mM LiBr added
Flow rate: 0.6 mL / min Detector: UV (280 nm)
(2) ¹ H NMR spectrum and ¹³ C NMR spectrum Apparatus: JNM-ECA700 manufactured by JEOL Datum Co., Ltd.
Solvent: CDCl ₃
Internal standard: Tetramethylsilane (3) Dynamic light scattering photometer (particle size measurement)
Equipment: FDLS-3000 manufactured by Otsuka Electronics Co., Ltd.
(4) Hot plate (pre-bake, post-bake)
Equipment: MH-180CS, MH-3CS, manufactured by AS ONE
(5) Probe-type ultrasonic irradiation device (dispersion processing)
Apparatus: UIP1000 manufactured by Hielscher Ultrasonics
(6) Ultrasonic cleaner (dispersion processing)
Equipment: FU-6H manufactured by Tokyo Glass Instrument Co., Ltd.
(7) Resistivity meter (surface resistance measurement)
Equipment: Loresta-GP, manufactured by Mitsubishi Chemical Corporation
Probe: In-line 4-probe probe ASP manufactured by Mitsubishi Chemical Corporation (distance between probes: 5 mm)
(8) Haze meter (total light transmittance measurement)
Device: NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
(9) Small high-speed cooling centrifuge (centrifugation)
Equipment: SRX-201, manufactured by Tommy Seiko Co., Ltd.
(10) Ultraviolet / visible / near infrared spectrophotometer (absorbance measurement)
Apparatus: UV-3600 manufactured by Shimadzu Corporation
Measurement wavelength: 400-1650nm

Abbreviations represent the following meanings.
DVB: Divinylbenzene (DVB-960, manufactured by Nippon Steel Chemical Co., Ltd.)
B-1: 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (VA-061 manufactured by Wako Pure Chemical Industries, Ltd.)
B-2: 2,2′-azobis (1-imino-1-pyrrolidino-2-methyl-propane) dihydrochloride (VA-067 manufactured by Wako Pure Chemical Industries, Ltd.)
MAIB: Dimethyl 2,2′-azobisisobutyrate (MAIB manufactured by Otsuka Chemical Co., Ltd.)
EPL: Epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) -modified ε-caprolactone (Epolyde GT401 manufactured by Daicel Chemical Industries, Ltd.)
JER: Epoxy resin (Japan Epoxy Resin Co., Ltd. jER (registered trademark) 828)
CNT-1: Unrefined MWCNT (“C Tube 100” manufactured by CNT, outer diameter 10-30 nm)
CNT-2: Fine MWCNT (Cheap Tubes “MWNTs> 95 wt% / outer diameter <8 nm”)
CNT-3: Unpurified SWCNT (HiPco manufactured by Carbon Nanotechnologies)
CNT-4: Medium diameter MWCNT (Bayer's “Baytubes C 150 P” outer diameter 5-20 nm)
CNT-5: Medium diameter MWCNT ("FloTube 9000" outer diameter 11 nm, manufactured by CNano Technology)
CNT-6: Medium diameter MWCNT (“VGCF-X” outer diameter 15 nm, manufactured by Showa Denko KK)
CNT-7: Large diameter MWCNT (Cheap Tubes “MWCNTs> 95 wt% / 20-40 nm” outer diameter 20-40 nm)
CNT-8: Extremely large diameter MWCNT (Cheap Tubes “MWCNTs> 95 wt% /> 50 nm”)
PVP: Polyvinylpyrrolidone (Tokyo Chemical Industry Co., Ltd. K15)
DMF: N, N′-dimethylformamide EG: ethylene glycol NMP: N-methyl-2-pyrrolidone THF: tetrahydrofuran DMSO: dimethyl sulfoxide IPA: 2-propanol PGME: propylene glycol monomethyl ether

[Example 1]
<Synthesis of hyperbranched polymer 1 using DVB and B-1>
A 200 mL reaction flask was charged with 44 g of acetic acid, and nitrogen was introduced for 5 minutes while stirring, and the mixture was heated until the internal temperature reached 100 ° C.
Into another 100 mL reaction flask were charged 2.6 g (20 mmol) of DVB, 3.8 g of B-1 (15 mmol, 75 mol% with respect to DVB) and 44 g of acetic acid. The mixture was cooled to 0 ° C. in an ice bath.
The contents were dropped into the acetic acid heated to 100 ° C. in the 200 mL reaction flask from the 100 mL reaction flask charged with DVB, B-1 and acetic acid over 45 minutes using a dropping pump. . After completion of dropping, the mixture was aged for 30 minutes.
Next, this reaction liquid was added to 294 g of THF to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure, and the obtained solid was redissolved in 19 g of water. The polymer was reprecipitated in a slurry state by slowly dropping 13.3 mL of 6N NaOH aqueous solution into this polymer aqueous solution and neutralizing. The slurry was filtered under reduced pressure, and the resulting solid was redissolved in 18 g of chloroform. This polymer solution was added to 294 g of hexane to reprecipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 2.1 g of the desired product (highly branched polymer 1) as a white powder.
The measurement results of ¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIG. 1 and FIG.
Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 34,000, and dispersion degree: Mw (weight average molecular weight) / Mn (number average molecular weight) was 3.9.

[Example 2]
<Synthesis of hyperbranched polymer 2 using DVB and B-1>
A 200 mL reaction flask was charged with 44 g of DMF, and nitrogen was allowed to flow for 5 minutes with stirring until the internal temperature reached 100 ° C.
In a separate 100 mL reaction flask was charged 2.6 g (20 mmol) DVB, 3.8 g B-1 (15 mmol, 75 mol% with respect to DVB), 6.1 g (50 mmol) benzoic acid and 44 g DMF while stirring. Nitrogen was introduced for 5 minutes to replace nitrogen, and the mixture was cooled to 0 ° C. in an ice bath.
From the 100 mL reaction flask charged with DVB, B-1, benzoic acid and DMF in DMF heated to 100 ° C. in the 200 mL reaction flask described above, the contents were allowed to flow for 45 minutes using a dropping pump. And dripped. After completion of dropping, the mixture was aged for 30 minutes.
Next, this reaction liquid was added to 260 g of diisopropyl ether to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure, and the obtained solid was redissolved in 44 g of water / methanol (mass ratio 1: 9). The polymer was reprecipitated in a slurry state by slowly dropping 13.3 mL of 6N NaOH aqueous solution into the polymer solution and neutralizing. This slurry was filtered under reduced pressure, and the resulting solid was redissolved in 44 g of chloroform. This polymer solution was added to 260 g of hexane to reprecipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 3.6 g of the desired product (highly branched polymer 2) as a white powder.
The measurement results of ¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS. 3 and 4.
Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 33,000, and dispersion degree: Mw / Mn was 15.8.

[Example 3]
<Synthesis of hyperbranched polymer 3 using DVB and B-1>
A 500 mL reaction flask was charged with 120 g of 1-propanol, nitrogen was introduced for 5 minutes with stirring, and the mixture was heated until 1-propanol was refluxed (standard boiling point 97 ° C.).
In another 200 mL reaction flask, 2.6 g (20 mmol) of DVB, 3.1 g of B-1 (12 mmol, 62 mol% based on DVB), and 120 g of 1-propanol were charged, and nitrogen was poured for 5 minutes while stirring. Replacement was performed.
From the 200 mL reaction flask charged with DVB, B-1 and 1-propanol in the refluxed 1-propanol in the 500 mL reaction flask, the contents were dropped over 90 minutes using a dropping pump. did. After completion of dropping, the mixture was aged for 1 hour.
Next, 1-propanol was distilled off from this reaction solution using a rotary evaporator, and the resulting residue was dissolved in 26 g of chloroform. This polymer solution was added to 260 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure, and the resulting solid was redissolved in 26 g of chloroform. This polymer solution was added to 260 g of hexane to reprecipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 2.5 g of the desired product (highly branched polymer 3) as a pale yellow powder.
The measurement results of ¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS. 5 and 6.
Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 47,000, and dispersion degree: Mw / Mn was 13.9.

[Example 4]
<Synthesis of hyperbranched polymer 4 using DVB and B-2>
A 200 mL reaction flask was charged with 42 g of EG / DMF (mass ratio 1: 1), and nitrogen was introduced for 5 minutes while stirring, and the mixture was heated until the internal temperature reached 100 ° C.
In a separate 100 mL reaction flask was charged 2.6 g (20 mmol) DVB, 3.5 g B-2 (10 mmol, 50 mol% with respect to DVB) and 42 g EG / DMF (mass ratio 1: 1) with stirring. Nitrogen was introduced for 5 minutes to replace nitrogen, and the mixture was cooled to 0 ° C. in an ice bath.
From the 100 mL reaction flask charged with DVB, B-2, and EG / DMF in EG / DMF heated to 100 ° C. in the 200 mL reaction flask, the contents were removed for 45 minutes using a dropping pump. It was dripped over. After completion of dropping, the mixture was aged for 30 minutes.
Next, this reaction solution was added to 294 g of THF to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure, and the obtained solid was redissolved in 42 g of water. The polymer was reprecipitated in a slurry state by slowly dropping and neutralizing 3.3 mL of 6N NaOH aqueous solution into the polymer aqueous solution. This slurry was filtered under reduced pressure, and the resulting solid was redissolved in 42 g of chloroform. This polymer solution was added to 260 g of hexane to reprecipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 3.1 g of the target product (highly branched polymer 4) as a brown powder.
The measurement results of ¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIG. 7 and FIG.

[Example 15]
<Synthesis of hyperbranched polymer 6 using DVB and B-1>
A 3 L reaction flask was charged with 180 g of 1-propanol, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until 1-propanol was refluxed (standard boiling point 97 ° C.).
In a separate 2 L reaction flask, 15.6 g (120 mmol) of DVB, 21.0 g of B-1 (84 mmol, 70 mol% with respect to DVB) and 720 g of 1-propanol were charged, and nitrogen was poured for 5 minutes while stirring. Replacement was performed.
From the 2L reaction flask charged with DVB, B-1 and 1-propanol in 1-propanol being refluxed in the 3L reaction flask, the contents were dropped over 70 minutes using a dropping pump. did. After completion of dropping, the mixture was aged for 2 hours.
Next, 820 g of 1-propanol was distilled off from this reaction solution using a rotary evaporator and added to 1,600 g of heptane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure, and the resulting solid was redissolved in 78 g of 1-propanol. This polymer solution was added to 3,100 g of water to reprecipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 22.1 g of the target product (highly branched polymer 6) as a white powder.
The measurement results of ¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS. 12 and 13. As the measurement solvent, d ₆ -DMSO to which a small amount of CDCl ₃ was added was used.
Moreover, although the molecular weight measurement by GPC of the target object was tried, it was not able to be measured on the said conditions.

[Example 16]
<Synthesis of hyperbranched polymer 7 using DVB and B-1>
A 3 L reaction flask was charged with 180 g of 1-propanol, and nitrogen was allowed to flow for 5 minutes with stirring, followed by heating until 1-propanol was refluxed (standard boiling point 97 ° C.).
In a separate 2 L reaction flask, 15.6 g (120 mmol) of DVB, 21.1 g of B-1 (84 mmol, 70 mol% with respect to DVB), and 720 g of 1-propanol were charged, and nitrogen was poured for 5 minutes while stirring. Replacement was performed.
From the 2L reaction flask charged with DVB, B-1 and 1-propanol in the 1-propanol being refluxed in the 3L reaction flask, the contents were dropped over 50 minutes using a dropping pump. did. After completion of dropping, the mixture was aged for 2 hours.
Next, 820 g of 1-propanol was distilled off from this reaction solution using a rotary evaporator and added to 1,600 g of heptane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure, and the resulting solid was redissolved in 78 g of 1-propanol. This polymer solution was added to 3,100 g of water to reprecipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 23.9 g of the target product (highly branched polymer 7) as a white powder.
14 and 15 show the measurement results of ¹ H NMR and ¹³ C NMR spectra of the obtained target product. For the measurement, apparatus: AVANCE III manufactured by BRUKER, solvent: d ₆ -DMSO to which a small amount of CDCl ₃ was added, and internal standard: tetramethylsilane were used.
Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 100,000, and dispersion degree: Mw (weight average molecular weight) / Mn (number average molecular weight) was 10.0.

[Reference Production Example 1]
<Synthesis of hyperbranched polymer 5 using DVB and MAIB>
A 500 mL reaction flask was charged with 74 g of toluene, and nitrogen was introduced for 5 minutes while stirring, and the mixture was heated until the toluene was refluxed (standard boiling point 111 ° C.).
In another 200 mL reaction flask, 3.9 g (30 mmol) of DVB, 5.5 g of MAIB (24 mmol, 80 mol% with respect to DVB) and 74 g of toluene were charged, and nitrogen was purged for 5 minutes while stirring.
The contents were added dropwise from the 200 mL reaction flask charged with DVB, MAIB and toluene into the refluxing toluene in the 500 mL reaction flask using a dropping pump over 1.5 hours. After completion of dropping, the mixture was aged for 6 hours.
Next, 121 g of toluene was distilled off from this reaction solution using a rotary evaporator and added to 391 g of methanol cooled to 0 ° C. to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 6.1 g of the desired product (highly branched polymer 5) as a white powder.
9 and 10 show the measurement results of ¹ H NMR and ¹³ C NMR spectra of the obtained target product.
Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 37,000, and dispersion degree: Mw / Mn was 2.6.

Fragments of monomer A and polymerization initiator B calculated from ¹³ C NMR spectra of hyperbranched polymers 1, 2, 3, 4, 6, 7 synthesized in Examples 1 to 4, Example 15, and Example 16. Table 1 shows the composition ratio (molar ratio) and the average particle diameter measured by a dynamic light scattering photometer.

[Example 5]
<Dispersion of CNT-1 using highly branched polymer 2 (1)>
As a dispersant, 0.50 g of the hyperbranched polymer 2 synthesized in Example 2 was dissolved in 49.25 g of NMP, and 0.25 g of CNT-1 was added to this solution as MWCNT. This mixture was subjected to ultrasonic treatment at room temperature (approximately 25 ° C.) for 30 minutes using a probe-type ultrasonic irradiation device to obtain a black MWCNT-containing dispersion liquid in which MWCNT was uniformly dispersed without a precipitate.
0.25 g of butyl cellosolve was added to 1.0 g of the above MWCNT-containing dispersion to prepare a composition for forming a thin film. The obtained composition 50 μL is uniformly spread on a glass substrate using an applicator having a slit width of 25.4 μm, and dried at 100 ° C. for 2 minutes, whereby a transparent and uniform MWCNT / highly branched polymer 2 thin film composite Was made. Thin film uniformity, surface resistance and total light transmittance of the obtained thin film composite were evaluated. The uniformity of the thin film was evaluated visually according to the following criteria. Each evaluation result is shown in Table 2.
<Thin film uniformity>
○: No clumps such as aggregates or film unevenness (light / dark) can be confirmed.
(Triangle | delta): The aggregate of MWCNT and a film | membrane nonuniformity (light / dark) are seen.
X: Aggregates of MWCNT and film unevenness (light / dark) are seen in almost all parts of the thin film, and cannot be evaluated as a film.

Separately, the above MWCNT-containing dispersion was allowed to stand at room temperature (approximately 25 ° C.) for 1 month, and then the presence of sediment in the dispersion was visually confirmed, and the dispersion stability of this dispersion was determined according to the following criteria. Evaluated. The evaluation results are shown in Table 2.
<Dispersion stability>
○: No sediment can be confirmed.
(Triangle | delta): A sediment is seen.
X: The dispersion state cannot be maintained, and most of the MWCNT appears as a sediment.

[Example 6]
<Dispersion of CNT-1 using highly branched polymer 2 (2)>
In Example 5, the same operation and evaluation were performed except that the addition amount of the hyperbranched polymer 2 was changed to 0.25 g and the amount of NMP was changed to 49.50 g. The evaluation results are shown in Table 2.

[Example 7]
<Dispersion of CNT-1 using highly branched polymer 4 (1)>
In Example 5, the same operation and evaluation were performed except that the dispersant was changed to the hyperbranched polymer 4 synthesized in Example 4. The evaluation results are shown in Table 2.

[Example 8]
<Dispersion of CNT-1 using hyperbranched polymer 4 (2)>
In Example 5, the same operation and evaluation were performed except that the dispersant and the amount of addition were changed to 0.25 g of the hyperbranched polymer 4 synthesized in Example 4 and the amount of NMP was changed to 49.50 g, respectively. . The evaluation results are shown in Table 2.

[Example 17]
<Dispersion of CNT-1 using highly branched polymer 6 (1)>
In Example 5, the same operation and evaluation were performed except that the dispersant was changed to the hyperbranched polymer 6 synthesized in Example 15. The evaluation results are shown in Table 2.

[Example 18]
<Dispersion of CNT-1 using highly branched polymer 6 (2)>
In Example 17, the same operation and evaluation were performed except that the dispersion solvent was changed from NMP to IPA. The evaluation results are shown in Table 2.

[Example 19]
<Dispersion of CNT-1 using highly branched polymer 6 (3)>
In Example 17, the same operation and evaluation were performed except that the dispersion solvent was changed from NMP to PGME. The evaluation results are shown in Table 2.

[Example 20]
<Dispersion of CNT-1 using highly branched polymer 7 (1)>
The same operations and evaluations were performed in Example 5 except that the dispersant was changed to the hyperbranched polymer 7 synthesized in Example 16. The evaluation results are shown in Table 2.

[Example 21]
<Dispersion of CNT-1 using highly branched polymer 7 (2)>
In Example 5, the same operation and evaluation were performed except that the dispersant and the amount of addition were changed to 0.25 g of the hyperbranched polymer 7 synthesized in Example 16 and the amount of NMP was changed to 49.50 g, respectively. . The evaluation results are shown in Table 2.

[Comparative Example 1]
<Dispersion of CNT-1 using highly branched polymer 5 (1)>
In Example 5, the same operation and evaluation were performed except that the dispersant was changed to the hyperbranched polymer 5 synthesized in Reference Production Example 1. The evaluation results are shown in Table 2.

[Comparative Example 2]
<Dispersion of CNT-1 using highly branched polymer 5 (2)>
In Example 5, the same operation and evaluation were carried out except that the dispersant and the amount added were changed to 0.25 g of the hyperbranched polymer 5 synthesized in Reference Production Example 1 and the amount of NMP was changed to 49.50 g, respectively. It was. The evaluation results are shown in Table 2.

[Comparative Example 3]
<Dispersion of CNT-1 using PVP (1)>
In Example 5, the same operation and evaluation were performed except that the dispersant was changed to PVP. The evaluation results are shown in Table 2.

[Comparative Example 4]
<Dispersion of CNT-1 using PVP (2)>
In Example 5, the same operations and evaluations were performed except that the dispersant and the amount added thereof were changed to 0.25 g of PVP and the amount of NMP was changed to 49.50 g, respectively. The evaluation results are shown in Table 2.

[Example 9]
<Dispersion of CNT-2 using hyperbranched polymer 2 (1)>
In Example 5, the same operation and evaluation were performed except that MWCNT was changed to CNT-2. The evaluation results are shown in Table 3.

[Example 10]
<Dispersion of CNT-2 using hyperbranched polymer 2 (2)>
In Example 5, the same operation and evaluation were performed except that MWCNT was changed to CNT-2, the addition amount of the hyperbranched polymer 2 was changed to 0.25 g, and the amount of NMP was changed to 49.50 g. The evaluation results are shown in Table 3.

[Example 11]
<Dispersion of CNT-2 using highly branched polymer 4>
The same operation and evaluation were performed except that MWCNT was changed to CNT-2 and the dispersant was changed to the hyperbranched polymer 4 synthesized in Example 4 in Example 5. The evaluation results are shown in Table 3.

[Example 22]
<Dispersion of CNT-2 using highly branched polymer 6>
The same operations and evaluations were performed except that in Example 5, MWCNT was changed to CNT-2 and the dispersant was changed to the highly branched polymer 6 synthesized in Example 15. The evaluation results are shown in Table 3.

[Example 23]
<Dispersion of CNT-2 using highly branched polymer 7>
The same operations and evaluations were performed except that in Example 5, MWCNT was changed to CNT-2 and the dispersant was changed to the highly branched polymer 7 synthesized in Example 16. The evaluation results are shown in Table 3.

[Comparative Example 5]
<Dispersion of CNT-2 using highly branched polymer 5>
The same operation and evaluation were performed except that MWCNT was changed to CNT-2 and the dispersant was changed to the hyperbranched polymer 5 synthesized in Reference Production Example 1 in Example 5. The evaluation results are shown in Table 3.

[Comparative Example 6]
<Dispersion of CNT-2 using PVP>
In Example 5, the same operation and evaluation were performed except that MWCNT was changed to CNT-2 and the dispersant was changed to PVP. The evaluation results are shown in Table 3.

[Example 24]
<Dispersion of CNT-4 using highly branched polymer 7>
The same operation and evaluation were performed except that in Example 5, MWCNT was changed to CNT-4 and the dispersant was changed to the highly branched polymer 7 synthesized in Example 16. The evaluation results are shown in Table 4.

[Example 25]
<Dispersion of CNT-5 using highly branched polymer 7>
In Example 24, the same operation and evaluation were performed except that MWCNT was changed to CNT-5. The evaluation results are shown in Table 4.

[Example 26]
<Dispersion of CNT-6 using highly branched polymer 7>
In Example 24, the same operation and evaluation were performed except that MWCNT was changed to CNT-6. The evaluation results are shown in Table 4.

[Example 27]
<Dispersion of CNT-7 using highly branched polymer 7>
In Example 24, the same operation and evaluation were performed except that MWCNT was changed to CNT-7. The evaluation results are shown in Table 4.

[Example 28]
<Dispersion of CNT-8 using highly branched polymer 7>
In Example 24, the same operation and evaluation were performed except that MWCNT was changed to CNT-8. The evaluation results are shown in Table 4.

[Comparative Example 9]
<Dispersion of CNT-4 using PVP>
In Example 5, the same operation and evaluation were performed except that MWCNT was changed to CNT-4 and the dispersant was changed to PVP. The evaluation results are shown in Table 4.

[Comparative Example 10]
<Dispersion of CNT-5 using PVP>
The same operation and evaluation were performed except that MWCNT was changed to CNT-5 in Comparative Example 9. The evaluation results are shown in Table 4.

[Comparative Example 11]
<Dispersion of CNT-6 using PVP>
The same operation and evaluation were performed except that MWCNT was changed to CNT-6 in Comparative Example 9. The evaluation results are shown in Table 4.

[Comparative Example 12]
<Dispersion of CNT-7 using PVP>
The same operation and evaluation were performed except that MWCNT was changed to CNT-7 in Comparative Example 9. The evaluation results are shown in Table 4.

[Comparative Example 13]
<Dispersion of CNT-8 using PVP>
The same operation and evaluation were performed except that MWCNT was changed to CNT-8 in Comparative Example 9. The evaluation results are shown in Table 4.

As shown in Table 2, when Examples 5, 7, 17, 20 and Comparative Example 3, and Examples 6, 8, 21, and Comparative Example 4 having the same CNT / dispersant mixing ratio were compared, the present invention was compared. CNT-1 thin film composites (Examples 5 to 8, Examples 17, 20, and 21) prepared using the above-described dispersants were obtained using PVP known as a CNT dispersant (Comparative Examples 3 and 4). ) And the total light transmittance was equal or higher. Furthermore, if the solvent (IPA or PGME) in which the dispersant of the present invention is dissolved, CNT can be dispersed in a solvent other than NMP (Examples 18 and 19), and widely applied to the dispersion of MWCNT. It became clear that we could do it. In addition, the uniformity of the thin film is also good, and it has become clear that the dispersant of the present invention is advantageous in obtaining a highly conductive and uniform thin film composite. In addition, Comparative Example 1 and Comparative Example 2 using the hyperbranched polymer 5 as a dispersant could not maintain the dispersion state, and the result that the polymer has no dispersion performance was obtained.
Further, in the dispersion of MWCNT (CNT-2) having a smaller outer diameter, as shown in Table 3, only when the dispersant of the present invention is used (Examples 9 to 11, Examples 22 and 23), MWCNT Thus, a MWCNT-containing dispersion having a uniform dispersion was obtained, and a thin film composite could be prepared. The use of MWCNT having a smaller outer diameter such as CNT-2 can be expected to improve the transparency of the thin film composite. Therefore, it was revealed that the dispersant of the present invention is advantageous in terms of transparency. .
Further, as shown in Table 4, the dispersant of the present invention can also be dispersed with MWCNTs commercially available from various manufacturers, and Example 24 and Comparative Example 9 (CNT-4), which have the same MWCNT species, Example 25 and Comparative Example 10 (CNT-5), Example 26 and Comparative Example 11 (CNT-6), Example 27 and Comparative Example 12 (CNT-7), and Example 28 and Comparative Example 13 (CNT-) Comparing 8), the MWCNT thin film composites produced using the dispersant of the present invention (Examples 24 to 28) were obtained when PVP known as a CNT dispersant was used (Comparative Examples 9 to 13). ) And the total light transmittance was equivalent or better. Furthermore, since the uniformity of the thin film is good, it is clear that the dispersant of the present invention is advantageous in obtaining a highly conductive and uniform thin film composite and is widely applicable in the dispersion of commercially available MWCNTs. became.

[Example 12]
<Dispersion of CNT-3 using highly branched polymer 2>
As a dispersant, 1 mg of hyperbranched polymer 2 synthesized in Example 2 was dissolved in 5 mL of NMP, and 0.5 mg of CNT-3 as SWCNT was added to this solution. This mixture is sonicated for 1 hour at room temperature using an ultrasonic cleaner, and centrifuged at 10,000 G for 1 hour at room temperature (approximately 25 ° C.) to recover a black transparent SWCNT-containing solution as a supernatant. did.
When the ultraviolet-visible near-infrared absorption spectrum of the obtained black transparent SWCNT-containing solution was measured, it was found that the semiconducting S ₁₁ band (1,400 to 1,000 nm), the S ₂₂ band (1,000 to 600 nm), and the metal The absorption of the sex band (600 to 450 nm) was clearly observed, and it was confirmed that SWCNT was dispersed to the isolated dispersion state.

[Example 29]
<Dispersion of CNT-3 using highly branched polymer 6>
The same operation as in Example 12 was performed except that the dispersant was changed to the hyperbranched polymer 6 synthesized in Example 15.
When the ultraviolet-visible near-infrared absorption spectrum of the obtained black transparent SWCNT-containing solution was measured, it was found that the semiconducting S ₁₁ band (1,400 to 1,000 nm), the S ₂₂ band (1,000 to 600 nm), and the metal The absorption of the sex band (600 to 450 nm) was clearly observed, and it was confirmed that SWCNT was dispersed to the isolated dispersion state.

[Example 30]
<Dispersion of CNT-3 using highly branched polymer 7>
The same operation as in Example 12 was performed except that the dispersant was changed to the hyperbranched polymer 7 synthesized in Example 16.
When the ultraviolet-visible near-infrared absorption spectrum of the obtained black transparent SWCNT-containing solution was measured, it was found that the semiconducting S ₁₁ band (1,400 to 1,000 nm), the S ₂₂ band (1,000 to 600 nm), and the metal The absorption of the sex band (600 to 450 nm) was clearly observed, and it was confirmed that SWCNT was dispersed to the isolated dispersion state.

[Comparative Example 7]
<Dispersion of CNT-3 using PVP>
In Example 12, the same operation was performed except that the hyperbranched polymer 2 was changed to PVP, but SWCNT could not be dispersed.

[Comparative Example 8]
<Dispersion with CNT-3 alone>
In Example 12, the same operation was performed except that the addition of the hyperbranched polymer 2 was omitted, but the SWCNT could not be dispersed.

[Example 13]
<Thermal curing of CNT-1 thin film composite using hyperbranched polymer 2 and JER>
As a dispersant, 0.50 g of the hyperbranched polymer 2 synthesized in Example 2 was dissolved in 49.25 g of NMP, and 0.25 g of CNT-1 as MWCNT was added to this solution. This mixture was subjected to ultrasonic treatment at room temperature (approximately 25 ° C.) for 30 minutes using a probe-type ultrasonic irradiation device to obtain a black MWCNT-containing dispersion liquid in which MWCNT was uniformly dispersed without a precipitate.
To 1.0 g of the above MWCNT-containing dispersion, 1.0 g of a 1.5 mass% NMP solution of a polyfunctional epoxy compound JER prepared in advance and 0.5 g of butyl cellosolve were added to prepare a composition for producing a thin film. 50 μL of the obtained composition is uniformly spread on a glass substrate using an applicator having a slit width of 25.4 μm, pre-baked at 100 ° C. for 10 minutes, and dried to obtain a transparent and uniform MWCNT / highly branched polymer 2 / Epoxy compound thin film composite was prepared. This thin film composite was further post-baked at 160 ° C. for 30 minutes for thermosetting.
The obtained thin film composite was evaluated for surface resistance before and after thermosetting, total light transmittance and pencil hardness. The pencil hardness was measured according to the handwriting method described in JIS K5400. The results are shown in Table 5.

[Example 14]
<Thermal curing of CNT-1 thin film composite using hyperbranched polymer 2 and EPL>
In Example 13, the same operation and evaluation were performed except that the polyfunctional epoxy compound was changed to EPL and the post-baking temperature was changed to 230 ° C. The evaluation results are shown in Table 5.

The thin films obtained in Examples 13 and 14 were uniform, and the dispersibility of MWCNT was maintained even when a thin film was prepared by adding a polyfunctional epoxy compound. Further, it was confirmed that the surface resistance value was lowered and the pencil hardness was greatly improved by thermosetting by post-baking. From this, it is clear that the hyperbranched polymer of the present invention used as a dispersant also acts as a curing accelerator for epoxy compounds, and can be suitably used for applications requiring hardness as a thin film. The result to be obtained.

JP-A-6-228824 JP 2000-44216 A JP 2008-24568 A JP 2005-75661 A JP 2005-162877 A JP 2008-24522 A

Claims (22)

1. It has an amino functional group or an imino functional group at the end, and is characterized by comprising a hyperbranched polymer having a weight average molecular weight of 1,000 to 2,000,000 measured in terms of polystyrene by gel permeation chromatography, Carbon nanotube dispersant.
2. A polymerization initiator B in which the hyperbranched polymer has a monomer A having two or more radically polymerizable double bonds in the molecule and an amino functional group or imino functional group in an amount of 5 to 200 mol% based on the monomer A. The carbon nanotube dispersant according to claim 1, which is a hyperbranched polymer obtained by polymerization in the presence of.
3. The carbon nanotube dispersant according to claim 1 or 2, wherein the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator having a heterocyclic amine structure.
4. The carbon nanotube dispersant according to claim 1 or 2, wherein the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator having a functional group represented by the formula [1].
   

   

   (In the formula [1], R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, or R ^1. , R ² and R ³ may be combined with the nitrogen atom to which they are bonded to form a ring.)
5. The carbon nanotube dispersant according to claim 2, wherein the polymerization initiator B having the amino functional group or imino functional group is a polymerization initiator represented by the formula [2].
   

   

   (In the formula [2], R ¹ , R ² and R ³ represent those defined in the formula [1], and R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 6 carbon atoms. To express.)
6. The highly branched polymer comprises a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer C having at least one radical polymerizable double bond in the molecule. It is a highly branched polymer obtained by polymerizing in the presence of a polymerization initiator B having an amino functional group or imino functional group in an amount of 5 mol% or more and 200 mol% or less with respect to the total mol of the monomer C. Item 4. The carbon nanotube dispersant according to Item 1.
7. The carbon nanotube dispersant according to claim 6, wherein the polymerization initiator B having the amino functional group or imino functional group is a polymerization initiator having a heterocyclic amine structure.
8. The carbon nanotube dispersant according to claim 6, wherein the polymerization initiator B having the amino functional group or imino functional group is a polymerization initiator having a functional group represented by the formula [1].
   

   

   (In the formula [1], R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, or R ^1. , R ² and R ³ may be combined with the nitrogen atom to which they are bonded to form a ring.)
9. The carbon nanotube dispersant according to claim 8, wherein the polymerization initiator B having the amino functional group or imino functional group is a polymerization initiator represented by the formula [2].
   

   

   (In the formula [2], R ¹ , R ² and R ³ represent those defined in the formula [1], and R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 6 carbon atoms. To express.)
10. The composition containing the carbon nanotube dispersing agent as described in any one of Claims 1 thru | or 9, and a carbon nanotube.
11. The composition according to claim 10, wherein the carbon nanotube is at least one selected from single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
12. The composition according to claim 10 or 11, wherein the carbon nanotube dispersant is attached or coordinated to a surface of the carbon nanotube to form a composite.
13. The composition according to any one of claims 10 to 12, further comprising an organic solvent.
14. The composition according to claim 13, wherein the carbon nanotube is dispersed in the organic solvent.
15. The composition according to claim 13, wherein the complex is dispersed in the organic solvent.
16. Furthermore, the composition as described in any one of Claims 10 thru | or 15 containing the thermosetting compound soluble in an organic solvent.
17. The composition according to claim 16, wherein the thermosetting compound is a polyfunctional epoxy compound.
18. A thin film obtained from the composition according to any one of claims 10 to 17.
19. The cured film obtained by heat-processing the thin film obtained from the composition of Claim 16 or Claim 17.
20. A step of preparing a mixture by mixing the carbon nanotube dispersant according to any one of claims 1 to 9, a carbon nanotube, and an organic solvent, and a step of mechanically treating the mixture. A process for producing a composition, characterized in that
21. The manufacturing method according to claim 20, wherein the mechanical treatment is ultrasonic treatment.
22. The method comprising: adding the carbon nanotubes to a solution obtained by dissolving the carbon nanotube dispersant in the organic solvent to prepare the mixture; and sonicating the mixture. 22. The production method according to 21.

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