JP2012170936A - Carbon nanotube dispersant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carbon nanotube dispersant, which can carry out an isolated dissolution of a carbon nanotube up to a single size in a solvent such as an organic solvent.SOLUTION: The carbon nanotube dispersant includes as a repeat unit a constitution in which for example, a tricarbonyl benzene structure as shown in formulas (14) and (15) is a branching point, and comprises a hyperbranched polymer in which the weight-average molecular weight measured relative to polystyrene standards by a gel permeation chromatography is 1,000 to 2,000,000. Since the hyperbranched polymer is excellent in dissolution capability for carbon nanotubes, it is possible to obtain a composition in which a carbon nanotube is contained in an isolated dissolution state.

Description

  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 a tricarbonylbenzene structure as a branch point, and a carbon nanotube-containing composition containing the dispersant.

Carbon nanotubes (hereinafter sometimes abbreviated as CNT) are being considered as a useful material for nanotechnology, and their potential for application in a wide range of fields has been studied.
There are many applications such as a method using a single CNT itself, such as a transistor or a probe for a microscope, an electron emission electrode, a fuel cell electrode, or a conductive composite in which CNTs are dispersed. The CNTs are roughly divided into methods that are used 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 disperse | distributed 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 or the like serving as a matrix material.
However, CNTs are generally difficult to disperse, and in normal composites, CNT dispersion is used incompletely, and it is difficult to say that the performance of carbon nanotubes is sufficiently developed.
This problem has also led to difficulties in various applications of carbon nanotubes. For this reason, various methods for improving dispersibility by surface modification or surface chemical modification of CNT have been studied.

As a method of dispersing such CNTs, for example, there is a method of adding CNTs to an aqueous solution containing a low molecular surfactant such as sodium dodecyl sulfate (see Patent Document 1), and these low molecular surfactants are used. In this case, the ability to form a thin film is low, and it is necessary to further add a polymerizable monomer or polymer in order to facilitate thinning, and the conductivity is impaired due to the presence of these non-conductive organic substances. There is.
Also known is a method of attaching a polymer having a coiled structure to the CNT surface. Specifically, a method of attaching poly-m-phenylene vinylene-co-dioctoxy-p-phenylene vinylene to the CNT surface (Patent Literature). 2) has also been proposed. Here, it is possible to disperse CNTs in an organic solvent in isolation, and the polymer is shown attached to one CNT. However, after dispersion to a certain extent once, aggregation occurs, and CNTs are deposited as precipitates. It was intended to be collected and could not be stored in a state where CNTs were dispersed for a long time.

Furthermore, a method for improving dispersibility by chemically modifying the CNT by adding a functional group is also known (see Non-Patent Document 1).
However, this method has a problem that the π-conjugated system constituting the CNT is easily destroyed by chemical modification, and the original characteristics of the CNT 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 that is a water-soluble polymer (for example, see Non-Patent Document 2) is also known. The range is limited.
In addition, 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 (see, for example, Patent Document 3) has been proposed. The diameter of CNT that can be stably dispersed is limited.
Furthermore, using a polyoxyethylene compound which is a nonionic surfactant, a method of dispersing in an amide polar organic solvent (see, for example, Patent Document 4), a method of dispersing in polyvinylamide with pyrrolidone in an amide polar organic solvent (For example, refer patent document 5), the method (for example refer patent document 6) etc. which are made to disperse | distribute in alcohol type organic solvent are also proposed.
However, in these techniques, the polymers used as the dispersant are all linear polymers, and knowledge about hyperbranched polymers has not been clarified.

By the way, the highly branched 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.
While the shape of the general polymer is string-like, the highly branched polymer actively introduces branching, so it has a unique shape that has a relatively sparse internal space and particle properties, It has many terminals that can be modified by the introduction of various functional groups, and by utilizing these characteristics, there is a possibility that CNTs can be highly dispersed as compared with a linear polymer.

A method (see, for example, Patent Document 7 and Non-Patent Document 3) in which such a hyperbranched polymer is focused as a CNT dispersant has already been proposed.
However, in order to maintain the isolated and dissolved state of CNTs over a long period of time, heat treatment is required in addition to mechanical treatment, and the dispersibility of CNTs was not so high.
In addition, each of the hyperbranched polymers used as CNT dispersants has a low yield during synthesis, and in order to improve the yield, it is necessary to use a large amount of a metal catalyst as a coupling agent. Since the metal component may remain in the polymer, the application may be limited in the use of the composite with CNT.

JP-A-6-228824 JP 2000-44216 A JP 2008-24568 A JP-A-2005-75661 JP 2005-162877 A JP 2008-24522 A International Publication No. 2008/139839 Pamphlet

Science, vol. 282, p. 95-98, 1998 CHEMICAL PYSICS LETTERS, Vol. 342, p. 265-271, 2001 Proceedings of the 56th Annual Meeting of the Society of Polymer Science, vol. 56, no. 1, p. 1463, 2007

  This invention is made | formed in view of such a situation, and it aims at providing the carbon nanotube dispersing agent which can carry out isolation dissolution of the carbon nanotube to the single size in media, such as an organic solvent.

  As a result of intensive studies in order to achieve the above object, the present inventors have found that a highly branched polymer containing a tricarbonylbenzene structure as a branching point has excellent CNT dispersibility, and this highly branched polymer is converted to CNT. When used as a dispersant, it was found that CNT (at least a part thereof) can be isolated and dissolved up to its single size, and the present invention has been completed.

That is, the present invention
1. A carbon nanotube dispersant characterized by comprising a highly branched polymer containing a tricarbonylbenzene structure as a branch point and having a weight average molecular weight of 1,000 to 2,000,000 measured by gel permeation chromatography in terms of polystyrene ,
2. 1 carbon nanotube dispersant in which the hyperbranched polymer has a structural unit represented by the formula (1) as a repeating unit;
(In the formula, R and R ′ represent a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms, and Ar represents an aryl group which may have a substituent. )
3. The carbon nanotube dispersant of 2, wherein Ar is at least one represented by formulas (2) to (12),
[Wherein, R ^{1 to} R ⁸⁰ are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom. Represents an alkoxy group which may have a branched structure of 1 to 10, W ¹ and W ² are each independently a single bond, CR ⁸¹ R ⁸² (R ⁸¹ and R ⁸² are independently hydrogen An atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (however, they may be combined to form a ring), C = O, O, S , SO, SO ₂ , or NR ⁸³ (R ⁸³ represents a hydrogen atom or an alkyl group optionally having a branched structure having 1 to 10 carbon atoms), and X ¹ and X ² are independent of each other. An alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms. Or the formula (13)
(Wherein R ^{84 to} R ⁸⁷ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group optionally having a branched structure having 1 to 10 carbon atoms, or 1 carbon atom) Represents an alkoxy group which may have a branched structure of 1 to 10, Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms. To express.)
Represents a group represented by ]
4). The carbon nanotube dispersant of 2, wherein the repeating unit is represented by the formula (14):
5. The carbon nanotube dispersant of 2, wherein the repeating unit is represented by the formula (15):
6). A composition comprising any one of 2 to 5 carbon nanotube dispersants and carbon nanotubes,
7). 6. The composition according to 6, wherein the carbon nanotube dispersant is attached to the surface of the carbon nanotube to form a composite;
8). 6 or 7 composition further comprising an organic solvent,
9. 8. The composition according to 8, wherein the carbon nanotube is dispersed in the organic solvent,
10. 9 compositions wherein the complex is dispersed or dissolved in the organic solvent;
11. The composition according to any one of 2 to 10, wherein the carbon nanotube is at least one selected from single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes,
A thin film obtained from the composition of any one of 12.7 to 11,
13. A method for producing a composition comprising preparing a mixture by mixing the carbon nanotube dispersant of any one of 1 to 5, a carbon nanotube, and an organic solvent, and mechanically treating the mixture,
14 13 manufacturing methods in which the mechanical treatment is ultrasonic treatment;
15. 14 manufacturing methods of preparing the mixture by adding carbon nanotubes to a solution obtained by dissolving the carbon nanotube dispersant in the organic solvent, and sonicating the mixture;
16. A hyperbranched polymer having the structural unit represented by formula (14) as a repeating unit;
17. Hyperbranched polymer having structural unit represented by formula (15) as repeating unit
I will provide a.

Since the dispersant of the present invention is composed of a highly branched polymer having a hyperbranched structure containing a tricarbonylbenzene structure as a branching point, it is excellent in carbon nanotube dispersibility.
By using the dispersant of the present invention, at least a part of the carbon nanotubes can be separated up to its single size and stably dispersed (without agglomeration) 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 each carbon nanotube is separated into individual pieces without causing the carbon nanotubes to become clumps, bundles or ropes due to mutual cohesive force. The state which is doing.
In addition, the carbon nanotubes can be dispersed simply by subjecting the composition containing the dispersant, the carbon nanotubes, and the organic solvent to a mechanical treatment such as ultrasonic treatment, and additional steps such as heat treatment can be omitted in the dispersion. And processing time can be shortened.
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 of 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 ¹ H-NMR spectrum diagram of a hyperbranched polymer obtained in Synthesis Example 1. FIG. 2 is a ¹ H-NMR spectrum diagram of a hyperbranched polymer obtained in Synthesis Example 2. FIG. 4 is a ¹ H-NMR spectrum diagram of a hyperbranched polymer obtained in Synthesis Example 3. FIG. 4 is a ¹ H-NMR spectrum diagram of a hyperbranched polymer obtained in Synthesis Example 4. FIG. 1 is a ¹ H-NMR spectrum diagram of a linear polymer obtained in Comparative Synthesis Example 1. FIG. 2 is a ¹ H-NMR spectrum diagram of a linear polymer obtained in Comparative Synthesis Example 2. FIG.

Hereinafter, the present invention will be described in more detail.
The carbon nanotube dispersant according to the present invention contains a tricarbonylbenzene structure as a branch point, and has a weight average molecular weight of 1,000 to 2,000,000 as measured by gel permeation chromatography (hereinafter referred to as GPC) in terms of polystyrene. It is made of a hyperbranched polymer having a hyperbranched structure.
Since this highly branched polymer is considered to exhibit high affinity for the conjugated structure of CNT through the π-π interaction derived from the aromatic ring of the tricarbonylbenzene structure, a high dispersibility of CNT is expected, Depending on the combination and conditions of the above-mentioned tricarbonylbenzenes and comonomers selected from diamines, various skeleton designs, functional group introductions, control of molecular weight and distribution, etc., and addition of functions are possible. Has characteristics. In addition, since it has a branched structure, it has a high solubility that cannot be seen in a straight chain, and a highly branched polymer containing tricarbonylbenzene as a branching point has excellent thermal stability, Application as organic EL is also expected because of its excellent hole transportability.

  In the present invention, if the weight average molecular weight of the polymer is less than 1,000, the dispersibility of CNTs may be significantly reduced or the dispersibility may not be exhibited. 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 the present invention, the repeating unit structure of the hyperbranched polymer having a tricarbonylbenzene structure as a branch point is not particularly limited, but a highly branched polyamide obtained from a tricarbonylbenzene derivative and an aromatic diamine is preferred, In particular, those represented by the following formula (1) are preferable.

(In the formula, R and R ′ represent a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms, and Ar represents an aryl group which may have a substituent. .)

  The alkyl group which may have a branched structure having 1 to 10 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n- Butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2 -Methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2, -Dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl- n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2 -Dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1, 1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, Cyclohexyl group, 1-methyl-cyclopentyl Group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3- Dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group 2-n-propyl-cyclopropyl group, 1-isopropyl-cyclopropyl group, 2-isopropyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2 -Ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group and the like.

  In the formula (1), the aryl group which may have a substituent is not particularly limited. However, in consideration of increasing the dispersibility of the carbon nanotube, in the present invention, the following formula (2) It is preferable to use at least one kind represented by (12) to (12), and since it provides a highly branched polymer with more excellent dispersibility of carbon nanotubes, it is particularly represented by formulas (2), (6) and (12). Aryl groups are preferred.

In formulas (2) to (12), R ^{1 to} R ⁸⁰ are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, or an alkyl group that may have a branched structure having 1 to 10 carbon atoms. Or an alkoxy group which may have a branched structure having 1 to 10 carbon atoms.
W ¹ and W ² are each independently a single bond, CR ⁸¹ R ⁸² (R ⁸¹ and R ⁸² are each independently a hydrogen atom or a branched structure having 1 to 10 carbon atoms. An alkyl group which may be combined to form a ring), C═O, O, S, SO, SO ₂ , or NR ⁸³ (R ⁸³ is hydrogen) Represents an atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group which may have a branched structure having 1 to 10 carbon atoms include the same ones as described above.
Examples of the ring formed by R ⁸¹ and R ⁸² together include a cyclopentane ring and a cyclohexane ring.
Examples of the alkoxy group which may have a branched structure having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group and t-butoxy group. , N-pentoxy group and the like.

X ¹ and X ² each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (13).

R ^{84 to} R ⁸⁷ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group that may have a branched structure having 1 to 10 carbon atoms, or a branched group having 1 to 10 carbon atoms. An alkoxy group which may have a structure is represented, and Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms.
Examples of the halogen atom, the alkyl group and the alkoxy group which may have a branched structure having 1 to 10 carbon atoms are the same as those described above.
Examples of the alkylene group which may have a branched structure having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.

  Specific examples of the aryl group represented by the above formulas (2) to (12) include those represented by the following formula, but are not limited thereto.

  Specific examples of the repeating unit containing a tricarbonylbenzene ring in the hyperbranched polymer suitably used in the present invention include those represented by the following formulas (14) and (15), but are not limited thereto. Absent.

An example is given and demonstrated about the manufacturing method of the hyperbranched polymer used as a carbon nanotube dispersing agent of the present invention.
For example, as shown in Scheme 1 below, a hyperbranched polymer having a repeating structure (14 ′) is obtained by reacting a trihalogenated benzenecarbonyl compound (16) and a diamino compound (17) in a suitable organic solvent. be able to.
Further, as shown in Scheme 2 below, a hyperbranched polymer having a repeating structure (14 ′) is obtained by using an equivalent amount of a trihalogenated benzenecarbonyl compound (16) and a diamino compound (17) in an appropriate organic solvent. It can also be synthesized from the compound (18) obtained by the reaction.
By using this method, a highly branched polymer can be produced inexpensively, easily and safely. Since this production method is significantly shorter than the reaction time for synthesizing a general polymer, it is a production method suitable for environmental considerations in recent years and can reduce CO ₂ emissions. Moreover, stable production is possible even if the production scale is greatly increased, and the stable supply system at the industrialization level is not impaired.

(In the formula, X represents a halogen atom independently of each other. R represents the same meaning as described above.)

(In the formula, X represents a halogen atom independently of each other. R represents the same meaning as described above.)

In the case of the method of Scheme 1, the amount of each raw material charged is arbitrary as long as the target polymer is obtained, but the diamino compound (17) 0. 01 to 10 equivalents are preferred.
As the organic solvent, various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, tetramethylurea, Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ′, N′-tetramethylmalonic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methylformamide, N, N′-dimethylpropylene urea Amide solvents such as, and mixed solvents thereof
Among these, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixed system thereof are preferable, and N, N-dimethylacetamide, N-methyl-2-pyrrolidone are particularly preferable. Is preferred.

In the reaction of Scheme 1 and the second stage reaction of Scheme 2, the reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, and is particularly preferably about -20 to 100 ° C. 10-50 degreeC is more preferable.
In the reaction of Scheme 1 and the second stage reaction of Scheme 2, various commonly used bases can be used.
Specific examples of this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, oxidized Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6 -Tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like.
The amount of the base added is preferably 1 to 100 equivalents and more preferably 1 to 10 equivalents per 1 equivalent of the trihalogenated benzenecarbonyl compound (16). These bases may be used as an aqueous solution.
In the polymer obtained using the compound represented by the formula (14 ′) as a raw material, it is preferable that the raw material component does not remain, but a part of the raw material may remain as long as the effect of the present invention is not impaired. .
In any of the scheme methods, after completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

In the present invention, at least one of the halogen atoms of the terminal tricarbonylbenzene ring is substituted with an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group. It may be capped with a group, alkoxy group, aralkyloxy group, aryloxy group, ester group or the like.
Examples of the alkyl group and alkoxy group are the same as those described above.
Specific examples of the ester group include a methoxycarbonyl group and an ethoxycarbonyl group.
Specific examples of the aryl group include a phenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, and a p-methoxy group. Phenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, Examples include 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.
Specific examples of the aralkyl group include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group, p-ethylphenylmethyl group, 2-propylphenyl group. Examples thereof include a methyl group, 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, α-naphthylmethyl group and the like.

  Specific examples of the alkylamino group include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, s-butylamino group, t-butylamino group, n -Pentylamino group, 1-methyl-n-butylamino group, 2-methyl-n-butylamino group, 3-methyl-n-butylamino group, 1,1-dimethyl-n-propylamino group, 1,2 -Dimethyl-n-propylamino group, 2,2-dimethyl-n-propylamino group, 1-ethyl-n-propylamino group, n-hexylamino group, 1-methyl-n-pentylamino group, 2-methyl -N-pentylamino group, 3-methyl-n-pentylamino group, 4-methyl-n-pentylamino group, 1,1-dimethyl-n-butylamino group, 1,2- Methyl-n-butylamino group, 1,3-dimethyl-n-butylamino group, 2,2-dimethyl-n-butylamino group, 2,3-dimethyl-n-butylamino group, 3,3-dimethyl- n-butylamino group, 1-ethyl-n-butylamino group, 2-ethyl-n-butylamino group, 1,1,2-trimethyl-n-propylamino group, 1,2,2-trimethyl-n- Examples include a propylamino group, a 1-ethyl-1-methyl-n-propylamino group, and a 1-ethyl-2-methyl-n-propylamino group.

Specific examples of the aralkylamino group include benzylamino group, methoxycarbonylphenylmethylamino group, ethoxycarbonylphenylmethylamino group, p-methylphenylmethylamino group, m-methylphenylmethylamino group, o-ethylphenylmethylamino group. M-ethylphenylmethylamino group, p-ethylphenylmethylamino group, 2-propylphenylmethylamino group, 4-isopropylphenylmethylamino group, 4-isobutylphenylmethylamino group, naphthylmethylamino group, methoxycarbonylnaphthylmethyl An amino group, an ethoxycarbonyl naphthylmethylamino group, etc. are mentioned.
Specific examples of the arylamino group include phenylamino group, methoxycarbonylphenylamino group, ethoxycarbonylphenylamino group, naphthylamino group, methoxycarbonylnaphthylamino group, ethoxycarbonylnaphthylamino group, anthranylamino group, pyrenylamino group, biphenylamino. Group, terphenylamino group, fluorenylamino group and the like.

  The alkoxysilyl group-containing alkylamino group may be any of a monoalkoxysilyl group-containing alkylamino group, a dialkoxysilyl group-containing alkylamino group, or a trialkoxysilyl group-containing alkylamino group. Methoxysilylpropylamino group, 3-triethoxysilylpropylamino group, 3-dimethylethoxysilylpropylamino group, 3-methyldiethoxysilylpropylamino group, N- (2-aminoethyl) -3-dimethylmethoxysilylpropylamino group Group, N- (2-aminoethyl) -3-methyldimethoxysilylpropylamino group, N- (2-aminoethyl) -3-trimethoxysilylpropylamino group and the like.

Specific examples of the aryloxy group include a phenoxy group, a naphthoxy group, an anthranyloxy group, a pyrenyloxy group, a biphenyloxy group, a terphenyloxy group, and a fluorenyloxy group.
Specific examples of the aralkyloxy group include benzyloxy group, p-methylphenylmethyloxy group, m-methylphenylmethyloxy group, o-ethylphenylmethyloxy group, m-ethylphenylmethyloxy group, p-ethylphenylmethyl group. Examples include an oxy group, 2-propylphenylmethyloxy group, 4-isopropylphenylmethyloxy group, 4-isobutylphenylmethyloxy group, α-naphthylmethyloxy group, and the like.

  These groups can be easily introduced by substituting the halogen atom of the trihalogenated benzenecarbonyl compound (16) with a monofunctional substance that provides a corresponding substituent, and, for example, shown in the following scheme 3 As described above, the hyperbranched polymer (19) having a phenylamino group at at least one terminal is obtained by adding an aniline derivative and reacting.

(In the formula, X and R represent the same meaning as described above.)

The terminal modification is performed by treating a hyperbranched polymer having a repeating structure (14 ′) obtained by reacting a trihalogenated benzenecarbonyl compound (16) and a diamino compound (17) with a monofunctional substance such as aniline. Alternatively, the compounds (16) and (17) may be treated by reacting them in the presence of a monofunctional substance such as aniline, but the solubility of the obtained hyperbranched polymer in an organic solvent is increased. In view of this, the latter method is preferable.
At this time, the amount of the monofunctional substance such as aniline is not particularly limited, but is preferably 0.01 to 10 equivalents per 1 equivalent of the trihalogenated benzenecarbonyl compound (16). .1 to 5 equivalents are more preferable.

The carbon nanotube-containing composition according to the present invention includes the carbon nanotube dispersant described above and carbon nanotubes.
Carbon nanotubes (CNT) are produced by arc discharge method, chemical vapor deposition method (CVD method), laser ablation method, etc. The CNT used in the present invention may be obtained by any method. . In addition, single-walled CNT (hereinafter referred to as SWCNT) in which one carbon film (graphene sheet) is wound in a cylindrical shape and two-layered CNT in which two graphene sheets are wound in a concentric shape. (Hereinafter referred to as DWCNT) and multi-layer CNT (hereinafter referred to as MWCNT) in which a plurality of graphene sheets are concentrically wound, but in the present invention, SWCNT, DWCNT, and MWCNT are each a single unit, Or a combination of several can be used.

  When producing SWCNT, DWCNT, and MWCNT by the above method, fullerene, graphite, and amorphous carbon are produced as by-products at the same time, 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 the CNT and may impair the original characteristics of the CNT. Therefore, it is desirable to use without purification.

The composition of the present invention may further contain an organic solvent capable of dissolving the dispersant (hyperbranched polymer).
Examples of such an organic solvent include ether compounds such as tetrahydrofuran (THF), diethyl ether, 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 and the like Alcohols; aliphatic hydrocarbons such as n-heptane, n-hexane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and the like. It can be used as a mixture or more.
In particular, NMP, methanol, and isopropanol are preferable from the viewpoint that the ratio of isolated dissolution of CNT can be improved, and ethylene glycol monoethyl ether and ethylene glycol monobutyl ether are used as additives that can also improve the film-forming property of the composition. It is desirable to contain a small amount of a solvent of glycol ethers such as propylene glycol monomethyl ether.

The method for preparing the composition of the present invention is arbitrary. When the dispersant (hyperbranched polymer) is liquid, the dispersant and CNT are mixed as appropriate, and when the dispersant is solid, it is melted. Then, it can be prepared by mixing with CNTs.
Moreover, when using an organic solvent, what is necessary is just to mix a dispersing agent, CNT, and an organic solvent in arbitrary orders, and to prepare a composition.
At this time, it is preferable to disperse a mixture of a dispersant, CNT, and an organic solvent, and this treatment can further improve the ratio of isolated dissolution of CNT. 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 CNT in the composition of the present invention can be about 1000: 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 -20 mass%, and it is more preferable to set it as about 0.005-10 mass%.
Furthermore, the concentration of CNTs in the composition is arbitrary as long as at least a part of the CNTs are isolated and dissolved, 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 composition of the present invention prepared as described above, it is presumed that the dispersant adheres to the surface of the CNT to form a complex.

The composition of the present invention can be mixed and mixed with a general-purpose synthetic resin soluble in the various organic solvents described above.
Specific examples of the general-purpose synthetic resin include polyolefin resins such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); PS (polystyrene) ), HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer), etc .; polycarbonate resin ; Vinyl chloride resin; polyamide resin; polyimide resin; (meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate Polyester resins such as PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate / adipate; 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 resin, etc. These thermosetting resins can be mentioned.

The CNT-containing composition (dispersion liquid) of the present invention is applied on an appropriate substrate such as PET, glass, ITO 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, it is possible to form a film.
The obtained thin film can be suitably used for an antistatic film utilizing the metallic properties of carbon nanotubes, a conductive material such as a transparent electrode, a photoelectric conversion device utilizing the semiconductor properties, an electroluminescent device, and the like.

Hereinafter, although a synthesis example, an Example, and a comparative example are 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: Modified to SHIMADZU SCL-10Avp GPC Column: Shodex K-804L + K-805L
Column temperature: 60 ° C
Solvent: N-methyl-2-pyrrolidone (1% by mass added LiCl)
Detector: UV (254 nm)
Calibration curve: Standard polystyrene (2) ¹ H-NMR spectrum Apparatus: JNM-ECA700 manufactured by JEOL Datum Co., Ltd.
Solvent: DMSO-d ₆
Internal standard: Tetramethylsilane (3) Hot plate (pre-baked)
Device: ND-2 manufactured by AS ONE Corporation
(4) Probe-type ultrasonic irradiation device (dispersion processing)
Apparatus: UIP1000 manufactured by Hielscher Ultrasonics
(5) 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)
(6) Haze meter (total light transmittance measurement)
Device: NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.
(7) Differential thermal balance (TG-DTA)
Device: TG-8120, manufactured by Rigaku Corporation
Temperature increase rate: 10 ° C / min Measurement temperature: 20-500 ° C
(8) Photo DSC
Device: DSC 204F1 Phoenix made by NETZSCH
Temperature increase rate: 30 ° C / min Measurement temperature: 25-300 ° C
(9) Micro shape measuring machine (surf coder)
Equipment: ET4000A manufactured by Kosaka Laboratory Ltd.

CNT-1: Unrefined MWCNT (“C Tube 100” manufactured by CNT, outer diameter of 10 to 30 nm)
PVP: Polyvinylpyrrolidone (Tokyo Chemical Industry Co., Ltd. K15)
NMP: N-methyl-2-pyrrolidone

[1] Synthesis of dispersant (tricarbonylbenzene-based hyperbranched polymer) [Synthesis Example 1]
In a 100 mL four-necked flask under nitrogen, 1,3,5-benzenetricarbonyltrichloride (5 g, 18.8 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and dimethylacetamide (35.3 g, manufactured by Junsei Chemical Co., Ltd.) 1,3-phenylenediamine (1.53 g, 14.1 mmol, manufactured by DuPont Co., Ltd.) and aniline (1.32 g, 14.1 mmol, manufactured by Junsei Chemical Co., Ltd.) were added to dimethylacetamide (35.3 g). The solution dissolved in Junsei Chemical Co., Ltd. was dropped at an internal temperature of −15 ° C. over 30 minutes for polymerization. After dropping, the mixture was stirred at room temperature for 1 hour, and the reaction solution was added to pure water (750 g) to cause reprecipitation. The resulting precipitate was filtered and dissolved again in THF (75 g, manufactured by Kanto Chemical Co., Inc.), and this was added to pure water (750 g) for reprecipitation. The obtained precipitate was filtered and dried in a vacuum dryer at 150 ° C. for 2 hours to obtain 5.5 g of a target tricarbonylbenzene-based hyperbranched polymer (hereinafter abbreviated as TmPDA-An). The measurement result of the ¹ H-NMR spectrum of TmPDA-An is shown in FIG.
The weight average molecular weight Mw measured by GPC of TmPDA-An in terms of polystyrene was 11725, and the polydispersity Mw / Mn was 4.28.

[Synthesis Example 2]
In a 100 mL four-necked flask under nitrogen, 1,3,5-benzenetricarbonyltrichloride (2 g, 7.53 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and N-methyl-2-pyrrolidone (12 g, Junsei Chemical Co., Ltd.) 3,3′-diaminodiphenylsulfone (1.4 g, 5.64 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and aniline (0.63 g, 6.76 mmol, manufactured by Junsei Chemical Co., Ltd.) Was dissolved in N-methyl-2-pyrrolidone (18 g, manufactured by Junsei Chemical Co., Ltd.) dropwise at 30 ° C. for 30 minutes for polymerization. After dropping, the mixture was stirred at room temperature for 1 hour, and the reaction solution was added to pure water (150 g) to cause reprecipitation. The resulting precipitate was filtered and dried at 150 ° C. for 2 hours with a vacuum dryer to obtain 2.5 g of a target tricarbonylbenzene-based hyperbranched polymer (hereinafter abbreviated as TAS-An). The measurement result of ¹ H-NMR spectrum of TAS-An is shown in FIG.
The weight average molecular weight Mw measured in terms of polystyrene by GPC of TAS-An was 102432, and the polydispersity Mw / Mn was 26.05.

[Synthesis Example 3]
In a 100 mL four-necked flask under nitrogen, 1,3,5-benzenetricarbonyltrichloride (5 g, 18.8 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and N-methyl-2-pyrrolidone (29.4 g, Junsei Chemical) 1), 3-Phenylenediamine (1.53 g, 14.1 mmol, manufactured by DuPont) N-methyl-2-pyrrolidone (29.4 g, manufactured by Junsei Chemical Co., Ltd.) The solution dissolved in was dripped at an internal temperature of −15 ° C. over 30 minutes for polymerization. After dripping, pure water (10 g) and N-methylpyrrolidone (10 g, manufactured by Junsei Chemical Co., Ltd.) were added and stirred for 1 hour, and this was added to pure water (750 g) for reprecipitation. The obtained precipitate was filtered and dried in a vacuum dryer at 150 ° C. for 2 hours to obtain 4.4 g of a target tricarbonylbenzene-based hyperbranched polymer (hereinafter abbreviated as TmPDA). The measurement result of ¹ H-NMR spectrum of TmPDA is shown in FIG.
The weight average molecular weight Mw measured in terms of polystyrene by GPC of TmPDA was 2717, and the polydispersity Mw / Mn was 2.77.

[Synthesis Example 4]
In a 50 mL four-necked flask under nitrogen, 1,3,5-benzenetricarbonyltrichloride (2 g, 7.53 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and N-methyl-2-pyrrolidone (13.2 g, Junsei Chemical) ), 3,3′-diaminodiphenylsulfone (0.94 g, 3.77 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and N-methyl-2-pyrrolidone (13.2 g, Junsei Chemical ( The solution dissolved in (made by Co., Ltd.) was dropped and polymerized at an internal temperature of -20 ° C. After dropping, pure water (2 g) was added dropwise and stirred at room temperature for 1 hour, and then the reaction solution was filtered and added to pure water (300 g) for reprecipitation. The resulting precipitate was filtered and dried in a vacuum dryer at 150 ° C. for 2 hours to obtain 1.35 g of a target tricarbonylbenzene hyperbranched polymer (hereinafter abbreviated as TAS). The measurement result of the ¹ H-NMR spectrum of TAS is shown in FIG.
The weight average molecular weight Mw measured by polystyrene conversion by TAS GPC was 85551, and the polydispersity Mw / Mn was 38.81.

[Comparative Synthesis Example 1]
Terephthaloyl chloride (3 g, 14.8 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and N-methyl-2-pyrrolidone (10.8 g, manufactured by Junsei Chemical Co., Ltd.) were charged into a 50 mL four-necked flask under nitrogen. 1,3-phenylenediamine (0.80 g, 7.39 mmol, manufactured by DuPont Co., Ltd.) in N-methyl-2-pyrrolidone (10.8 g, manufactured by Junsei Chemical Co., Ltd.) The polymerization was conducted dropwise at -15 ° C over 30 minutes. After dropping, the mixture was stirred at room temperature for 1 hour, pure water (3 g) was added dropwise and stirred for 30 minutes, and the reaction solution was added to pure water (240 g) to cause reprecipitation. The resulting precipitate was filtered and dried at 150 ° C. for 2 hours with a vacuum dryer to obtain 1.6 g of a target dicarbonylbenzene-based linear polymer (hereinafter abbreviated as TPmPDA). The measurement result of the ¹ H-NMR spectrum of TPmPDA is shown in FIG.
The weight average molecular weight Mw measured by GPC of TPmPDA in terms of polystyrene was 2792, and the polydispersity Mw / Mn was 2.83.

[Comparative Synthesis Example 2]
In a 50 mL four-necked flask under nitrogen, terephthaloyl chloride (3 g, 14.8 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and N-methyl-2-pyrrolidone (16.3 g, manufactured by Junsei Chemical Co., Ltd.) were added. First, 3,3′-diaminodiphenylsulfone (2.75 g, 11.1 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in N-methyl-2-pyrrolidone (16.3 g, manufactured by Junsei Chemical Co., Ltd.). The solution was polymerized dropwise at an internal temperature of −15 ° C. over 30 minutes. After dropping, the mixture was stirred at room temperature for 1 hour, pure water (3 g) was added dropwise and stirred for 30 minutes, and then the reaction solution was added to pure water (240 g) for reprecipitation. The obtained precipitate was filtered and dried at 150 ° C. for 2 hours with a vacuum dryer to obtain 4.5 g of a target dicarbonylbenzene linear polymer (hereinafter abbreviated as TPAS). The measurement result of ¹ H-NMR spectrum of TPAS is shown in FIG.
The weight average molecular weight Mw measured by polystyrene conversion by GPC of TPAS was 9157, and the polydispersity Mw / Mn was 4.01.

[Thermal analysis of each polymer]
For each of the polymers obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2, the glass transition temperature (Tg) was measured by DSC, and the 5% weight loss temperature (Td 5%) was measured by TG-DTA. The results are shown in Table 1.

[2] Production of carbon nanotube-containing composition and thin film [Example 1] Dispersion of CNT-1 using TmPDA-An 0.50 g of TmPDA-An obtained in Synthesis Example 1 was dissolved in 49.25 g of NMP, and this solution 0.25 g of CNT-1 was added. 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, 0.25 g of cyclohexanone was added 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 to obtain a transparent and uniform MWCNT / highly branched polymer thin film composite. Produced.

[Example 2] Dispersion of CNT-1 using TAS-An MWCNT-containing dispersion and MWCNT were obtained in the same manner as in Example 1 except that TmPDA-An was changed to TAS-An obtained in Synthesis Example 2. / A hyperbranched polymer thin film composite was prepared.

[Example 3] Dispersion of CNT-1 using TmPDA A MWCNT-containing dispersion and a MWCNT / highly branched polymer were obtained in the same manner as in Example 1 except that TmPDA-An was changed to TmPDA obtained in Synthesis Example 3. A thin film composite was prepared.

[Comparative Example 1] Dispersion of CNT-1 using TPmPDA (linear polymer) MWCNT-containing dispersion in the same manner as in Example 1 except that TmPDA-An was changed to TPmPDA obtained in Comparative Synthesis Example 1. And MWCNT / linear polymer thin film composites.

[Comparative Example 2] Dispersion of CNT-1 using TPAS (linear polymer) MWCNT-containing dispersion in the same manner as in Example 1 except that TmPDA-An was changed to TPAS obtained in Comparative Synthesis Example 2. And MWCNT / linear polymer thin film composites.

[Comparative Example 3] Dispersion of CNT-1 using PVP A MWCNT-containing dispersion and a MWCNT / linear polymer thin film composite were prepared in the same manner as in Example 1 except that TmPDA-An was changed to PVP.

The thin film uniformity, surface resistance, and total light transmittance of the thin film composites obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated. The uniformity of the thin film was evaluated visually according to the following criteria. Each evaluation result is shown in Table 2.
(1) Thin film uniformity ○: No clumps or irregularities such as aggregates can be confirmed.
(Triangle | delta): The aggregate and film nonuniformity of MWCNT are seen.
X: Aggregates and film unevenness of MWCNT are seen in most parts of the thin film, and evaluation as a film cannot be performed.

Separately, after each MWCNT-containing dispersion is allowed to stand at room temperature (approximately 25 ° C.) for 1 month, the presence of sediment in the dispersion is visually confirmed, and the dispersion stability of the dispersion is determined according to the following criteria. Evaluated. The evaluation results are also shown in Table 2.
(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.

As shown in Table 1, when Examples 1 to 3 and Comparative Examples 1 and 2 using a linear polymer having a similar skeleton were compared, the dispersants of Synthesis Examples 1 to 3 were higher in CNT concentration. It can be seen that the use of a dispersant having a highly branched structure is advantageous in dispersing CNT because it is stably dispersed.
Moreover, when Examples 1-3 and PVP which is a well-known dispersing agent with the same CNT / dispersing agent mixing ratio are compared, when the dispersing agent of the synthesis examples 1-3 was used, when the thin film was prepared As a result, the surface resistance value stably showed a level of 10 ³ to 10 ⁴ Ω / □, and the total light transmittance was equivalent or higher.
From the above points, it was revealed that the dispersant of the present invention is advantageous in obtaining a highly conductive and uniform thin film composite.
Furthermore, from the results of Example 1 and Example 3, the properties (surface resistance value, total light transmittance) of the thin film composite obtained can be adjusted by the amines (functional groups) used in the reaction, and the thin film composite It can be expected that the properties of the dispersion of the present invention are improved, and the dispersant of the present invention is also advantageous in this respect.

[3] Solvent resistance test of carbon nanotube-containing composition film [Example 4]
The film thickness and characteristics (surface resistance, total light transmittance) of the film obtained by further drying the MWCNT / highly branched polymer thin film composite produced in Example 1 at 100 ° C. for 10 minutes were measured.
Moreover, the film thickness and characteristic of the film | membrane which immersed the thin film composite after a heating for 5 minutes in NMP, and dried for 15 minutes at 100 degreeC were measured again. The results are shown in Table 3.

[Example 5]
The film thickness and characteristics (surface resistance, total light transmittance) of a film obtained by further drying the MWCNT / highly branched polymer thin film composite produced in Example 1 for 10 minutes at 200 ° C. were measured.
Moreover, the film thickness and characteristic of the film | membrane which immersed the thin film composite after a heating for 5 minutes in NMP, and dried for 15 minutes at 100 degreeC were measured again. The results are shown in Table 3.

[Comparative Example 4]
The film thickness and characteristics (surface resistance, total light transmittance) of a film obtained by further drying the MWCNT / linear polymer thin film composite prepared in Comparative Example 3 at 100 ° C. for 10 minutes were measured.
Moreover, the film thickness and characteristic of the film | membrane which immersed the thin film composite after a heating for 5 minutes in NMP solution and dried for 15 minutes at 100 degreeC were measured again. The results are shown in Table 3.

[Comparative Example 5]
The film thickness and characteristics (surface resistance, total light transmittance) of a film obtained by further drying the MWCNT / linear polymer thin film composite produced in Comparative Example 3 at 200 ° C. for 10 minutes were measured.
Moreover, the film thickness and characteristic of the film | membrane which immersed the thin film composite after a heating for 5 minutes in NMP solution and dried for 15 minutes at 100 degreeC were measured again.
The results of Examples 4 and 5 and Comparative Examples 4 and 5 are shown in Table 3.

As shown in Table 3, the film thickness after firing at each temperature of Examples 4 and 5 and Comparative Examples 4 and 5 was in the region of 0.11 to 0.13 μm.
In addition, in the films obtained by immersing the obtained films in NMP and then dried, a decrease in the film thickness was observed, but it can be seen that the higher the baking temperature, the higher the remaining film ratio.
When Examples 4 and 5 are compared with Comparative Examples 4 and 5, in the example using the highly branched polymer, the remaining film ratio was 62% even at a temperature increase of 100 ° C., and 77% at a temperature increase of 200 ° C. Although a high residual film rate was exhibited, in PVP, a residual film rate of 48% at 100 ° C., a residual film rate of 52% at 200 ° C., and an increase in the residual film rate due to the firing temperature were hardly confirmed.
The reason for this is that the dispersant of the present invention has many reactive ends such as amino groups and carboxylic acid groups in the molecule. Therefore, condensation within the molecule or between molecules occurs due to temperature rise, and the dispersant has an end. This is thought to be because the curing of the film proceeds even at a low temperature when compared with a non-linear polymer (PVP).
From the above points, it can be said that the dispersant of the present invention is advantageous in obtaining a thin film composite having excellent solvent resistance.

Claims (17)

  A carbon nanotube dispersant comprising a highly branched polymer containing a tricarbonylbenzene structure as a branch point 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 carbon nanotube dispersant according to claim 1, wherein the hyperbranched polymer has a structural unit represented by the formula (1) as a repeating unit.
(In the formula, R and R ′ represent a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms, and Ar represents an aryl group which may have a substituent. ) The carbon nanotube dispersant according to claim 2, wherein the Ar is at least one kind represented by formulas (2) to (12).
[Wherein, R ^{1 to} R ⁸⁰ are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or 1 carbon atom. Represents an alkoxy group which may have a branched structure of 1 to 10, W ¹ and W ² are each independently a single bond, CR ⁸¹ R ⁸² (R ⁸¹ and R ⁸² are independently hydrogen An atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (however, they may be combined to form a ring), C = O, O, S , SO, SO ₂ , or NR ⁸³ (R ⁸³ represents a hydrogen atom or an alkyl group optionally having a branched structure having 1 to 10 carbon atoms), and X ¹ and X ² are independent of each other. An alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms. Or the formula (13)
(Wherein R ^{84 to} R ⁸⁷ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group optionally having a branched structure having 1 to 10 carbon atoms, or 1 carbon atom) Represents an alkoxy group which may have a branched structure of 1 to 10, Y ¹ and Y ² each independently represent an alkylene group which may have a single bond or a branched structure of 1 to 10 carbon atoms. To express.)
Represents a group represented by ] The carbon nanotube dispersant according to claim 2, wherein the repeating unit is represented by the formula (14).
The carbon nanotube dispersant according to claim 2, wherein the repeating unit is represented by the formula (15).
  The composition containing the carbon nanotube dispersing agent of any one of Claims 2-5, and a carbon nanotube.   The composition according to claim 6, wherein the carbon nanotube dispersant is attached to the surface of the carbon nanotube to form a composite.   The composition according to claim 6 or 7, further comprising an organic solvent.   The composition according to claim 8, wherein the carbon nanotubes are dispersed in the organic solvent.   The composition according to claim 9, wherein the complex is dispersed or dissolved in the organic solvent.   The composition according to any one of claims 2 to 10, wherein the carbon nanotube is at least one selected from single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.   The thin film obtained from the composition of any one of Claims 7-11.   The manufacturing method of the composition which mixes the carbon nanotube dispersing agent of any one of Claims 1-5, a carbon nanotube, and an organic solvent, prepares a mixture, and mechanically processes this mixture.   The manufacturing method according to claim 13, wherein the mechanical treatment is ultrasonic treatment.   The method according to claim 14, wherein the mixture is prepared by adding carbon nanotubes to a solution obtained by dissolving the carbon nanotube dispersant in the organic solvent, and the mixture is subjected to ultrasonic treatment. A hyperbranched polymer having the structural unit represented by formula (14) as a repeating unit.
A hyperbranched polymer having a structural unit represented by formula (15) as a repeating unit.