TW201107373A - Carbon nanotube dispersing/solubilizing agent - Google Patents

Abstract

Disclosed is a carbon nanotube dispersing/solubilizing agent which is composed of a hyperbranched polymer that contains a triazine ring represented, for example, by formula (14), (15) or (16) as a repeating unit and has a weight average molecular weight of 1,000-4,000,000 in terms of polystyrene as determined by gel permeation chromatography. Since the hyperbranched polymer has excellent carbon nanotube dissolving power, a composition in which carbon nanotubes are isolatedly dissolved can be obtained using the hyperbranched polymer as a solubilizing agent.

Description

201107373 VI. Description of the Invention: [Technical Field] The present invention relates to a carbon nanotube dispersion, a solubilizing agent, and more particularly, to a highly branched polymer containing a triazine ring as a repeating unit The carbon nanotubes are composed of a dispersing agent. [Prior Art] Carbon nanotubes (hereinafter, sometimes referred to simply as CNTs) have been studied for a wide range of applications in terms of useful materials for nanotechnology. The use is roughly divided into: a transistor or a microscope probe, etc., using a separate method of CNT itself, and an electron-releasing electrode or a fuel cell electrode, or a conductive composite of dispersed CNT, etc., collecting a majority The method of using CNTs to form a block. When a single CNT is used, a method in which CNTs are added to a solvent and irradiated with ultrasonic waves, and only a single dispersed CNT is taken out by electrophoresis or the like is used. Further, in the conductive composite used for the block, it is necessary to satisfactorily disperse the CNT in the polymer or the like which becomes the base material. However, CNTs are generally difficult to disperse, and their dispersion is incomplete in a composite obtained by a general dispersion method. Therefore, the dispersion is improved by various methods such as surface modification of CNT or surface chemical modification. For the method of modifying the surface of the CNT, for example, a method of adding CNT to an aqueous solution containing a surfactant such as sodium dodecylsulfonate (refer to -5 to 201107373 Patent Document 1: JP-A-6-22 8 824 Bulletin). However, in this method, since the non-conductive organic substance adheres to the surface of the CNT, the conductivity is impaired. Further, a method of attaching a polymer having a helical structure to a surface of a CNT is known, and specifically, a solvent containing a poly-m-phenylene-vinyl-co-dioctyloxy-p-phenylene-vinyl group A method of separating and refining a precipitated CNT composite by adding CNTs has been proposed (Patent Document 2: JP-A-2000-442166), and the polymer-based conjugate system is incomplete, and is also damaged at this time. Conductivity of CNTs Further, a method of performing chemical modification to enhance dispersibility by a single-layer CNT addition functional group or the like is also known (Non-Patent Document 1: Science, Vol. 2 82, 1989). However, in this method, the π-conjugated structure which constitutes the CNT by chemical modification is easily destroyed, and the original characteristics of the CNT are also impaired at this time. As described above, when the surface of the CNT is modified, the dispersibility of the CNT can be somewhat improved, but another problem that the original characteristic of the CNT having high conductivity or the like is damaged is caused. Further, in the above-described method, a block of CNTs of several mm order can be reduced to a block of several μm, but dissolved (dispersed) to a size of CNT alone (diameter: 0.8 to 100 nm), that is, isolated and dissolved It is impossible. In this case, Patent Document 2 discloses a case where a polymer is attached around one CNT, but the method of this document is temporarily dispersed to a certain extent, and agglomerates and precipitates to capture CNTs, which does not allow CNTs to pass through for a long period of time. Save in a dissolved state. -6-201107373 In addition, in Patent Document 1, a conjugated polymer is used as a solubilizing agent (dispersant), and as a result of coating the CNT surface with a conjugated polymer, CNTs are uniformly dispersed in the resin, so that they can be used. The original conductivity of CNT has been reported. In this technique, a conjugated polymer which is used as a dispersing agent is developed because of a conjugated structure, and it is advantageous in terms of conductivity or semiconductor characteristics. However, in Patent Document 1, the conjugated polymer is only for revealing a linear polymer, and the knowledge about the highly branched polymer is not clear. Further, in order to solve the above problems, a method of dispersing CNTs by a water-soluble polymer such as polyvinylpyrrolidone is also known (Non-Patent Document 2: Carbon > Vol. 41, pp. 797 -8 09 * 2003), but it is water soluble, so its application range is limited. In addition, a method of dispersing a compound having a basic functional group in an organic solvent of a ketone type has been proposed as a method of using an organic solvent (Patent Document 3: JP-A-2008-24568), but no basic functional group is involved. It is specified in detail that the diameter of the CNT which can be stably dispersed is limited. Further, a method of dispersing a polyoxyethylene compound of a nonionic surfactant in a polar organic solvent of a guanamine type (Patent Document 4: JP-A-2005-7566 1), and dispersing it by polyvinylpyrrolidone The method of the melamine-based polar organic solvent (Patent Document 5: JP-A-2005-162877) and the method of dispersing it in an alcohol-based organic solvent (Patent Document 6: JP-A-2008-24522) have also been put forward. However, even in this technique, a polymer which is used as a dispersing agent is a linear polymer, and the knowledge about the highly branched polymer is not clear. 201107373 In addition, the technology of the high-branched polymer 1 is focused on the CNT dispersant (Non-Patent Document 3: The 56th Polymer Society Annual Conference Pre-Collection Vol. 56, No. 1, p. 1 463, 2007) has also been proposed. The highly branched polymer is a star polymer, a dendrimer classified as a dendritic polymer, a hyperbranched polymer or the like, and has a branched polymer in the skeleton. Such a highly branched polymer is generally a rope-like shape, but is actively introduced into a branch, so that it is used as a dispersing agent, and it is possible to exhibit excellent CNT isolation as compared with a linear polymer. Disperse and dissolve energy. However, in the technique of Non-Patent Document 3 in which a highly branched polymer is used as a dispersing agent, the state in which the CNT is isolated and dispersed for a long period of time is required, and heat treatment is required in addition to the mechanical treatment, and the solubilization energy of the CNT is not so high. CITATION LIST PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT Patent Document 4: JP-A-2005-292801 Patent Document 5: JP-A-2005-162877, Patent Document 6: JP-A-2008-24522, Non-Patent Document Non-Patent Document 1: Science, Vol. 282, 1998 Non-Patent Document 2: Carbon, Vol. , pp. 797-809, 2003 Non-Patent Document 3: The 56th Annual Meeting of the Polymer Society Annual Conference, -8-201107373 ν〇1·56, Νο·1, ρ.1 463, 2007. SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object thereof is to provide a carbon nanotube which can be dissolved in a medium of an organic solvent or the like to its individual size. Tube solubilizer. Dispersant. Means for Solving the Problem The inventors of the present invention have found that the highly branched polymer containing a triazine ring as a repeating unit is excellent in dispersion and dissolution energy of a carbon nanotube, in order to achieve the above object. And when the hyperbranched polymer is used as the carbon nanotube dispersion/solubilizing agent, the carbon nanotubes (at least a part of them) can be dissolved in isolation to their individual sizes, and the present invention is completed. That is, the present invention provides: 1 - a carbon nanotube dispersion/solubilizing agent, which is determined by a polystyrene conversion obtained by a gel permeation chromatography layer containing a triazine ring as a repeating unit. It is composed of a highly branched polymer having a weight average molecular weight of 1,000 to 4,000,000. 2. The carbon nanotube dispersion/solubilizing agent according to Item 1, wherein the repeating unit is represented by the following formula (1). 201107373

(wherein R and R1 represent a hydrogen atom or an alkyl group which may have a branched structure of 1 to 10 carbon atoms, and Ar represents an aryl group which may have a substituent). 3. The carbon nanotube dispersion/solubilizing agent according to Item 1, wherein the Ar is at least one of the formulae (2) to (12). [Chemical 2] R1 R2 ϋ (2) (3) R?5 R24 R?3 R22Jrh one (6)

R3^ R33 R35 (4) R31 R33R3^ I ^R30 R28 (5) , R29 40 R39

R41 - W (8) iRf R37A:.

(7) (10)

R (11) R78 R77 R?6

[wherein R1 to R8Q independently represent a hydrogen atom, a halogen atom, a carboxyl group, or an alkyl group having a branched structure having a carbon number of 1 to 1 Å, or may be -10-201107373 having a carbon number of 1 to 10 The alkoxy group of the branched structure, w1 and W2 independently of each other represent a single bond, and CR81R82 (R81 and R82 independently represent a hydrogen atom or an alkyl group having a branched structure of 1 to 1 carbon atoms (however, such It may also be - to form a ring)), C = 0, 0, S, S0, S02, or NR83 (R83 represents a hydrogen atom or an alkyl group which may also have a branched structure of 1 to 1 carbon number), X1 And X2 independently of each other to represent a single bond, or a branched alkyl group having a branched structure of 1 to 1 Å, or a formula (13) [Chemical 3] J (R87 R: R* Y2-^. Π 3) (wherein R84 to R87 independently represent a hydrogen atom, a halogen atom, a carboxyl group, a fluorenyl group, or an alkyl group having a branched structure having a carbon number of 1 to 1 Å, or may have a carbon number of 1 to 1 Å. The alkoxy group ''1' and γ2 of the branched structure each independently represent a single bond or a group which may also have a branched alkyl group having a branched structure of 1 to 10 carbon atoms). 4. The carbon nanotube dispersion according to item 2, the solubilizing agent' wherein the above-mentioned repeating unit is represented by the following formula (14). -11 - 201107373 [化4]

(14) The carbon nanotube dispersion/solvent according to item 2, wherein the repeating unit is represented by the following formula (15).

6. The carbon nanotube dispersion/solubilizing agent according to Item 2, wherein the repeating unit is represented by the following formula (16). [Chemical 6]

7. A composition comprising the carbon-12-201107373 nanotube dispersion of any one of items 2 to 6. a solubilizing agent and a carbon nanotube. 8. The composition according to Item 7, wherein the carbon nanotube dispersion/solubilizing agent is attached to a surface of the carbon nanotube to form a composite. 9. The composition according to Item 7 or 8, which further comprises an organic solvent. The composition according to item 9, wherein the carbon nanotube is dispersed in the organic solvent. 11. The composition according to item 9, wherein the aforementioned complex is dispersed or dissolved in the aforementioned organic solvent. 12. The composition according to any one of items 2 to 11, wherein the carbon nanotube is at least one selected from the group consisting of a single carbon nanotube, a two carbon nanotube, and a multilayer carbon nanotube. A film which can be obtained from the composition of any one of items 7 to 12. 1 a method for producing a composition by mixing a carbon nanotube dispersion/solubilizing agent, a carbon nanotube, and an organic solvent according to any one of items 1 to 6 to prepare a mixture, and mechanically treating the mixture . The manufacturing method of item 14, wherein the mechanical treatment is ultrasonic treatment. 16. The production method according to item 15, wherein the mixture is prepared by adding a carbon nanotube to a solution obtained by dissolving the carbon nanotube dispersion/solubilizing agent in the organic solvent, and ultrasonically treating the mixture. EFFECTS OF THE INVENTION-13-201107373 The carbon nanotube dispersion/solubilizing agent of the present invention is composed of a highly branched polymer containing a triazine ring, so that the carbon nanotubes can be dispersed and dissolved in an excellent energy. The carbon nanotubes are dissolved in isolation to their individual sizes. Therefore, a carbon nanotube-containing composition in which the carbon nanotubes (at least a part thereof) are dispersed in an isolated dissolved state can be easily obtained by using the solubilizing agent' of the present invention. Since this composition can easily adjust the amount of the carbon nanotubes, it can be suitably used as a semiconductor material, a conductor material, or the like. MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The carbon nanotube dispersion/solubilizing agent of the present invention has a weight average molecular weight measured by polystyrene conversion obtained by a gel permeation chromatography (hereinafter referred to as GPC) containing a triazine ring as a repeating unit. 1, 〇〇〇 ~ 4,000,000 high-branched polymer. The highly branched polymer containing the triazine ring as a repeating unit is excellent in stability and exhibits excellent hole transportability, and is therefore expected to be applied to organic EL. Further, the use of an appropriate dopant such as an anion such as a peroxy acid ion, an iodide ion, a bromide ion or a sulfate ion to exhibit an approximate conductivity of the conductor is also expected to be utilized as a conductive polymer. In the present invention, if the weight average molecular weight of the polymer is less than 100 00, the solubilization energy of the carbon nanotubes is remarkably lowered, or if the solubilization energy cannot be exerted, if it exceeds 4, 〇〇〇, 〇〇〇, it is difficult to handle when the carbon nanotubes are solubilized. More preferably, the weight average molecular weight is -14 to 201107373 1,000 to 2,000,000 of highly branched polymer. The repeating unit containing a triazine ring is not particularly limited, but in the present invention, it is preferably one represented by the following formula (1). [Chemistry 7]

(wherein R and R1 represent a hydrogen atom or an alkyl group which may have a branched structure having a carbon number of 1 to 10, and Ar represents an aryl group which may have a substituent) ° may also have a carbon number of 1 to 1 Å. The base of the branch structure is not particularly limited, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a third butyl group, and a ring. Butyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 丨-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl 1,1,1-dimethyl-n-propyl, 1,2-methyl-n-propyl, 2,2-dimethyl-n-propyl, oxime-ethyl-n-propyl, cyclopentyl, 1_Methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1-2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1_ Ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl - n-pentyl, indole 1-dimethyl-n-butyl, anthracene, 2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl Base, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, N Ethyl n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, hydrazine, 2,2-dimethyl-n-propyl, 1-ethyl-1 -methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclo-15- 201107373 hexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl -cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-di Methyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3·dimethyl -cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2 -trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl 2-Ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, and the like. In the formula (1), the aryl group which may have a substituent is not particularly limited. However, in consideration of the improvement of the dispersing and dissolving energy of the carbon nanotubes, in the present invention, it is preferable to use the following formula (2) to (() 12) at least one of the above, since a highly branched polymer which is more excellent in dissolution (dispersion) of the carbon nanotubes can be obtained, it is particularly preferable to exhibit the formulas (4), (6) and (12). Aryl. -16- 201107373 [Chem. 8] R1 R2

(6) R31 rK3r3vVr3° R r28 (7) (8)

D77 d76

(12) R70 R71 R66 r67 ri (11) In the formulae (2) to (12), R1 to R8° independently of each other represent a hydrogen atom, a halogen atom, a carboxyl group or a fluorenyl group, and may have a carbon number of 1 to 1 Å. An alkyl group having a branched structure or an alkoxy group having a branched structure having a carbon number of 1 to 1 Å. W1 and W2 independently of each other represent a single bond, CR81R82 (R81 and R82 independently represent a hydrogen atom or an alkyl group which may have a branched structure having a carbon number of 1 to 10 (however, these may form a ring together)), C = 0, 0, S, SO, S02, or NR83 (R83 represents a hydrogen atom or an alkyl group which may also have a branched structure of 1 to 10 carbon atoms). The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Further, the alkyl group having a branched structure having a carbon number of 1 to 1 Å may be, for example, the same as described above. -17-201107373 Further, a ring formed by R81 and R82 together may, for example, be a cyclopentane ring or a cyclohexane ring. The alkoxy group which may have a branched structure having a carbon number of 1 to 10 may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, or a third group. Butoxy, n-pentyloxy and the like. X1 and X2 each independently represent a single bond, and may have an alkyl group having a branched structure of 1 to 10 carbon atoms or a group represented by the formula (13). [Chemistry 9]

〇3) R84 to R87 independently represent a hydrogen atom, a halogen atom, a carboxyl group, a fluorenyl group, an alkyl group having a branched structure of 1 to 10 carbon atoms, or a branched structure having a carbon number of 1 to 10. The alkoxy group, Y1 and Y2, independently of each other, represents a single bond or an alkylene group which may have a branched structure having a carbon number of 1 to 10. The halogen atom, the alkyl group which may have a branched structure having a carbon number of 1 to 1 Å, and the alkoxy group may, for example, be the same as described above. Examples of the stretching base having a branched structure of 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 (1 2) are, for example, those represented by the following formulas, but are not limited thereto. -18- 201107373 [化10]

Specific examples of the repeating unit of the triazine ring in the hyperbranched polymer which is suitably used in the present invention include those represented by the following formulas (14) to (16), but are not limited thereto. Wait. [化11]

-19-201107373 An example of a method for producing a hyperbranched polymer which can be used as a carbon nanotube dispersion/solubilizing agent of the present invention will be described. For example, as shown in the following mechanism 1, a highly branched polymer having a repeating structure (15') can be used to halogenate cyanuric acid (17) and a bisaminophenyl hydrazine compound having an amine group (18). It is obtained by reacting in a suitable organic solvent. Further, as shown in the following mechanism 2, the highly branched polymer having a repeating structure (15) is a halogenated cyanuric acid (17) and a bisaminophenyl hydrazine compound having an amine group (18). The compound (1 9 ) obtained by reacting in an appropriate amount in an appropriate organic solvent can also be synthesized. The compound represented by the formulas (17) and (18) can be, for example, a commercially available product manufactured by Aldrich Co., Ltd. or Tokyo Chemical Industry Co., Ltd. Using this method, highly branched polymers can be produced inexpensively, simply and safely. This production method is significantly shorter than the reaction time when a general polymer is synthesized. Therefore, it is suitable for a manufacturing method in consideration of the environment in recent years, and the amount of C〇2 discharged can be reduced. In addition, even if the manufacturing scale is greatly increased, it is possible to create a stable supply system that is not degraded in industrialization. -20- 201107373 [Chem. 12]

Agency 1 X

N person N

X Yi N people X (17) +

(wherein X represents each other independently of a halogen atom. R represents the same meaning as described above.) Mechanism 2 [Chem. 13]

S 201107373 (wherein X represents a halogen atom independently of each other. R represents the same meaning as described above.) In the method of the mechanism 1, the feed amount of each raw material is arbitrary only for the purpose of obtaining the polymer, but is relative to the halogenated melamine. The acid compound (17) is 1 equivalent, preferably 0.01 to 10 equivalents based on the diamine compound (18). As the organic solvent, various solvents generally used in such a reaction can be used, and examples thereof include tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethylammonium, and N-methyl-2-. Pyrrolidone, tetramethyl urea, hexamethylphosphoniumamine, N,N-dimethylacetamide, N-methyl-2-piperidone, N,N-dimethylethylene urea, > ,^1',1^'-tetramethyl maleate amide, :^-methyl caprolactam, N-acetylpyridinium, N,N-diethylacetamide, N-B Base-2-pyrrolidone, N,N-dimethylpropionate decylamine, N,N-dimethylisobutylguanamine, N-methylformamide, hydrazine, Ν'-dimethyl propylene urea, etc. A solvent such as a guanamine solvent or a mixed solvent thereof. Among them, it is preferably a mixture of hydrazine, hydrazine-dimethylformamide, dimethyl hydrazine, hydrazine-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, and the like, particularly suitable It is Ν, Ν-dimethylacetamide, Ν-methyl-2-pyrrolidone. In the reaction of the mechanism 1 and the second stage of the reaction of the mechanism 2, the reaction temperature may be appropriately set within a range from the melting point of the solvent to be used to the boiling point of the solvent, but is preferably 〇150. (: Left and right, more preferably 60 to 100. (^) In the first stage of the mechanism 2, the reaction temperature may be appropriately set within a range from the melting point of the solvent to be used to the boiling point of the solvent, but particularly preferably - 10~50. About 〇, more preferably -10~l 〇 ° C. In the reaction of the above mechanism 1 and the second stage of the reaction of the mechanism 2, -22-201107373 can use various bases generally used. Specific examples thereof include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, sodium ethoxide, sodium acetate, triethylamine, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, and oxidation. Magnesium, calcium oxide, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, fluorinated planer, alumina, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methyl Hexahydropyridine, 2,2,6,6-tetramethyl-N-methylhexahydropyridine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, etc. The amount of base added relative to halogenation The cyanuric acid compound (17) is preferably used in an amount of from 1 to 100 equivalents, particularly preferably from 1 to 10 equivalents. Further, these bases may also be used in the form of an aqueous solution. The polymer obtained by using the compound represented by the formula (1 8 ) and the formula (1 8 ) as a raw material is preferably such that the raw material component does not remain. However, if the effect of the present invention is not impaired, a part of the raw material may remain. Even in any of the institutions In the method, after the reaction is completed, the product can be easily purified by a reprecipitation method, etc. Further, in the present invention, at least one of the halogen atoms of the terminal triamethylene ring may be an alkyl group or an aralkyl group. An aryl group, an alkylamino group, an alkylamino group containing an alkoxycarbenyl group, an aralkylamino group, an arylamine group, an alkoxy group, an aralkyloxy group, an aryloxy group, an ester group, etc. The alkyl group and the alkoxy group are, for example, 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 and an o-chloro group. Phenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, -23- 201107373 p-methoxyphenyl, p-nitro Phenylphenyl, p-cyanophenyl, α-naphthyl, cold-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-onion, 2 - a group, a 9-bacteria group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, etc. Specific examples of the aralkyl group include a benzyl group and a p-methyl group. Phenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, α-naphthylmethyl, etc. Specific examples of the alkylamine group include, for example, a methylamino group, an ethylamino group, and a positive C-propyl group. Amino group, isopropylamino group, n-butylamino group, isobutylamino group, second butylamino group, tert-butylamino group, n-pentylamino group, 1-methyl-n-butyl group Amino, 2-methyl-n-butylamino, 3-methyl-n-butylamino, 1, dimethyl-n-propylamino, 1,2-dimethyl-n-propylamine , 2,2-dimethyl-n-propylamino, 1-ethyl-n-propylamino, n-hexylamino '1-methyl-n-pentylamino, 2-methyl-n-pentyl Amino, 3-methyl-n-pentylamino, 4-methyl-n-pentylamino, 1,1-dimethyl-n-butylamino, 1,2-dimethyl-n-butyl Amino group, 1,3-dimethyl-n-butylamino group, 2,2- Methyl-n-butylamino, 2,3-dimethyl-n-butylamino, 3,3-dimethyl-n-butylamino, 1-ethyl-n-butylamino, 2- Ethyl-n-butylamino, 1,1,2-trimethyl-n-propylamino, 1,2,2-trimethyl-n-propylamino, 1-ethyl-1-methyl · n-propylamino, 1-ethyl-2-methyl-n-propylamino. Specific examples of the aralkylamino group include a benzylamino group 'methoxycarbonylphenylmethylamino group, an ethoxycarbonylphenylmethylamino group, a p-methylphenylmethylamino group, and m-Methylphenylmethylamino, o-ethylphenylmethylamine-24- 201107373, m-ethylphenylmethylamino, p-ethylphenylmethylamino, 2- Propyl phenylmethylamino, 4-isopropylphenylmethylamino, 4-isobutylphenylmethylamino, naphthylmethylamino, methoxycarbonylnaphthylmethylamino And ethoxycarbonylnaphthylmethylamino group and the like. Specific examples of the arylamine group include a phenylamino group, a methoxycarbonylphenylamino group, an ethoxycarbonylphenylamino group, a naphthylamino group, a methoxycarbonylnaphthylamino group, and an ethoxy group. A carbonylnaphthylamino group, an onionylamino group, a mercaptoamine group, a biphenylamino group, a terphenylamino group, a mercaptoamine group, or the like. The alkylamino group containing an alkoxycarbenyl group is an alkylamino group containing a monoalkoxycarbenyl group, an alkylamino group containing a dialkoxycarbenyl group, and a trialkoxycarboalkyl group. Any of the alkylamino groups may also be exemplified, and specific examples thereof include 3-trimethoxycarbamidopropylamino group, 3-triethoxymethanealkylpropylamino group, and 3-dimethyl group. Oxyformyl propylamino group, 3-methyldiethoxyethoxyformamidopropylamino, N-(2-aminoethyl)-3-dimethylmethoxyformane Alkylamino, N-(2-aminoethyl)-3-methyldimethoxycarbamidopropylamino, N-(2-aminoethyl)-3-trimethoxymethyl Alkylpropylamino group and the like. Specific examples of the aryloxy group include a phenoxy group, a naphthyloxy group, an onionoxy group, a decyloxy group, a biphenyloxy group, a terphenyloxy group, a decyloxy group and the like. Specific examples of the aralkyloxy group include a benzyloxy group, a p-methylphenylmethyloxy group, a m-methylphenylmethyloxy group, an o-ethylphenylmethyloxy group, and the like. m-Ethylphenylmethyloxy, p-ethylphenylmethyloxy, 2-propylphenylmethyloxy, 4-isopropylphenylmethyloxy, 4-isobutyl Phenylmethyloxy, α-naphthylmethyloxy, and the like. -25- 201107373 These groups are easily substituted by a compound which gives a substituent corresponding to a halogen atom on a triazine ring. For example, as shown in the following formula 3, an aniline derivative is added and reacted to obtain A hyperbranched polymer (20) having a phenylamine group at least one end. [Chem. 14]

(wherein, X and R have the same meanings as described above.) The carbon nanotube-containing composition of the present invention contains the carbon nanotube dispersion/solubilizing agent described above and a carbon nanotube. The carbon nanotube (CNT) system can be produced by an arc discharge method, a chemical vapor deposition method (CVD method), a laser lift-off method, or the like, but the CNT used in the present invention can also be produced by any of the methods. And get it. In addition, a single-layer CNT (hereinafter referred to as SWCNT) in which one carbon film of CNT is wound into a cylindrical shape, and two layers of CNTs in which two graphene sheets are wound into a concentric shape ( Hereinafter, it is described as DWCNT), and a plurality of CNTs (hereinafter referred to as MWCNT) which are concentrically wound with a plurality of graphene sheets. However, in the present invention, SWCNT, DWCNT, and -26-201107373 MWCNT can be respectively Monomers, or a combination of plurals. When SWCNT, DWCNT, or MWCNT is produced by the above method, fullerene, graphite, or amorphous carbon is simultaneously produced as a by-product, and catalytic metals such as nickel, iron, cobalt, and antimony remain, and thus sometimes These impurities must be removed and refined. The removal of impurities is carried out by acid treatment with nitric acid, sulfuric acid or the like while ultrasonic treatment is effective. However, in the acid treatment with nitric acid, sulfuric acid or the like, the conjugated CNTs which constitute the CNTs are destroyed, and the original properties of the CNTs may be impaired. Therefore, it is preferred to use them without purification. CNT is a method in which the electrical properties of the graphene sheet are taken from the metallic property to the semiconductor by the coiling method (helicality, palmarity). The palm-to-palm line of CNT is defined by the palm spectrum (R = nai + ma2 , but m, η is an integer) as shown in Figure 1. When n = m and nm = 3p (but p is an integer), the metal properties are At other times (nm, η - m, Table 3 p ), the properties of the semiconductor are known, respectively. Therefore, when SWCNT is particularly used, it is important to selectively dissolve (disperse) a certain composition. By using the triazine ring-based hyperbranched polymer of the present invention as a solubilizing agent (dispersing agent) for CNT, it is possible to obtain a composition which selectively dissolves CNT having a specific palmity. The composition of the present invention may further contain an organic solvent having a dissolving power of the above-mentioned dispersion, solubilizing agent (hyperbranched polymer). Examples of such an organic solvent include ether compounds such as THF and diethyl ether; halogenated hydrocarbons such as dichloromethane and chloroform; and guanamine compounds such as dimethylformamide and N-methylpyrrolidone (NMP). ; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone 'cyclohexanone; methanol, ethanol, -27- 201107373 alcohols such as isopropanol and propanol; n-heptane, n-hexane, cyclohexane An aliphatic hydrocarbon such as an aliphatic hydrocarbon, an aromatic hydrocarbon such as benzene, toluene, xylene or ethylbenzene, and the like, and preferably THF, chloroform, NMP or cyclohexane. Further, the organic solvent may be used alone or in combination of two or more. In particular, the ratio of the isolated dissolution of the CNTs is preferably THF or NMP, and further, it is preferably a NMP alone solvent or a solvent containing the film forming property of the composition. When the preparation method of the composition of the present invention is arbitrary, and the dispersion/solubilizer (polymer) is in a liquid state, the dispersion/solubilizer and CNT are appropriately mixed, and when the dispersion/solubilizer is a solid, after melting, It can be prepared by mixing with CNTs. Further, when an organic solvent is used, the composition may be prepared by mixing a dispersion/solubilizing agent, a CNT, and an organic solvent in an arbitrary order. In this case, it is preferable to subject the mixture composed of the dispersion/solubilizing agent, the CNT, and the organic solvent to a solubilization treatment, thereby further increasing the ratio of isolated dissolution of the CNT. The solubilization treatment may be, for example, a wet treatment such as a ball mill, a granulating mill or a jet honing machine, or an ultrasonic treatment using a bath type or probe type ultrasonic cleaning machine, but if the treatment efficiency is considered, it is preferable to be super Sound processing. The time for the solubilization treatment is arbitrary, but it is preferably from about 5 minutes to about 1 hour, more preferably from about 30 minutes to about 5 hours. Further, before the solubilization treatment, appropriate heat treatment may be carried out. 混合 The mixing ratio of the solubilizing agent to the CNT in the composition of the present invention is 280-201107373. The mass ratio is about 1000:1 to 1:100. In addition, the concentration of the solubilizing agent in the composition using the organic solvent is not particularly limited as long as it can dissolve the CNT in the organic solvent, but in the present invention, it is preferably 0.00 in the composition. 1 to 20% by mass, more preferably 0.005 to 10% by mass. Further, the concentration of the CNT in the composition is preferably at least a part of the CNTs solubilized (solubilized), but in the present invention, it is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5 in the composition. quality%. The composition of the present invention prepared as described above is a presumed that a solubilizing agent adheres to the surface of the CNT to form a composite. The composition of the present invention may be compounded by mixing with a general-purpose synthetic resin which is soluble in the above various organic solvents. Specific examples of the synthetic resin for general use include polyolefin resins such as polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), and ethylene-ethyl acrylate copolymer (EE A ). , styrene resin such as polystyrene (PS), impact-resistant polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), A vinyl chloride resin, a polyurethane resin, a phenol resin, an epoxy resin, an amine resin, an unsaturated polyester resin, or the like. Specific examples of the synthetic synthetic engineering plastics include, for example, polyamide resin, polycarbonate resin, polyphenylene ether resin, modified polyphenylene ether resin, polyethylene terephthalate (PET), and polybutylene terephthalate. Polyester resin such as diester (PBT), polyketal resin, polyfluorene resin, polyphenylene sulfide resin, polyamine -29-201107373 amine resin, and the like. Coating method for ITO, etc. Metallic semiconductive The CNT-containing composition of the present invention is applied to a suitable substrate of p ET or glass, by a clock method, a spin coating method, a bar coating method, a light or dip coating method. The film is formed by coating by a suitable method. The film obtained can be suitably used for an antistatic film using a carbon nanotube or a conductive material such as a transparent electrode, or a photoelectric conversion element or an electroluminescent device having a biological property. [Embodiment] Embodiments of the Invention JEOL- Hereinafter, examples and comparative examples will be described more specifically, but the present invention is not limited to the following examples. [1 H-NMR] Apparatus: Varian NMR System 400 NB (400 MHz) EC A 700 (700 MHz) Measurement solvent: DMSO - d 6 Reference material: tetramethyl decane (TMS) (6 O.Oppm) [GPC] Apparatus: Tosoh (Stock) HLC-8200 GPC Pipe Column: Shodex KF-804L + KF-8 05L Column Temperature: 40 °C Solvent: Tetrahydrofuran Detector: UV ( 2 54nm ) Calibration Line: Standard Polystyrene -30 - 201107373 [Ultraviolet visible light spectrophotometer] Device: (share) manufactured by Shimadzu Corporation: SHIMADSUUV-3600 [Example 1] Synthesis of polymer compound [1] [Chem. 15]

[1] nh2 Naphthalene-1,5-diamine (6.33 g, 0.02 mol) was dissolved in 220 ml of tetrahydrofuran (THF) in a 500 ml four-necked flask equipped with a reflux column, and cooled to 3 ° C in an ice bath. After cooling, 2,4,6·trichloro-1,3,5-triazine (3.68 g, 0.02 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 30 ml of THF was slowly dropped, and after stirring, it was stirred for 1 〇. . The flask was transferred from an ice bath to an oil bath, and the temperature was raised to 7 (TC, 1% aqueous potassium carbonate solution was dropped. After the dropwise addition, the mixture was stirred for 4 hours. After the stirring was stopped, the aqueous phase was removed, and the organic phase was concentrated to methanol (500 ml). The mixed solvent of ion-exchanged water (200 ml) was reprecipitated. The precipitate was filtered, dissolved in THF (50 ml), and re-precipitated with methanol (500 ml) and ion-exchanged water (50 ml). The pressure dryer was dried at 40 ° C for 6 hours to obtain the desired polymer compound [1] (3.68 g). The measurement results of the Η-NMR spectrum of the polymer compound [1] are shown in Fig. 2 . The obtained polymer compound [1] is a compound having a structural unit represented by (1), -31 - 201107373, and the weight average molecular weight Mw measured by GPC is 1500, and the polydispersity is obtained. Mw (weight average molecular weight) / Μη (number average molecular weight) was 1.13. [Example 2] Synthesis of polymer compound [2] [Chem. 16]

The naphthalene-1,5-diamine used in Example 1 was substituted with 9,9-bis(4-aminophenyl)anthracene (manufactured by Aldrich), and the same procedure as in Example 1 was carried out to obtain the object. The polymer compound [2] (1.74 g). The measurement results of the 1H-NMR spectrum of the polymer compound [2] are shown in Fig. 3 . The polymer compound [2] obtained has a structural unit represented by the formula (1), and the weight average molecular weight Mw measured by GPC is 2700' polydispersity Mw (weight average) The molecular weight) / Μ η (number average molecular weight) was 1.40. [Example 3] Synthesis of polymer compound [3] -32- 201107373 [Chem. 17]

The naphthalene-1,5.diamine used in Example 1 was substituted with 3,4-diaminobenzophenone, and the same procedure as in Example 1 was carried out to obtain the desired polymer compound [3]. ( 1.68g ). The measurement results of the 1H-NMR spectrum of the polymer compound [3] are shown in Fig. 4 . The polymer compound [3] obtained has a structural unit represented by the formula (1), and the weight average molecular weight Mw measured in terms of polystyrene obtained by GP C is 2100, and the polydispersity Mw (weight) The average molecular weight) / Mn (number average molecular weight) was 1.29. [Example 4

Synthesis of [4] -33- 201107373

Add 9,9-bis(4-aminophenyl)phosphonium (9.29 g, 〇.〇27 mol) to a 200 ml four-necked flask under air, dissolved in 80 ml of dimethylacetamide, and heated in an oil bath. To l〇〇 °C. Thereafter, polymerization was started by adding 1,3,5-trichloro-2,4,6-tris(3.698, 〇.〇2111〇1) dissolved in 20 ml of dimethylacetamide. After 5 minutes, aniline (3_34 g, 〇.036 mol) was added, and the mixture was stirred for 10 minutes to stop the polymerization. After allowing to cool to room temperature, it was reprecipitated in a 1000 ml aqueous solution of dissolved potassium carbonate (15 g '0.1 1 mol). The precipitate was filtered, and redissolved in THF 50 m1' in 540 ml of hexane and 60 ml of ethanol. The precipitate obtained by filtration was dried in a vacuum dryer at 4 ° C for 6 hours to obtain 12.4 g of the desired polymer compound [4] (hereinafter, simply referred to as HB-TFA90). The results of measurement of 1H-NMR spectrum of HB-TFA90 are shown in Fig. 5. The obtained HB-TFA9 fluorene has a structural unit represented by the formula (1), and the weight average molecular weight Mw measured by GPC is 9200' polydispersity Mw/Mn is 2.33°. -34-201107373 [Example 5] 9,9-bis(4-aminophenyl)anthracene (6.93 g, ruthenium) was used for the synthesis of the polymer compound [4] obtained by blocking the end of aniline having a different molecular weight. 20 mol), 1,3,5-trichloro-2,4,6-triazine (3.69 g, 0.02 0 mol), aniline (3.36 g, 0.036 mol), and synthesized in the same manner as in Example 4 to obtain a molecular weight The polymer compound [4] (hereinafter referred to as "HB-TFA42") which is different from that of Example 4 was used. The results of the measurement of the 1H-NMR spectrum of HB-TFA42 are shown in Fig. 6. The obtained HB-TFA56 has a weight average molecular weight Mw of 4,200' polydispersity Mw/Mn as a compound of the structural unit shown in (1), which is determined by GPC. . 96. [Example 6] 9,9-bis(4-aminophenyl)anthracene (5.9 (^, 0.017111〇1)) was used for the synthesis of the polymer compound [4] obtained by blocking the terminal aniline having a different molecular weight. 1,3,5-trichloro-2,4,6-triazine (3.69 g, 0.020 mol), aniline (3.35 g, 0.06 mol), which was synthesized in the same manner as in Example 4 to obtain a molecular weight and Example 4 The polymer compound [4] (hereinafter abbreviated as HB-TFA20) is 10_8 g. The measurement results of the 1H-NMR spectrum of HB-TFA20 are shown in Fig. 7. The HB-TFA20 system has the formula (1). The weight average molecular weight Mw of the compound of the structural unit measured by GPC was 2,900, and the polydispersity Mw/Mn was 1.68. -35 - 201107373 [Example 7] Preparation of SWCNT dispersion was carried out 1 mg of the polymer compound [1] obtained in Example 1 was dissolved in NMP 5 ml to prepare an NMP solution, and then SWCNT (Unydim· Inc. product name Unydim (registered trademark) Carbon Nanotubes) 〇. 5 mg was added. Bath-type ultrasonic irradiation was used. The device (Tokyo Glass Instruments Co., Ltd., Fine FU-6H type) was subjected to ultrasonic treatment at room temperature for 1 hour. Further, the mixture was centrifuged at 1 0000 G (room temperature) for 1 hour (small high-speed cooling centrifuge, manufactured by Tommy Seiko SRX-201) to form a supernatant to obtain a black transparent SWCNT-containing solution. [Example 8] Preparation of SWCNT Dispersion A black transparent SWCNT-containing solution was obtained in the same manner as in Example 7 except that the polymer compound obtained in Example 2 was used (2 卩 ^). [Example 9] SWCNT dispersion The preparation of the liquid was carried out in the same manner as in Example 7 except that the polymer compound I obtained in Example 3; 3 彳 & % was obtained, and a solution of black μ yue 2 # SWCNT was obtained. [Example 1 〇] SWCNT Preparation of Dispersion A black transparent SWCNT-containing solution was obtained in the same manner as in Example 7 except that the polymer compound I; 4;) (HB. TFA9®) obtained in Example 4 was used. [Embodiment 11] Preparation of SWCNT dispersion liquid A black transparent SWCNT-containing solution was obtained in the same manner as in Example 7 except that the polymer compound [4彳 (HB TFA42) obtained in Example 5 was used. 〔real Dispersion of SWCNT] Preparation Example 12 except that in Example 6 of the obtained polymer compound [4 '(hb. TFA20), the rest of the train do the same in Example 7 to obtain a solution of a black transparent SWCNT-containing embodiment. The ultraviolet-visible near-infrared absorption spectrum of each of the SWCNT-containing solutions obtained in the above Examples 7 to 12 was measured (measurement device: SHIMADZU UV-3600), and the semiconductor S11 band (1400 to 100om) and the S22 band (1000) were clearly observed. ~600nm), and the absorption of the metallic band (60 0~45 Onm), confirming that SWCNT is dissolved in isolation (refer to Figures 8~13) [Comparative Example 1] In addition to the use of poly(ethylene) ruthenium ketone (PVP) The SWCNT dispersion liquid was prepared in the same manner as in Example 4 except that the SWCNT dispersion was low (see Fig. 14). BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the spectrum of the palm of the carbon nanotube. -37- 201107373 Figure 2 shows the polymer compound obtained in Example 1 [! a plot of the 1H-NMR spectrum. Fig. 3 is a view showing a 1H-NMR chart of the polymer compound [2] obtained in Example 2. Fig. 4 is a view showing a 1H-NMR chart of the polymer compound [3] obtained in Example 3. Fig. 5 is a view showing a 1H-NMR chart of the polymer compound [4] obtained in Example 4. Fig. 6 is a chart showing the 1H-NMR chart of the polymer compound [4] obtained in Example 5. Fig. 7 is a chart showing the 1H-NMR chart of the polymer compound [4] obtained in Example 6. Fig. 8 is a view showing the ultraviolet-visible-near-infrared absorption spectrum of the polymer compound [1] /SWCNT dispersion obtained in Example 7, and Figure 9 is a view showing the polymer compound obtained in Example 8 [2]. FIG. 1 is a diagram showing the ultraviolet-visible-near-infrared absorption spectrum of the polymer compound [3] /SWCNT dispersion obtained in Example 9. Fig. 11 is a graph showing the polymer compound [4]/SWCNT 'liquid@UV-visible near-infrared absorption spectrum obtained in Example 10. -38-201107373 Fig. 12 is a graph showing the ultraviolet-visible-near-infrared absorption spectrum of the polymer compound [4)/SWCNT dispersion obtained in Example 11. Fig. 1 is a graph showing the ultraviolet-visible-near-infrared absorption spectrum of the polymer compound [4]/SWCNT dispersion obtained in Example 12. Fig. 14 is a graph showing the ultraviolet-visible-near-infrared absorption spectrum of the PVP/SWCNT dispersion obtained in Comparative Example 1. -39-

Claims (1)

201107373 VII. Patent application scope: 1. A carbon nanotube dispersion. The solubilizer' is a weight determined by polystyrene conversion containing a triamethylene ring as a repeating unit and analyzed by gel permeation chromatography. It is composed of a highly branched polymer having an average molecular weight of i,000 to 4,000,000. 2. The carbon nanotube dispersion/solvent according to claim 1, wherein the repeating unit is represented by the following formula (1) (wherein R and R1 represent a hydrogen atom or a group of a branch structure which may have a branched structure of 1 to 1 Å, and Ar represents an aryl group which may have a substituent). 3. The carbon nanotube dispersion/solvent according to claim 2, wherein the Ar is at least one of the formulas (2) to (1 2) -40 - 201107373 In the formula, R1 to R8Q independently represent a hydrogen atom, a halogen atom, a carboxyl group, a fluorenyl group, an alkyl group having a branched structure having a carbon number of 1 to 10, or a branched structure having a carbon number of 1 to 10. The alkoxy group, w1 and W2 independently of each other represent a single bond, and CR81R82 (wherein R81 and R82 independently represent a hydrogen atom or an alkyl group which may have a branched structure having a carbon number of 1 to 10 (however, these may be combined together) Forming a ring)), C = 0, 0, S, SO, S〇2, or NR83 (R83 represents a hydrogen atom or an alkyl group which may also have a branched structure of 1 to 10 carbon atoms), and 'X1 and X2 are independent of each other An alkyl group which may have a single bond or a branched structure having a carbon number of 1 to 10, or a formula (13) -41 - 201107373 (13) (wherein R84 to R87 each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a fluorenyl group, an alkyl group having a branched structure of 1 to 10 carbon atoms, or may have a carbon number of 1 to 10; The alkoxy group of the branched structure, Y1 and Y2 independently of each other represent a single bond or a group which may also have a branched alkyl group having a branched structure of from 1 to 10). 4. The carbon nanotube dispersion/solvent of claim 2, wherein the repeating unit is represented by the following formula (14). 5. The carbon nanotube dispersion according to item 2 of the patent application scope, the solubilizing agent, wherein the aforementioned repeating unit is represented by the following formula (15) -42- 201107373 6. The carbon nanotube dispersion/solvent of claim 2, wherein the repeating unit is represented by the following formula (16). A composition comprising a carbon nanotube dispersion, a solubilizing agent and a carbon nanotube according to any one of claims 2 to 6. 8. The composition of claim 7, wherein the carbon nanotube dispersion/solubilizing agent is attached to a surface of the carbon nanotube to form a composite. 9) A composition according to claim 7 or 8 which further contains an organic solvent. 10. The composition of claim 9, wherein the carbon nanotubes are dispersed in the aforementioned organic solvent. -43- 201107373 11. The composition of claim 9 wherein the aforementioned composite is dispersed or dissolved in the aforementioned organic solvent. 12. The composition of any one of claims 2 to 11 wherein the carbon nanotube is at least one selected from the group consisting of a single carbon nanotube, a two carbon nanotube, and a multilayer carbon nanotube. . A film obtained by the composition of any one of claims 7 to 12 of the patent application. 1 4 . A method for producing a composition, which is obtained by mixing a carbon nanotube dispersion of any one of the first to sixth aspects of the patent application, a solubilizing agent, a carbon nanotube and an organic solvent to prepare a mixture, and then mechanically This mixture was treated sexually. 15. The manufacturing method of claim 14, wherein the aforementioned mechanical treatment is ultrasonic processing. 16. The production method according to claim 15, wherein a carbon nanotube is added to a solution obtained by dissolving the carbon nanotube dispersion/solubilizing agent in the organic solvent to prepare the mixture, and ultrasonicizing Treat this mixture. -44 -