Resin composition and method for improving electrical conductivity

Abstract

To provide a resin composition exhibiting high conductivity.SOLUTION: A resin composition contains a resin, a carbon nanotube, and a compound of formula (1). In the formula, X1a and X1b each independently represents a group represented by formula (X1).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition containing carbon nanotubes (CNTs) and a method for improving electrical conductivity (electrical conductivity). [Background technology]

[0002] Taking advantage of the excellent characteristics based on its unique chemical structure, fluorene derivatives are used in various fields as materials for forming organic semiconductors and optical components, and are usually used as resins containing fluorene derivatives as monomer components. U.S. Patent No. 2299948 (Patent Document 1) describes that 9,9-di-(β-carbamoyl-ethyl)fluorene represented by the following formula is useful as an intermediate for preparing synthetic resins.

[0003] [ka] [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Patent No. 2,299,948 Summary of the Invention [Problem to be solved by the invention]

[0005] In the examples of Patent Document 1, 9,9-di-(β-cyanoethyl)fluorene is reacted with sulfuric acid under specific conditions to prepare the above-mentioned 9,9-di-(β-carbamoyl-ethyl)fluorene.

[0006] However, Patent Document 1 does not state or suggest anything about using 9,9-di-(β-carbamoyl-ethyl)fluorene as an additive for resins, particularly about using it as an additive for improving the electrical conductivity (electrical conductivity) of resins.

[0007] Therefore, an object of the present invention is to provide a resin composition that exhibits high electrical conductivity (or low electrical resistance). [Means for solving the problem]

[0008] As a result of intensive research to achieve the above object, the inventors discovered that the electrical conductivity can be greatly improved by adding a fluorene derivative having a specific chemical structure to a resin together with carbon nanotubes, and thus completed the present invention.

[0009] That is, the resin composition of the present invention contains a resin, carbon nanotubes, and a compound represented by the following formula (1).

[0010] [ka]

[0011] [In the formula, R 1 represents a substituent, k represents an integer of 0 to 8, R 2a , R 2b , R 2c and R 2d each independently represents a hydrogen atom or a substituent, R 3a and R 3b each independently represents a hydrogen atom or a substituent, X 1a and X 1b are each independently represented by the following formula (X1)

[0012] [ka]

[0013] (In the formula, R 4 and R 5 each independently represents a hydrogen atom or a hydrocarbon group, or R 4 and R 5 and are bonded to each other to form a heterocycle together with the adjacent nitrogen atom. The formula represents a group represented by the formula: In the formula (1), R 4 and R 5 Both of R may be a hydrocarbon group. 4 and R 5 may both be linear or branched alkyl groups. The carbon nanotubes may be single-walled or multi-walled carbon nanotubes. The resin may include at least one selected from polyolefin-based resins and polycarbonate-based resins. The ratio of the compound represented by formula (1) may be about 0.1 to 10 parts by mass relative to 100 parts by mass of the resin, the ratio of the carbon nanotubes may be about 0.1 to 20 parts by mass relative to 100 parts by mass of the resin, and the ratio of the compound represented by formula (1) to the carbon nanotubes may be the former / latter (mass ratio)=about 1 / 0.5 to 1 / 5.

[0014] The present invention encompasses a method for improving the electrical conductivity of a resin (a method for reducing resistance or a method for preventing electrostatic charge) by adding the compound represented by formula (1) and carbon nanotubes to the resin. The method may include a primary mixing step of mixing the compound represented by formula (1) and the carbon nanotubes, and a secondary mixing step of adding the mixture obtained in the primary mixing step to the resin.

[0015] The present invention also includes an additive for improving the electrical conductivity of a resin, which is a conductive agent (a conductivity improver (or imparting agent), a conductive material, or an antistatic agent) containing a compound represented by formula (1) and carbon nanotubes.

[0016] In addition, the present invention may solve the following problems as a secondary object.

[0017] That is, another object of the present invention is to provide a resin composition which can achieve both high electrical conductivity and high impact strength.

[0018] It is still another object of the present invention to provide a method for improving the electrical conductivity of a resin, and an additive (conductive agent) for improving the electrical conductivity of a resin.

[0019] In this specification and claims, the number of carbon atoms of a substituent is represented as C1, C6, C 10 For example, an alkyl group with one carbon atom is represented as "C1 alkyl" and an aryl group with 6 to 10 carbon atoms is represented as "C 6-10 It is indicated as "aryl". Effect of the Invention

[0020] The resin composition of the present invention exhibits high electrical conductivity (or electric conductivity) because it contains a combination of a fluorene derivative having a specific chemical structure, carbon nanotubes, and a resin. Although high electrical conductivity and high impact strength are usually in a trade-off relationship, the resin composition of the present invention can surprisingly achieve both properties. The present invention can provide a method for improving the electrical conductivity of a resin by adding the fluorene derivative and carbon nanotubes to the resin. The present invention can also provide a conductive agent containing the fluorene derivative and carbon nanotubes. [Brief description of the drawings]

[0021] [Figure 1] FIG. 1 is a 1H-NMR spectrum of DEAA-FL obtained in Synthesis Example 1. [Diagram 2] FIG. 2 is a 1H-NMR spectrum of DMAA-FL obtained in Synthesis Example 2. [Diagram 3] FIG. 3 is a 1H-NMR spectrum of NIPAM-FL obtained in Synthesis Example 3. [Figure 4] FIG. 4 is a 1H-NMR spectrum of AAD-FL obtained in Synthesis Example 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] The resin composition contains at least a resin, carbon nanotubes (CNTs), and a compound represented by the following formula (1) (hereinafter also referred to as a fluorene derivative), and the fluorene derivative and CNTs (or a composite thereof) function as a conductive agent (a conductivity enhancing (or imparting) agent, a conductive material, or an antistatic agent).

[0023] [Fluorene derivatives]

[0024] [ka]

[0025] [In the formula, R 1 represents a substituent, k represents an integer of 0 to 8, R 2a , R 2b , R 2c and R 2d each independently represents a hydrogen atom or a substituent, R 3a and R 3b each independently represents a hydrogen atom or a substituent, X 1a and X 1b each independently represents a group represented by the following formula (X1):

[0026] [ka]

[0027] (In the formula, R 4 and R 5 each independently represents a hydrogen atom or a hydrocarbon group, or R 4 and R 5 and bonded to each other to form a heterocycle with the adjacent nitrogen atom).

[0028] In the formula (1), the group R 1The substituent may be a non-reactive substituent that is inactive in the reaction, and examples thereof include a cyano group; a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; and a hydrocarbon group such as an alkyl group or an aryl group. The aryl group is preferably a C 6-10 Aryl groups are preferred. 1 The substituent is preferably a cyano group, a halogen atom, or an alkyl group, and more preferably an alkyl group.

[0029] Examples of the alkyl group include C methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, and t-butyl groups. 1-12 Alkyl groups, preferably C 1-8 Alkyl groups, especially methyl groups, etc. 1-4 Examples of such groups include alkyl groups.

[0030] In addition, the group R 1 When the number of substitutions k is more than one (2 or more), two or more groups R 1 The types of R may be the same or different, and two or more groups R substituted on different benzene rings. 1 The types of may be the same or different. 1 The bonding positions (substitution positions) of are not particularly limited as long as they are positions 1 to 8 of the fluorene ring, and examples thereof include positions 2, 7, and 2,7 of the fluorene ring.

[0031] The number of substitutions k may be, for example, an integer of about 0 to 6, and the preferred ranges are integers of 0 to 4, 0 to 3, and 0 to 2 in the following stepwise order, and are preferably 0 or 1, and particularly preferably 0. In addition, in the two benzene rings constituting the fluorene ring, the group R 1 The number of substitutions in each of the above may be different from each other, but is usually the same.

[0032] R 2a , R 2b , R 2c and R 2dThe substituent represented by the formula (I) may be a non-reactive substituent that is inactive in the reaction, and examples thereof include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

[0033] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups. 1-10 The alkyl group is preferably a linear or branched C 1-6 Alkyl groups, more preferably linear or branched C 1-4 It is an alkyl group.

[0034] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 Cycloalkyl groups are included.

[0035] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl group (or tolyl group), dimethylphenyl group (or xylyl group), etc. 1-4 Examples include alkyl-phenyl groups.

[0036] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of such groups include alkyl groups.

[0037] R 2a , R 2b , R 2c and R 2d Preferred examples of the substituent represented by the formula: 1-6 Alkyl group, C 1-5 Alkyl group, C 1-4 Alkyl group, C 1-3 is an alkyl group, more preferably C 1-2 It is an alkyl group, in particular a methyl group.

[0038] Preferred R 2a , R 2b , R 2c , R 2d is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom. 2c and R 2d is preferably a hydrogen atom, and the preferred R 2a and R 2b is a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom (i.e., R 2a , R 2b , R 2c and R 2d are preferably hydrogen atoms.

[0039] Also, R 2a , R 2b , R 2c , R 2d The types of may be different from each other, but R 2a and R 2b are the same, and R 2c and R 2d are preferably identical.

[0040] R 3a and R 3b The substituent represented by may be a non-reactive substituent that is inactive in the reaction, and examples of such a substituent include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Examples of such a hydrocarbon group include the above-mentioned R 2a and R 2b Examples of the substituent represented by the formula (I) include the same groups as the hydrocarbon groups exemplified above.

[0041] R 3a and R 3b Among the substituents represented by the formula (I), preferred substituents are alkyl groups, and preferred alkyl groups are as follows, in the order of steps: 1-6 Alkyl group, C 1-5 Alkyl group, C1-4 Alkyl group, C 1-3 is an alkyl group, more preferably C 1-2 It is an alkyl group, in particular a methyl group.

[0042] Also, the preferred R 3a and R 3b is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0043] X 1a and X 1b (or formula (X1)), R 4 and R 5 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and groups formed by combining a plurality of these groups.

[0044] Examples of the alkyl group include linear or branched C alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, neopentyl, hexyl, octyl, and decyl groups. 1-12 Alkyl groups and the like.

[0045] Examples of the cycloalkyl group include C cyclopentyl and cyclohexyl groups. 5-10 cycloalkyl groups, etc.

[0046] Examples of the aryl group include C phenyl, alkylphenyl, biphenylyl, and naphthyl groups. 6-12 Examples of the alkylphenyl group include mono- to tri-C alkylphenyl groups such as methylphenyl group (or tolyl group), dimethylphenyl group (or xylyl group), etc. 1-4 Examples include alkyl-phenyl groups.

[0047] Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of such groups include alkyl groups.

[0048] R 4 and R 5 Of the hydrocarbon groups represented by the formula (I), preferred are linear or branched alkyl groups, and more preferred are linear or branched C 1-8 Alkyl group, linear or branched C 1-6 Alkyl group, linear or branched C 1-4 Alkyl groups, particularly linear or branched C groups such as methyl, ethyl, and isopropyl groups. 1-3 Alkyl groups are preferred, and linear or branched C groups are preferred because they have better dispersibility (or compatibility) with resins. 2-4 Alkyl groups are preferred, and linear or branched C 2-3 R is an alkyl group. 4 and R 5 When both are hydrocarbon groups, R 4 and R 5 may be different from each other, but are preferably the same.

[0049] Also, R 4 and R 5 and bond to each other to form adjacent nitrogen atoms [i.e., R 4 , R 5and a nitrogen atom that bonds with a carbonyl group to form an amide group (amide bond or carboxylic acid amide)], the heterocycle (N-containing heterocycle) may contain the nitrogen atom as a heteroatom, and may further contain one or more heteroatoms in addition to the nitrogen atom, as necessary. Examples of the heteroatom that may further contain include a nitrogen atom, an oxygen atom, a sulfur atom, and the like, and may contain at least one heteroatom selected from these, and preferably contains at least an oxygen atom. The number of heteroatoms constituting the heterocycle may be, for example, about 1 to 3, preferably 1 to 2, and more preferably 2. The heterocycle is often, for example, a 5- to 7-membered ring (5- to 7-membered heterocycle), preferably a 5- or 6-membered ring, and more preferably a 6-membered ring. The heterocycle may be aromatic, but is preferably non-aromatic.

[0050] Representative examples of the heterocycle include heterocycles containing one or more nitrogen atoms, such as a pyrrolidine ring, a piperidine ring, a homopiperidine ring (an azepane ring, a hexahydroazepine ring, or a hexamethyleneimine ring), and heterocycles containing a nitrogen atom and a heteroatom of a different kind, such as a morpholine ring. Of these, preferred are non-aromatic 5- to 7-membered heterocycles containing a nitrogen atom and a heteroatom of a different kind, particularly an oxygen atom, such as a morpholine ring.

[0051] In formula (X1), R adjacent to the nitrogen atom 4 and R 5 may both be hydrogen atoms; one may be a hydrogen atom and the other a hydrocarbon group; R 4 and R 5 may both be hydrocarbon groups or may be linked together to form a heterocycle. That is, the group [-C(=O)-X 1a ], [-C(=O)-X 1b may be an unsubstituted amide group (primary amide group); a monosubstituted amide group (or an N-substituted amide group); or a disubstituted amide group (or an N,N-disubstituted amide group). 1a and X 1bThe types of may be different from each other, but are preferably the same.

[0052] From the viewpoint of effectively improving the electrical conductivity, the group [-C(=O)-X 1a ], [-C(=O)-X 1b is preferably a mono- or di-substituted amide group, specifically R 4 and R 5 At least one of the groups is preferably a hydrocarbon group, and particularly preferably the group [-C(=O)-X 1a ], [-C(=O)-X 1b ] is a disubstituted amide group, in particular R 4 and R 5 Preferably, both are hydrocarbon groups.

[0053] Also, R 4 or R 5 When at least one of, and preferably both of, is a hydrocarbon group, the hydrocarbon group is preferably an aliphatic hydrocarbon group such as an alkyl group or a cycloalkyl group, more preferably an alkyl group, and further preferably a linear or branched C group such as a methyl group, an ethyl group, or an isopropyl group. 1-6 Alkyl groups, especially linear or branched C 1-4 Alkyl groups are preferred, particularly linear or branched C groups such as ethyl groups. 1-3 Alkyl groups are preferred.

[0054] Although it is not clear why the addition of fluorene derivatives improves electrical conductivity, it is speculated that this enables the CNTs to be adequately dispersed in the resin while suppressing their aggregation, and efficiently forms a network structure (conductive path) in which the CNTs are in contact with or connected to each other.

[0055] Representative compounds represented by the formula (1) include, for example, compounds represented by the formula (1) in which R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R4 and R 5 In particular, 9,9-bis(2-carbamoyl)C such as 9,9-bis(2-carbamoylethyl)fluorene and 9,9-bis(2-carbamoylpropyl)fluorene. 2-3 alkyl" fluorene, etc.; in formula (1), R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 wherein one of the groups is a hydrogen atom and the other is an alkyl group, specifically, for example, 9,9-bis[2-(NC)-fluorene such as 9,9-bis[2-(N-methylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N-methylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N-ethylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N-isopropylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N-isopropylcarbamoyl)propyl]fluorene, and 9,9-bis[2-(N-butylcarbamoyl)ethyl]fluorene. 1-6 Alkyl-carbamoyl)C 2-3 alkyl]fluorene, etc.; in formula (1), R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5is an alkyl group, specifically, for example, 9,9-bis[2-(N,N-diC] such as 9,9-bis[2-(N,N-dimethylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N,N-dimethylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N,N-diethylcarbamoyl)ethyl]fluorene, 9,9-bis[2-(N,N-diethylcarbamoyl)propyl]fluorene, 9,9-bis[2-(N,N-diisopropylcarbamoyl)ethyl]fluorene, and 9,9-bis[2-(N,N-dibutylcarbamoyl)ethyl]fluorene. 1-6 Alkyl-carbamoyl)C 2-3 alkyl]fluorene, etc.; in formula (1), R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 and bond to each other to form a 5- to 7-membered heterocycle which may further contain at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom in addition to the nitrogen atom constituting the amide group, specifically, for example, 9,9-bis[2-(N-containing heterocycle-N-yl-carbonyl) compounds such as 9,9-bis[2-(morpholin-4-yl-carbonyl)ethyl]fluorene, 9,9-bis[2-(morpholin-4-yl-carbonyl)propyl]fluorene, 9,9-bis[2-(pyrrolidin-1-yl-carbonyl)ethyl]fluorene, 9,9-bis[2-(piperidin-1-yl-carbonyl)ethyl]fluorene, and 9,9-bis[2-(homopiperidin-1-yl-carbonyl)ethyl]fluorene. 2-3 alkyl]fluorene and the like.

[0056] These fluorene derivatives may be used alone or in combination of two or more. 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R3b is a hydrogen atom or a methyl group, R 4 and R 5 and R are hydrogen atoms (unsubstituted amide compounds); 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 A compound in which one is a hydrogen atom and the other is an alkyl group (N-alkyl substituted compound); 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 A compound in which both of the above are alkyl groups (N,N-dialkyl substituted compound) is preferred, and from the viewpoint of more effectively improving the electrical conductivity, an N-alkyl substituted compound or an N,N-dialkyl substituted compound is preferred, and an N,N-dialkyl substituted compound is more preferred.

[0057] Preferred N-alkyl substituted compounds include 9,9-bis[2-(NC 1-6 Alkyl-carbamoyl)C 2-3 alkyl]fluorene, and more preferably 9,9-bis[2-(NC 2-5 Alkyl-carbamoyl)C 2-3 Among them, 9,9-bis[2-(NC alkyl)fluorene such as 9,9-bis[2-(N-isopropylcarbamoyl)ethyl]fluorene is preferred. 2-4 Alkyl-carbamoyl)C 2-3 Alkyl]fluorene is preferred.

[0058] Preferred N,N-dialkyl substituted compounds include 9,9-bis[2-(N,N-diC 1-6 Alkyl-carbamoyl)C 2-3alkyl]fluorene, and more preferably 9,9-bis[2-(N,N-diC 1-4 Alkyl-carbamoyl)C 2-3 Among them, 9,9-bis[2-(N,N-dialkyl)fluorene such as 9,9-bis[2-(N,N-dimethylcarbamoyl)ethyl]fluorene and 9,9-bis[2-(N,N-diethylcarbamoyl)ethyl]fluorene are preferred. 1-3 Alkyl-carbamoyl)C 2-3 Alkyl]fluorenes are preferred, and 9,9-bis[2-(N,N-dimethylcarbamoyl)ethyl]fluorene is particularly preferred.

[0059] (Method of producing fluorene derivative) The method for producing the compound represented by formula (1) is not particularly limited. For example, the compound may be prepared by reacting a compound represented by formula (2) below with compounds represented by formulas (3a) and (3b) below (Michael addition reaction).

[0060] [ka]

[0061] (In the formula, R 1 and k are the same as in the above formula (1), including preferred embodiments.

[0062] [ka]

[0063] (In the formula, R 2a , R 2b , R 2c and R 2d , R 3a and R 3b , X 1a and X 1b are the same as those in the above formula (1), including preferred embodiments thereof.

[0064] A representative example of the compound represented by the formula (2) is 9H-fluorene.

[0065] In addition, in the compounds represented by the formulas (3a) and (3b), R 2a , R 2b , R 2c and R 2d Depending on the type, it may be either the E or Z form.

[0066] Representative compounds represented by the formulas (3a) and (3b) include, for example, compounds represented by the formula (1) specifically exemplified by R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 Compounds in which both are hydrogen atoms, specifically (meth)acrylamide, etc.; R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 In the above formula, one of the NC groups is a hydrogen atom and the other is an alkyl group. Specifically, N-isopropyl (meth)acrylamide and other NC groups are 1-6 Alkyl-(meth)acrylamide, etc.; R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 In particular, N,N-diC such as N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide. 1-6 Alkyl-(meth)acrylamide; R 2a , R 2b , R 2cand R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, R 4 and R 5 are bonded to each other to form a 5- to 7-membered heterocycle which may further contain at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom in addition to the nitrogen atom constituting the amide group, specifically, an N-(meth)acryloyl N-containing heterocycle such as N-(meth)acryloylmorpholine, etc. It is preferable that the compounds represented by the formulas (3a) and (3b) are the same compound.

[0067] The ratio of the amount of the compound represented by the formula (2) to the total amount of the compounds represented by the formulas (3a) and (3b) may be, for example, the former / latter (molar ratio)=about 1 / 2 to 1 / 10, and preferred ranges are, in the following stepwise order, 1 / 2 to 1 / 5, 1 / 2.01 to 1 / 3, and 1 / 2.03 to 1 / 2.1.

[0068] The reaction may usually be carried out in the presence of a base, such as a metal hydroxide, a metal carbonate or hydrogen carbonate, or a metal alkoxide.

[0069] Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as barium hydroxide.

[0070] Examples of metal carbonates or hydrogen carbonates include alkali metal carbonates or hydrogen carbonates such as sodium carbonate, potassium carbonate, and sodium hydrogen carbonate.

[0071] Examples of metal alkoxides include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0072] These bases can be used alone or in combination of two or more. Among these bases, metal hydroxides are preferred, and alkali metal hydroxides such as potassium hydroxide are more preferred. The ratio of the base may be, for example, about 0.001 to 0.1 mol, and preferably 0.01 to 0.05 mol, relative to 1 mol of the compound represented by the formula (2).

[0073] The reaction may be carried out in the presence or absence of a phase transfer catalyst. Examples of the phase transfer catalyst include tetraalkylammonium halides such as tetrabutylammonium bromide (TBAB) and trioctylmethylammonium chloride. These phase transfer catalysts can be used alone or in combination of two or more. Among these phase transfer catalysts, TBAB is preferred. The ratio of the phase transfer catalyst may be, for example, about 0.001 to 0.1 mol, and preferably 0.01 to 0.05 mol, relative to 1 mol of the compound represented by the formula (2).

[0074] The reaction may be carried out in the absence or presence of a solvent inert to the reaction, such as water, alcohols such as methanol and ethanol, ethers such as cyclic ethers and chain ethers, sulfoxides such as dimethyl sulfoxide (DMSO), and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0075] Examples of cyclic ethers include 1,4-dioxane and tetrahydrofuran. Examples of chain ethers include dialkyl ethers such as diethyl ether and diisopropyl ether, and glycol ethers. Examples of the glycol ethers include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0076] Examples of the aliphatic hydrocarbons include hexane and dodecane. Examples of the alicyclic hydrocarbons include cyclohexane. Examples of the aromatic hydrocarbons include toluene and xylene.

[0077] These solvents may be used alone or in combination of two or more. Among these solvents, a mixed solvent of water, a sulfoxide such as DMSO, and an aromatic hydrocarbon such as toluene is preferred. Water may be added in the form of an aqueous solution of the above-mentioned base. The amount of the solvent used is not particularly limited as long as it does not hinder the progress of the reaction, and may be, for example, about 10 to 500 mL, preferably 50 to 200 mL, relative to 100 g of the total amount of the compounds represented by the formulas (2), (3a), and (3b).

[0078] The reaction may be carried out under an inert gas atmosphere, for example, under an atmosphere of nitrogen or a rare gas such as helium or argon. The reaction temperature is, for example, 50 to 200° C., preferably 80 to 100° C. The reaction time is not particularly limited and may be, for example, about 0.5 to 10 hours.

[0079] After completion of the reaction, the reaction mixture may be separated and purified, if necessary, by a conventional separation and purification method, for example, neutralization, washing, extraction, filtration, decantation, concentration, dehydration, drying, crystallization, chromatography, or a combination of these methods.

[0080] (Characteristics of fluorene derivatives) The fluorene derivative obtained as described above may be in a crystalline or amorphous form. When it is in a crystalline form, the melting point is the same as that of the group [-C(=O)-X 1a ], [-C(=O)-X 1b When the group [-C(=O)-X 1a ], [-C(=O)-X 1bWhen the group [-C(=O)-X 1a ], [-C(=O)-X 1b When [] is a disubstituted amide group, the temperature may be, for example, about 50 to 200°C, preferably 70 to 180°C, and more preferably 80 to 160°C.

[0081] The 5% mass loss temperature of the fluorene derivative may be, for example, about 200 to 400° C., and preferably is, in the following stepwise order, 230 to 380° C., 250 to 360° C., 280 to 350° C., 300 to 340° C., and 310 to 330° C. As described above, the fluorene derivative has high heat resistance and can therefore be effectively used as a conductive agent even in high-temperature environments.

[0082] In addition, the fluorene derivative has excellent solubility in a solvent. In particular, in the formula (1), the group [-C(=O)-X 1a ], [-C(=O)-X 1b Compounds in which ] is a disubstituted amide group appear to be more soluble in a wider variety of solvents.

[0083] In this specification and claims, the melting point and 5% mass loss temperature can be measured by the method described in the examples below.

[0084] [Carbon nanotubes (CNT)] The carbon nanotube (CNT) may be any CNT having a nano-sized diameter (nanoscale carbon tube), and various types of conventional CNTs may be used. The space inside the tube of the CNT may contain a metal, for example, iron.

[0085] Representative CNTs include (i) single-walled or multi-walled carbon nanotubes, (ii) amorphous nanoscale carbon tubes, (iii) nanoflake carbon tubes, and (iv) iron-carbon composites consisting of at least one carbon nanotube (a) selected from nanoflake carbon tubes and nested multi-walled carbon nanotubes, and iron carbide or iron (b), with the iron carbide or iron (b) filling the inner space of the carbon nanotube (a). These carbon nanotubes can be used alone or in combination of two or more kinds.

[0086] A single-walled or multi-walled carbon nanotube (i) is a hollow carbon material in which a graphite sheet, i.e., a carbon atom plane or a graphene sheet of a graphite structure is closed in a tube shape, and its diameter is on the nanometer scale, and the wall structure has a graphite structure. Among carbon nanotubes having such a structure, a carbon nanotube having a wall structure in which a single graphite sheet is closed in a tube shape is called a single-walled carbon nanotube (SWCNT), and a carbon nanotube having a structure in which multiple graphite sheets are closed in a tube shape and nested is called a multi-walled carbon nanotube (nested multi-walled carbon nanotube or MWCNT). The single-walled carbon nanotube and the multi-walled carbon nanotube may be used alone or in combination.

[0087] The size of the single-walled carbon nanotubes is, for example, a diameter (average diameter) of 0.4 to 10 nm and a length (average length) of 1 to 500 μm, preferably a diameter of 0.7 to 5 nm and a length of 1 to 100 μm, and more preferably a diameter of 0.7 to 2 nm and a length of 1 to 20 μm.

[0088] The size of the multi-walled carbon nanotubes is, for example, a diameter (average diameter) of 1 to 100 nm and a length (average length) of 1 to 500 μm, preferably a diameter of 1 to 50 nm and a length of 5 to 100 μm, more preferably a diameter of 1 to 40 nm and a length of 10 to 50 μm, and particularly preferably a diameter of 5 to 20 nm and a length of 20 to 30 μm.

[0089] The bulk density (tapping method) of the multi-walled carbon nanotubes is, for example, 0.03 to 0.2 g / cc, preferably 0.05 to 0.15 g / cc, and more preferably 0.06 to 0.14 g / cc.

[0090] Examples of the amorphous nanoscale carbon tubes (ii) include nanotubes described in WO00 / 40509 (Japanese Patent No. 3355442), that is, nanoscale carbon tubes having a main skeleton made of carbon, a diameter of 0.1 to 1000 nm, and an amorphous structure, which have a linear morphology, and in which, in an X-ray diffraction method (incident X-rays: CuKα), the planar spacing (d002) of the carbon net plane (002) measured by a diffractometer method is 3.54 Å or more, particularly 3.7 Å or more, the diffraction angle (2θ) is 25.1 degrees or less, particularly 24.1 degrees or less, and the half-width of the 2θ band is 3.2 degrees or more, particularly 7 degrees or more.

[0091] Examples of the nanoflake carbon tubes (iii) include carbon nanotubes formed by assembling a plurality of, usually a large number of, flake-shaped graphite sheets in a patchwork or paper mache configuration.

[0092] An example of the iron-carbon composite (iv) is the iron-carbon composite described in JP 2002-338220 A, that is, an iron-carbon composite comprising (a) a carbon tube selected from the group consisting of nanoflake carbon tubes and nested multi-walled carbon nanotubes, and (b) iron carbide or iron, in which 10 to 90% of the space inside the carbon tube (a) is filled with the iron carbide or iron (b).

[0093] Among these carbon nanotubes, from the viewpoint of an excellent balance between electrical conductivity, cost efficiency, etc., single-walled or multi-walled carbon nanotubes and iron-carbon composites consisting of nested multi-walled carbon nanotubes and iron carbide or iron are preferred, with single-walled or multi-walled carbon nanotubes being particularly preferred, and multi-walled carbon nanotubes being particularly preferred.

[0094] [resin] Examples of the resin include curable resins (thermo- or photo-curable resins), thermoplastic resins, etc. These resins can be used alone or in combination of two or more kinds.

[0095] Examples of the curable resin include phenolic resins such as resol type phenolic resins and novolac type phenolic resins; amino resins such as urea resins, melamine resins, and guanamine resins; furan resins; unsaturated polyester resins; diallyl phthalate resins; vinyl ester resins (or epoxy (meth)acrylate resins); polyfunctional (meth)acrylate resins; epoxy resins; urethane resins; polyimide resins such as bismaleimide resins; silicone resins, etc. These curable resins can be used alone or in combination of two or more.

[0096] Examples of thermoplastic resins include polyolefin resins, styrene resins, (meth)acrylic resins, vinyl acetate resins, vinyl chloride resins, fluororesins, polyester resins, polycarbonate resins (PC), polyamide resins (PA), polyacetal resins (POM), polyphenylene ether resins (PPE), polyether ketone resins, phenoxy resins, polyketone resins, polyphenylene sulfide resins (PPS), polysulfone resins, cellulose derivatives, thermoplastic polyimide resins, polyether nitrile resins, thermoplastic elastomers (TPE), etc. These thermoplastic resins can be used alone or in combination of two or more.

[0097] Examples of styrene resins include polystyrene (PS) such as general-purpose polystyrene (GPPS) and syndiotactic polystyrene (SPS), and styrene copolymers. Examples of styrene copolymers include styrene-methyl methacrylate copolymer (MS resin), styrene-acrylonitrile copolymer (AS resin), rubber component-containing styrene resin or rubber-grafted styrene copolymer. Examples of rubber component-containing styrene resin or rubber-grafted styrene copolymer include high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), AXS resin, methyl methacrylate-butadiene-styrene copolymer (MBS resin), and the like. Examples of AXS resins include acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), acrylonitrile-(ethylene-propylene-diene rubber)-styrene copolymer (AES resin), and the like.

[0098] Examples of the (meth)acrylic resin include homopolymers or copolymers of (meth)acrylic monomers such as polymethyl methacrylate (PMMA) and (meth)acrylic acid-(meth)acrylic acid ester copolymers.

[0099] Examples of vinyl acetate resins include polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetal, etc. Examples of polyvinyl acetal include polyvinyl formal (PVF), polyvinyl butyral (PVB), etc.

[0100] Examples of vinyl chloride resins include vinyl chloride resins and vinylidene chloride resins. Examples of vinyl chloride resins include vinyl chloride homopolymers (PVC); vinyl chloride copolymers such as vinyl chloride-vinyl acetate copolymers, etc. Examples of vinylidene chloride resins include vinylidene chloride copolymers such as vinylidene chloride-vinyl chloride copolymers and vinylidene chloride-acrylonitrile copolymers, etc.

[0101] Examples of fluororesins include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), and ethylene-chlorotrifluoroethylene copolymer (ECTFE).

[0102] Examples of polyester resins include polyalkylene arylate resins, polyarylate resins, liquid crystal polyesters (LCPs), etc. Examples of polyalkylene arylate resins include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), poly 1,4-cyclohexyldimethylene terephthalate (PCT), polyethylene naphthalate, etc.

[0103] Examples of polyamide resins (PA) include aliphatic polyamide resins such as polyamide 6 and polyamide 66, aromatic polyamide resins such as poly-m-phenylene isophthalamide and poly-p-phenylene terephthalamide, and aramid resins.

[0104] Examples of polyetherketone resins include polyetherketone resin (PEK), polyetheretherketone resin (PEEK), and polyetherketoneetherketoneketone (PEKEKK).

[0105] Examples of the polyketone resin include aliphatic polyketone resins.

[0106] Examples of polysulfone resins include polysulfone resin (PSF) and polyethersulfone (PES).

[0107] Examples of the cellulose derivatives include cellulose esters such as nitrocellulose, cellulose acetate, and cellulose acetate propionate, and cellulose ethers such as ethyl cellulose.

[0108] Examples of thermoplastic polyimide resins include polyetherimide (PEI) and polyamideimide.

[0109] Examples of thermoplastic elastomers (TPEs) include polystyrene-based TPEs, polyolefin-based TPEs (TPOs), polydiene-based TPEs, chlorine-based TPEs, fluorine-based TPEs, polyurethane-based TPEs (TPUs), polyester-based TPEs (TPEEs), and polyamide-based TPEs (TPAs).

[0110] Of these resins, the resin composition preferably contains at least a thermoplastic resin. In the resin composition, the proportion of the thermoplastic resin may be selected from a range of, for example, about 1% by mass or more relative to the total resin, and the preferred ranges are as follows, in the following stepwise order: 10% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, 95% by mass or more, and particularly substantially 100% by mass.

[0111] Among the thermoplastic resins, it is preferable to include at least one selected from polyolefin-based resins and polycarbonate-based resins.

[0112] (Polyolefin resin) Polyolefin resins have low polarity and it is difficult to disperse carbon nanotubes, which are a carbon material, in them. However, by combining them with the specific fluorene derivative represented by the above formula (1), the dispersion can be made more effective or efficient.

[0113] Examples of polyolefin resins include linear olefin resins containing α-olefin as a main polymerization component, and cyclic olefin resins containing cyclic olefins as polymerization components. Examples of cyclic olefin resins include cyclic olefin copolymers (COC) such as ethylene-norbornene copolymers, addition or ring-opening polymers of cyclic olefins such as polynorbornene, polydicyclopentadiene, polycyclopentadiene, or hydrogenated products thereof, or hydrogenated products thereof. These polyolefin resins can be used alone or in combination of two or more kinds. Among these polyolefin resins, linear olefin resins are preferred.

[0114] Examples of α-olefins that are polymerization components of chain olefin resins include α-C olefins such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. 2-20 Olefins, etc., preferably α-C 2-10 Olefins, more preferably α-C such as ethylene and propylene 2-6 It is an olefin.

[0115] The chain olefin resin may be a homopolymer or a copolymer of the α-olefin. The polymerization components in the copolymer may contain two or more kinds of α-olefins, or may contain a copolymerizable monomer different from the α-olefin. The copolymer may be a random copolymer, a block copolymer, a graft copolymer, or the like.

[0116] Examples of the copolymerizable monomer different from the α-olefin include a (meth)acrylic monomer, an unsaturated carboxylic acid or an acid anhydride thereof, a vinyl carboxylate, and a diene.

[0117] Examples of the (meth)acrylic monomer include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, N-substituted (meth)acrylamide, (meth)acrylonitrile, etc. Examples of the (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid glycidyl, etc. Examples of the (meth)acrylic acid alkyl esters include (meth)acrylic acid C esters such as (meth)acrylic acid methyl ester and (meth)acrylic acid ethyl ester. 1-10 Examples of the N-substituted (meth)acrylamides include mono- or dialkyl (meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-isopropyl (meth)acrylamide.

[0118] Examples of the unsaturated carboxylic acid or its anhydride include (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, and anhydrides thereof (such as maleic anhydride).

[0119] Examples of the vinyl carboxylate include saturated vinyl carboxylates such as vinyl acetate and vinyl propionate.

[0120] Examples of dienes include non-conjugated alkadienes such as 1,4-hexadiene, 1,7-octadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene, and conjugated alkadienes such as butadiene and isoprene.

[0121] These copolymerizable monomers can be used alone or in combination of two or more. When the chain olefin resin contains a copolymerizable monomer, the ratio of the copolymerizable monomer to the total constitutional units may be, for example, about 90 mol% or less, and preferably, in the following stepwise manner, 70 mol% or less, 50 mol% or less, 30 mol% or less, 20 mol% or less, and 10 mol% or less. The ratio is, for example, 0.01 to 30 mol%, and preferably, in the following stepwise manner, 0.1 to 20 mol% and 1 to 10 mol%.

[0122] Representative chain olefin resins include poly α-C resins such as polyethylene resins, polypropylene resins, poly-1-butene resins, and poly-4-methyl-1-pentene resins. 2-6 These polyolefin resins can be used alone or in combination of two or more. Among these polyolefin resins, polyethylene resins and polypropylene resins are preferred.

[0123] Examples of polyethylene resins include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMWPE), ethylene-(α-C 3-10 olefin) copolymers, modified polyethylene, chlorinated polyethylene, ionomers, etc. 3-10 Examples of the polyolefin copolymer include an ethylene-propylene copolymer, an ethylene-(1-butene) copolymer, an ethylene-propylene-(1-butene) copolymer, an ethylene-(4-methyl-1-pentene) copolymer, etc. Examples of the modified polyethylene include maleic anhydride modified polyethylene, etc.

[0124] In addition, ethylene-(α-C 3-10 In copolymers such as olefin copolymers, the proportion of ethylene (or ethylene units) may be, for example, about 60 mol % or more, or about 70 to 99.5 mol %, based on the total polymerization components (monomers).

[0125] The polyethylene resin may be prepared using a multi-site catalyst such as a Ziegler catalyst, or a single-site catalyst such as a metallocene catalyst, and a polyethylene resin prepared using a metallocene catalyst is preferred.

[0126] These polyethylene resins can be used alone or in combination of two or more. Among these polyethylene resins, ethylene-(α-C 3-10 Olefin) copolymers are preferred, and ethylene-(α-C copolymers prepared by metallocene catalysts are preferred. 3-10 Olefin copolymers are more preferred.

[0127] The density of polyethylene resin is, for example, 0.87 to 1 g / cm 3 The preferred range is 0.88 to 0.98 g / cm3 in the following order: 3 , 0.885~0.95g / cm 3 , 0.895~0.92g / cm 3 , 0.9~0.91g / cm 3 In the present specification and claims, the density can be measured in accordance with JIS K 7122.

[0128] The weight average molecular weight Mw of the polyethylene resin may be selected, for example, from the range of about 10,000 to 10,000,000. The number average molecular weight Mn may be selected, for example, from the range of about 10,000 to 1,000,000. The molecular weight distribution (Mw / Mn) may be selected, for example, from the range of about 1 to 50. In this specification and claims, the weight average molecular weight, number average molecular weight, and molecular weight distribution can be measured by GPC in terms of standard polystyrene.

[0129] The melt flow rate (MFR) (unit: g / 10 min) of the polyethylene resin may be, for example, about 1 to 50, and preferred ranges are the following stepwise ranges: 2 to 30, 3 to 25, 4 to 20, 5 to 18, 6 to 15, and 8 to 12. In this specification and claims, the MFR of the polyethylene resin can be measured in accordance with JIS K 6922-2.

[0130] The polypropylene-based resin may be polypropylene (or a propylene homopolymer), a copolymer of propylene and another copolymerizable monomer, or a modified polypropylene. Examples of the copolymer of propylene and another copolymerizable monomer or the modified polypropylene include copolymers of propylene and another α-C copolymer, such as a propylene-ethylene copolymer, a propylene-(1-butene) copolymer, and a propylene-ethylene-(1-butene) copolymer. 2-10 Examples include copolymers with olefins, maleic anhydride modified polypropylene, and chlorinated polypropylene.

[0131] Also, propylene and other α-C 2-10 In a copolymer of propylene and other copolymerizable monomers, such as a copolymer with an olefin, or a modified polypropylene, the proportion of propylene (or propylene units) is, for example, 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more, based on the total polymerization components (monomers). The proportion may be, for example, 80 to 99.5 mol%, preferably 85 to 99 mol%, and more preferably 94 to 98 mol%.

[0132] The copolymer of propylene and another copolymerizable monomer or the modified polypropylene may be a random copolymer, a block copolymer or a graft copolymer.

[0133] In addition, examples of polypropylene-based resins include high-density polypropylene (high crystallinity polypropylene (HCPP)), medium-density polypropylene, low-density polypropylene (low crystallinity polypropylene (LCPP)), and very low-density polypropylene (very low crystallinity polypropylene (VLCPP)) from the viewpoint of crystallinity. The polypropylene-based resin may be a polypropylene-based resin having stereoregularity such as isotactic polypropylene (IPP) or syndiotactic polypropylene (SPP) from the viewpoint of stereoregularity, or may be a polypropylene-based resin having no stereoregularity such as atactic polypropylene (APP). The polypropylene-based resin having stereoregularity may be a polypropylene-based resin having a narrow molecular weight distribution obtained by using a metallocene catalyst.

[0134] These polypropylene-based resins may be used alone or in combination of two or more. Among these polypropylene-based resins, polypropylene (propylene homopolymer) is preferred.

[0135] The weight average molecular weight Mw of the polypropylene resin may be selected, for example, from the range of about 10,000 to 10,000,000. The number average molecular weight Mn may be selected, for example, from the range of about 10,000 to 1,000,000. The molecular weight distribution (Mw / Mn) may be selected, for example, from the range of about 1 to 50. In this specification and claims, the weight average molecular weight, number average molecular weight, and molecular weight distribution can be measured by GPC in terms of standard polystyrene.

[0136] The melt flow rate (MFR) (unit: g / 10 min) of the polypropylene resin may be, for example, about 0.5 to 55, and preferred ranges are the following stepwise ranges: 1 to 50, 2 to 40, 3 to 30, 4 to 20, 5 to 15, 6 to 12, and 8 to 10. In this specification and claims, the MFR of the polyethylene resin can be measured at a test condition of 230° C. in accordance with JIS K 7210.

[0137] (Polycarbonate resin) The polycarbonate resin may be an aliphatic polycarbonate resin, but is preferably an aromatic polycarbonate resin such as a bi- or bisphenol type polycarbonate resin.

[0138] Examples of bi- or bisphenols that are polymerization components for forming bi- or bisphenol-type polycarbonate resins include bisphenols such as bis(hydroxyaryl)alkanes, bis(hydroxyaryl)-arylalkanes, bis(hydroxyaryl)cycloalkanes, bis(hydroxyaryl)ethers, bis(hydroxyaryl)ketones, bis(hydroxyaryl)sulfides, bis(hydroxyaryl)sulfoxides, bis(hydroxyaryl)sulfones, and 9,9-bis(hydroxyaryl)fluorenes; biphenols; and alkylene oxide (alkylene carbonate or haloalkanol) adducts thereof.

[0139] Examples of bis(hydroxyaryl)alkanes include bis(hydroxyphenyl)alkanes such as bis(4-hydroxyphenyl)methane (bisphenol F), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol AD), 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), and 2,2-bis(4-hydroxyphenyl)-3-methylbutane. 1-6 Alkanes; bis(hydroxy-C) such as 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C) and 2,2-bis(4-hydroxy-3-isopropylphenyl)propane (bisphenol G) 1-6 Alkyl-phenyl)C 1-6 Alkanes; bis(hydroxyphenylphenyl) C such as 2,2-bis(4-hydroxy-3-phenylphenyl)propane 1-6 Alkanes and the like.

[0140] Examples of bis(hydroxyaryl)-arylalkanes include bis(hydroxyphenyl)-mono- or diphenyl-C such as 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP) and bis(4-hydroxyphenyl)-diphenylmethane (bisphenol BP). 1-6 Alkanes and the like.

[0141] Examples of bis(hydroxyaryl)cycloalkanes include bis(hydroxyphenyl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclopentane and 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z). 5-10 Cycloalkanes; bis(hydroxyphenyl)-mono- and tri-C such as 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC). 1-6 Alkyl-C 5-10 Cycloalkanes and the like.

[0142] Examples of the bis(hydroxyaryl) ethers include bis(hydroxyphenyl) ethers such as bis(4-hydroxyphenyl) ether.

[0143] Examples of the bis(hydroxyaryl)ketones include bis(hydroxyphenyl)ketones such as bis(4-hydroxyphenyl)ketone.

[0144] Examples of the bis(hydroxyaryl)sulfides include bis(hydroxyphenyl)sulfides such as bis(4-hydroxyphenyl)sulfide.

[0145] Examples of the bis(hydroxyaryl)sulfoxides include bis(hydroxyphenyl)sulfoxides such as bis(4-hydroxyphenyl)sulfoxide.

[0146] Examples of the bis(hydroxyaryl)sulfones include bis(hydroxyphenyl)sulfones such as bis(4-hydroxyphenyl)sulfone (bisphenol S).

[0147] Examples of the 9,9-bis(hydroxyaryl)fluorenes include 9,9-bis(hydroxyphenyl)fluorene such as 9,9-bis(4-hydroxyphenyl)fluorene; 9,9-bis(hydroxy-mono or di-C such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene. 1-6 9,9-bis(hydroxy-mono or di-C alkyl-phenyl)fluorene; 9,9-bis(hydroxy-mono or di-C alkyl-phenyl)fluorene, such as 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene 6-10 arylphenyl)fluorene; and 9,9-bis(hydroxynaphthyl)fluorenes such as 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene.

[0148] Examples of biphenols include o,o'-biphenol, m,m'-biphenol, and p,p'-biphenol.

[0149] Examples of alkylene oxide (alkylene carbonate or haloalkanol) adducts of bisphenols or biphenols include C 2-4 Alkylene oxide adducts, etc. The number of moles of alkylene oxide (alkylene carbonate or haloalkanol) added may be, for example, about 2 to 20 moles per mole of the bisphenols or biphenols.

[0150] The bisphenol-type polycarbonate resin may be formed by using these bisphenols alone or in combination of two or more. Among these bisphenols, bis(hydroxyaryl)alkanes are preferred, and bis(hydroxyphenyl)alkanes such as bisphenol F, bisphenol AD, and bisphenol A are preferred. 1-4 Alkanes are more preferred, with bisphenol A being especially preferred.

[0151] The polycarbonate resin may be a polyester carbonate resin copolymerized with a dicarboxylic acid component. Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids such as adipic acid, alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and ester-forming derivatives thereof. Examples of the ester-forming derivatives include alkyl esters such as methyl esters and ethyl esters, acid halides such as acid chlorides, and acid anhydrides.

[0152] These polycarbonate resins can be used alone or in combination of two or more. The preferred polycarbonate resins are bis(hydroxyphenyl) C, such as bisphenol A polycarbonate resins. 1-6 It is a polycarbonate resin that uses alkanes as polymerization components.

[0153] These polyolefin resins and polycarbonate resins can be used alone or in combination of two or more. Among the polyolefin resins and polycarbonate resins, polyolefin resins are preferred, and among them, linear olefin resins such as polyethylene resins and polypropylene resins are preferred, and polypropylene resins are particularly preferred. When the fluorene derivative has a highly polar amide group, i.e., a group [-C(=O)-X 1a ], [-C(=O)-X 1b], it appears that the electrical conductivity can be effectively improved, possibly because the material can be unexpectedly dispersed in non-polar or low-polarity resins (or non-polar polymers) such as polyolefin resins.

[0154] [Other ingredients] The resin composition may further contain other components as necessary in addition to the resin, carbon nanotubes, and the compound represented by the formula (1). Examples of other components include conventional additives, such as fillers or reinforcing agents such as silica, talc, and mica; colorants such as dyes and pigments; flame retardants such as phosphorus-based flame retardants, halogen-based flame retardants, and inorganic flame retardants; flame retardant assistants; plasticizers; lubricants; stabilizers such as antioxidants, ultraviolet absorbers, and heat stabilizers; release agents; conductive agents; antistatic agents; surfactants; dispersants; flow control agents; leveling agents; defoamers; surface modifiers; stress reducing agents; antibacterial agents; preservatives; curing agents; curing accelerators; and solvents (solvents or dispersion media).

[0155] These additives may be used alone or in combination of two or more. The proportion of these additives is not particularly limited, and is, for example, 10% by mass or less, preferably 3% by mass or less, based on the entire resin composition. The proportion may be, for example, about 0.01 to 5% by mass, preferably 0.1 to 1% by mass.

[0156] The other components may be contained in the resin composition, or may be contained in a conductive agent for preparing the resin composition (the conductive agent prepared in the primary mixing step described below).

[0157] [Preferable ratio in resin composition] The proportion of the fluorene derivative represented by the formula (1) may be selected from the range of, for example, about 0.01 to 20 parts by mass relative to 100 parts by mass of the resin, and preferred ranges are 0.1 to 10 parts by mass, 1 to 7 parts by mass, 1.5 to 5 parts by mass, and more preferably 2 to 4 parts by mass, in the following stepwise order. If the proportion of the fluorene derivative represented by the formula (1) is too low, the electrical conductivity may not be effectively improved, and conversely, if it is too high, the physical properties, particularly the mechanical properties such as impact strength, may be reduced.

[0158] The proportion of the carbon nanotubes may be selected from the range of, for example, about 0.01 to 30 parts by mass relative to 100 parts by mass of the resin, and preferred ranges are 0.1 to 20 parts by mass, 1 to 15 parts by mass, 3 to 10 parts by mass, 4 to 9 parts by mass, and more preferably 5 to 8 parts by mass in the following stepwise order. If the proportion of the carbon nanotubes is too low, the electrical conductivity may not be effectively improved, and conversely, if it is too high, mechanical properties such as impact strength may be reduced.

[0159] The ratio of the fluorene derivative represented by the formula (1) to the carbon nanotubes may be selected from a range of, for example, the former / latter (mass ratio)=about 1 / 0.1 to 1 / 10, and the preferred ranges are 1 / 0.5 to 1 / 5, 1 / 0.8 to 1 / 4, 1 / 1 to 1 / 3, 1 / 1.2 to 1 / 2.8, 1 / 1.5 to 1 / 2.5, and more preferably 1 / 1.7 to 1 / 2.3 in the following stepwise manner. The ratio may be the ratio in the resin composition, or the ratio in the conductive agent of the present invention described later. If the ratio of the fluorene derivative represented by the formula (1) is too small, the CNTs cannot be dispersed in the resin, and aggregates are likely to be generated, which may prevent the conductivity from being effectively improved, and if the ratio of the carbon nanotubes is too small, it may be difficult to efficiently form a conductive path (or route), which may prevent the conductivity from being effectively improved.

[0160] When the fluorene derivative, CNT, and resin are combined in the above ratios, the CNTs are easily dispersed in the resin without agglomerating, and conductive paths are efficiently formed (perhaps because the dispersion state is suitable for forming conductive paths), which effectively improves conductivity. In other words, the fluorene derivative appears to be able to suppress the formation of CNT agglomerates in the resin and disperse them, while not dispersing them excessively, and to promote the formation of a network structure (conductive paths) in which the CNTs are in contact with or connected to each other.

[0161] [Method of producing resin composition (method of improving electrical conductivity) and characteristics] The resin composition of the present invention can be prepared by a method of mixing (or kneading) the resin, the carbon nanotubes, the fluorene derivative represented by the formula (1), and, if necessary, the other components described above. That is, in the present invention, the conductivity of the resin can be improved by adding (or mixing) the compound represented by the formula (1) and the carbon nanotubes to the resin.

[0162] Mixing (or kneading) may be a conventional method such as dry or wet mixing, melt kneading, etc. Mixing (or kneading) may be performed using a conventional device, for example, a mixer (kneader or stirrer) such as a roll (mixing roll), ball mill, tumble mixer, ribbon blender, Henschel mixer, kneader, Banbury mixer, etc., extruder such as a granulating extruder, single screw or twin screw extruder, etc. These devices may be used alone or in combination of two or more kinds.

[0163] The mixing (kneading) temperature and time may be appropriately selected depending on the type of fluorene derivative and resin, and may be, for example, 10 to 300° C., preferably 20 to 200° C., and more preferably 80 to 120° C., and the mixing (kneading) time may be, for example, about 1 to 10 minutes. In addition, when the resin contains a curable resin, the temperature and time may be such that the curable resin does not completely cure.

[0164] In the above method, all the components may be mixed (or kneaded) together to prepare the composition, and such a method of mixing all the components together may reduce the resistivity. In addition, from the viewpoint of suppressing scattering and improving handling (operability or safety), the method may include a primary mixing step (pre-mixing step or conductive agent preparation step) of mixing the carbon nanotubes and the fluorene derivative represented by the formula (1) to prepare a mixture (conductive agent), and a secondary mixing step (or conductive agent addition step) of mixing the mixture obtained in the primary mixing step with a resin.

[0165] (Primary mixing process (pre-mixing process or conductive agent preparation process)) In the primary mixing step, the fluorene derivative and the CNT are mixed (or kneaded) to prepare a conductive agent. The conductive agent of the present invention may contain at least the fluorene derivative and the CNT, and the preferred ratio of the fluorene derivative to the CNT is the same as that described in the section [Preferred ratio in the resin composition] above.

[0166] In addition, the conductive agent may further contain conventional additives as exemplified in the section on other components, if necessary, and when the conductive agent contains these components, they may be mixed with the fluorene derivative and the CNT in the primary mixing step. The total amount of the fluorene derivative and the CNT in the conductive agent of the present invention is, for example, 10% by mass or more, preferably 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, 95% by mass or more, and more preferably 100% by mass, that is, it is preferable that the conductive agent is substantially formed only by the fluorene derivative and the CNT.

[0167] The mixing method in the primary mixing step is not particularly limited, and can be mixed by a conventional mixing (or kneading) method in the presence or absence of a solvent. When mixing in the absence of a solvent, it is preferable to heat to a temperature equal to or higher than the melting point of the fluorene derivative and melt knead. Among these methods, the method of mixing in the presence of a solvent is preferable from the viewpoint of simplicity and convenience.

[0168] Examples of the solvent include water; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl propyl ketone, di-n-propyl ketone, diisopropyl ketone, and cyclohexanone; nitriles such as acetonitrile, propionitrile, and benzonitrile; cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; amides such as formamide, acetamide, dimethylformamide, and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; sulfolanes such as sulfolane; aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and halogenated hydrocarbons such as dichloromethane, dichloroethane, trichloroethylene, and dichlorobenzene.

[0169] These solvents can be used alone or in combination of two or more. Among these solvents, water, alcohols, hydrocarbons, halogenated hydrocarbons, etc. are preferred, and from the viewpoint of handling, etc., aqueous solvents such as water and alcohols, especially water, are preferred.

[0170] The solvent capable of dissolving the fluorene derivative can be appropriately selected depending on the type of the fluorene derivative, and examples thereof include alcohols such as methanol, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene, and halogenated hydrocarbons such as dichloromethane. Examples of the aqueous solvent include water, C 1-3 Among these, aromatic hydrocarbons such as toluene, water, and C 1-2 Alkanols are preferred, and water is especially preferred.

[0171] The ratio of the solvent can be selected from the range of, for example, about 10 to 10,000 parts by mass relative to 100 parts by mass of CNTs, and is, for example, 100 to 1,000 parts by mass, preferably 200 to 800 parts by mass, and more preferably 300 to 500 parts by mass. If the ratio of the solvent is too high, there is a risk of a decrease in productivity.

[0172] As a mixing method, a conventional method can be used, for example, a method of mixing or kneading CNT, a fluorene derivative, and a solvent using a conventional device such as a mixer (kneader or stirrer) or an extruder, a method of immersing CNT in a solution containing a fluorene derivative and a solvent, etc. Among these methods, the method of mixing or kneading using a device is preferred.

[0173] Examples of commonly used devices include mixers (kneaders or stirrers) and extruders exemplified in the above section [Method for producing a resin composition (Method for improving electrical conductivity)]. These devices can be used alone or in combination of two or more. Among these devices, extruders such as a granulating extruder, and mixers such as a mixing roller, a kneader, a Banbury mixer, and a Henschel mixer may be used, with the Henschel mixer being preferred.

[0174] When using an extruder, the CNT, the fluorene derivative, and the solvent may be charged and mixed all at once, or the CNT and the fluorene derivative may be mixed in advance, and then the solvent may be charged and mixed. The peripheral speed of the screw in the extruder is, for example, 1 to 300 m / min, preferably 50 to 150 m / min. The mixing temperature is not particularly limited, and may be room temperature.

[0175] The mixture obtained by these methods may be used as it is as a conductive agent, but it is preferable to remove the solvent by drying treatment. The drying treatment may be natural drying, but from the viewpoint of productivity, a method of heating and / or reducing pressure is preferable.

[0176] The heating method can be a conventional method, for example, a method using a stationary hot air dryer, a vacuum dryer, a rotary evaporator, or a mixing dryer such as a conical dryer or a Nauter dryer. The heating temperature can be appropriately selected depending on the type of solvent, and is, for example, 40 to 300°C, preferably 60 to 180°C, and more preferably 80 to 160°C.

[0177] The method for reducing the pressure can also be a conventional method, for example, a method using an oil pump, an oilless pump, an aspirator, a rotary evaporator, etc. The pressure in the reduction method is, for example, 0.00001 to 0.05 MPa, and preferably 0.00001 to 0.03 MPa.

[0178] When a lump-shaped conductive agent is obtained using a mixer, the lump-shaped conductive agent may be granulated (or particulated) by pulverization or the like in order to improve the ease of handling.

[0179] (Secondary mixing process (conductive agent addition process)) In the secondary mixing step, the mixture (conductive agent) containing the fluorene derivative and CNT obtained in the primary mixing step is mixed (or kneaded) with a resin to prepare a resin composition. When the resin composition contains the other components, the other components may be mixed with the conductive agent in the secondary mixing step.

[0180] The mixing method is not particularly limited and may be appropriately selected depending on the type of resin and the form of the desired resin composition. For example, it may be a conventional mixing (or kneading) method in the presence or absence of a solvent, specifically, dry or wet mixing, melt kneading, etc., and when the resin contains a thermoplastic resin, melt kneading is preferred.

[0181] For mixing (or kneading), a conventional device such as a mixer (kneader or stirrer) or an extruder exemplified in the above section [Method for producing a resin composition (Method for improving electrical conductivity)] may be used. These devices may be used alone or in combination of two or more. Representative devices include mixers such as a mixing roller, kneader, or Banbury mixer, and extruders such as a single-screw or twin-screw extruder, with a single-screw or twin-screw extruder being preferred.

[0182] The mixing (or kneading) conditions such as the kneading temperature can be appropriately selected depending on the type of resin, and a resin composition in which the conductive agent is uniformly dispersed can be easily prepared by a conventional method.

[0183] The form of the resin composition is not particularly limited, and may be a solid form such as a pellet, or a liquid form such as a solution (or dispersion). The resin composition may be molded by a conventional molding method such as injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, and casting molding to produce a molded product. When the resin composition is a curable composition (when the resin contains a curable resin), active energy (or active energy rays) such as thermal energy and / or light energy may be applied to the curable composition to form a cured product, and the cured product may be used as a molded product.

[0184] The shape of the molded body is not particularly limited and can be selected depending on the application. For example, it may be a one-dimensional structure such as a line or thread shape, a two-dimensional structure such as a film, sheet or plate shape, or a three-dimensional structure such as a block, rod, hollow or complex shape.

[0185] (Characteristics of resin composition) Since the resin composition exhibits high electrical conductivity, the surface resistivity (unit: Ω / □) of the resin composition is, for example, 1×10 2 ~1×10 8 , preferably 1 x 10 5 ~1×10 7 , and more preferably 5 × 10 5 ~1×10 6More preferably, it may be 1×10 2 ~1×10 6 , especially 1×10 3 ~1×10 4 The volume resistivity (unit: Ω·cm) of the resin composition is, for example, 1×10 1 ~1×10 6 , preferably 1 x 10 4 ~1×10 5 , and more preferably 3×10 4 ~8×10 4 More preferably, it may be 1×10 1 ~1×10 4 , especially 1×10 2 ~1×10 3 It is.

[0186] In the present specification and claims, the surface resistivity and volume resistivity can be measured in accordance with JIS K 6911, specifically, by the method described in the examples below.

[0187] Generally, high electrical conductivity and high impact strength tend to be in a trade-off relationship. However, the resin composition of the present invention can effectively improve electrical conductivity without significantly decreasing mechanical properties such as impact strength, and can often achieve both properties. Therefore, the Charpy impact strength (unit: kJ / m 2 ) may be, for example, about 1 to 100 depending on the type of resin, and particularly when the resin contains a polyolefin resin such as a polypropylene resin, it is, for example, 2 to 8, preferably 3 to 7, and more preferably 4 to 6.

[0188] In this specification and claims, the Charpy impact strength can be measured in accordance with JIS K 7111, and specifically, can be measured by the method described in the examples below.

[0189] The melt volume rate (MVR, unit: cm) of the resin composition 3 / 10 min) may be, for example, about 0.1 to 100 depending on the type of resin, and when the resin contains a polyolefin resin such as a polypropylene resin, it is, for example, 0.1 to 10, preferably 0.5 to 5, and more preferably 1 to 3, and when the resin contains a polycarbonate resin such as an aromatic polycarbonate resin, it is, for example, 1 to 100, preferably 5 to 90. When the resin contains a polycarbonate resin such as an aromatic polycarbonate resin, it appears that the MVR is easily improved by adding a fluorene derivative, particularly the unsubstituted amide compound, even when CNTs are contained.

[0190] In this specification and claims, MVR can be measured in accordance with JIS K 7210-1 B method, specifically, by the method described in the examples below. EXAMPLES

[0191] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Details of the evaluation methods and reagents used are shown below.

[0192] [Evaluation method] (HPLC) The HPLC (high performance or high performance liquid chromatograph) device used was the "LCMS-2020" manufactured by Shimadzu Corporation, and the column used was the "KINTEX XB-C18" manufactured by Shimadzu Corporation. The mobile phase was changed from acetonitrile / water (volume ratio) = 50 / 50 to 95 / 5 over 10 minutes, and then held at 95 / 5 for 5 minutes.

[0193] ( 1 H-NMR) The sample was dissolved in a heavy solvent (CDCl3) containing tetramethylsilane as an internal standard, and the NMR spectrum was measured using a nuclear magnetic resonance spectrometer (BRUKER's "AVANCE III HD"). 1 H-NMR spectrum was measured.

[0194] (Melting Point) The measurement was performed using a BUCHI "Melting point M-565" at a temperature of 50°C and a heating rate of 0.5°C / min.

[0195] (5% mass reduction temperature) Using a thermogravimetry-differential thermal analyzer (TG-DTA) (PerkinElmer's "TGA-4000"), the temperature at which the sample lost 5% by mass was measured under conditions of a nitrogen atmosphere, a measurement temperature range of 50 to 400°C, and a heating rate of 10°C / min.

[0196] (Conductive) For the resin compositions obtained in the examples and comparative examples, the surface resistivity [Ω / □] and volume resistivity [Ω·cm] were measured using a resistivity meter ("Hiresta UP" manufactured by Mitsubishi Chemical Analytical Co., Ltd.) in accordance with JIS K 6911 under the conditions of a measurement probe: URS probe and a measurement voltage: 10 V. The surface resistivity and volume resistivity were measured at a total of six points on the front and back surfaces of three test pieces, and the average values ​​were calculated.

[0197] (Charpy impact strength) The resin compositions obtained in the examples and comparative examples were measured 10 times using a digital impact tester ("DG-CB" manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with JIS K 7111. The average value was used as the Charpy impact strength [kJ / m 2 The notch shape was B, and the hammer was 2.0J (base resin: PP) or 7.5J (base resin: PC).

[0198] (Melt Volume Rate (MVR)) Measurements were performed in accordance with JIS K 7210-1 B method under the following conditions: holding time: 5 minutes, temperature: 230°C (base resin: PP) or 300°C (base resin: PC), test load: 2.16kgf (base resin: PP) or 1.20kgf (base resin: PC).

[0199] [Reagents, etc.] (raw materials) N,N-Diethylacrylamide: "DEAA (registered trademark)" manufactured by KJ Chemicals, Inc. N,N-Dimethylacrylamide: "DMAA (registered trademark)" manufactured by KJ Chemicals Co., Ltd. N-isopropylacrylamide: "NIPAM (registered trademark)" manufactured by KJ Chemicals Co., Ltd. N-Acryloylmorpholine: "ACMO (registered trademark)" manufactured by KJ Chemicals Co., Ltd. Acrylamide: Fujifilm Wako Pure Chemical Industries, Ltd. (others) DMSO: Dimethyl sulfoxide, manufactured by Kanto Chemical Co., Ltd. Toluene: Kanto Chemical Co., Ltd. TBAB: Tetrabutylammonium bromide, manufactured by Tokyo Chemical Industry Co., Ltd. KOH: Potassium hydroxide, manufactured by Kanto Chemical Co., Ltd. Isopropanol: Kanto Chemical Co., Ltd. (resin) PP: Polypropylene resin, Prime Polypro (registered trademark) manufactured by Prime Polymer Co., Ltd. ) J105G PC: Bisphenol A polycarbonate, "Iupilon PC S-3000" manufactured by Mitsubishi Engineering Plastics Corporation (Carbon Nanotubes) CNT: Multi-walled carbon nanotubes, Kumho's "K-Nanos 100T".

[0200] [Synthesis Example 1] 9H-fluorene (19.4g; 0.117mol), DMSO (30mL), toluene (30mL), TBAB (0.6g; 0.0019mol), and N,N-diethylacrylamide (30.5g; 0.24mol) were charged into a reactor equipped with a magnetic stirrer and a three-way cock, and the atmosphere was replaced with nitrogen. The temperature was then raised to 65°C, and complete dissolution was confirmed. A 48% by mass KOH aqueous solution (0.56g; 0.0048mol (4.8mmol) in terms of KOH) was added to the resulting solution, which was then heated to 90°C and stirred for 2 hours. The reaction was terminated when the disappearance of 9H-fluorene was confirmed by HPLC. The resulting reaction solution was cooled to 50°C, and 10% by mass HCl aqueous solution (0.9g; 0.0025mol (2.5mmol) in terms of HCl) and ion-exchanged water (17mL) were added and stirred to neutralize, after which toluene (18.1g) and saturated saline (36.1g x 3 times) were added and an extraction operation was performed. The resulting extract was cooled to 0°C and left to stand overnight, whereupon white crystals precipitated. The crystals were filtered out and washed with ion-exchanged water (37.3mL) and isopropanol (10mL), yielding the target product represented by the following formula (1-1) (DEAA-FL, 30.2g; yield 61.4%).

[0201] The melting point of the obtained DEAA-FL was 87 to 89°C, and the 5% mass loss temperature was 294°C. 1 The H-NMR results are shown below and in FIG.

[0202] [ka]

[0203] 1 H-NMR (CDCl3, 300MHz): δ(ppm)=7.69-7.72(2H, m), 7.27-7.43(6H, m), 3.18(4H, q), 2.79(4H, q), 2.42-2.48(4H, m), 1.47-1.53(4H, m), 0.96(6H, t), 0.76(6H, t).

[0204] [Synthesis Example 2] 9H-fluorene (19.4g; 0.117mol), DMSO (30mL), toluene (30mL), TBAB (0.6g; 0.0019mol), and N,N-dimethylacrylamide (23.8g; 0.24mol) were charged into a reactor equipped with a magnetic stirrer and a three-way cock, and the atmosphere was replaced with nitrogen. The temperature was then raised to 65°C, and complete dissolution was confirmed. A 48% by mass KOH aqueous solution (0.56g; 0.0048mol (4.8mmol) in terms of KOH) was added to the resulting solution, which was then heated to 90°C and stirred for 2 hours. The reaction was terminated when the disappearance of 9H-fluorene was confirmed by HPLC. The resulting reaction solution was cooled to 50°C, and a 10% by mass HCl aqueous solution (0.9 g; 0.0025 mol (2.5 mmol) in terms of HCl) and ion-exchanged water (17 mL) were added and stirred, whereupon white crystals gradually precipitated, forming a white suspension. The suspension was filtered and washed with hot water (77.7 mL) and isopropanol (15 mL), yielding the target product (DMAA-FL, 30.0 g; yield 82.4%) represented by the following formula (1-2).

[0205] The melting point of the obtained DMAA-FL was 158 to 159°C, and the 5% mass loss temperature was 318°C. 1 The H-NMR results are shown below and in FIG.

[0206] [ka]

[0207] 1 H-NMR (CDCl3, 300MHz): δ (ppm) = 7.70-7.71 (2H, m), 7.27-7.41 (6H, m), 2.74 (6H, s), 2.51 (6H, s), 2.42-2.47 (4H, m), 1.48-1.54 (4H, m).

[0208] [Synthesis Example 3] 9H-fluorene (19.4g; 0.117mol), DMSO (30mL), toluene (30mL), TBAB (0.6g; 0.0019mol), and N-isopropylacrylamide (27.2g; 0.24mol) were charged into a reactor equipped with a magnetic stirrer and a three-way cock, and the atmosphere was replaced with nitrogen. The temperature was then raised to 65°C, and complete dissolution was confirmed. A 48% by mass KOH aqueous solution (0.56g; 0.0048mol (4.8mmol) in terms of KOH) was added to the resulting solution, which was then heated to 90°C and stirred for 2 hours. The reaction was terminated when the disappearance of 9H-fluorene was confirmed by HPLC. The resulting reaction solution was cooled to 50°C, and a 10% by mass HCl aqueous solution (0.9 g; 0.0025 mol (2.5 mmol) in terms of HCl) and ion-exchanged water (17 mL) were added and stirred, whereby white crystals gradually precipitated, forming a white suspension. The suspension was filtered and washed with hot water (77.7 mL) and isopropanol (15 mL), yielding the target product (NIPAM-FL, 32.8 g; yield 71.4%) represented by the following formula (1-3).

[0209] The melting point of the obtained NIPAM-FL was 235 to 237°C, and the 5% mass loss temperature was 257°C. 1 The H-NMR results are shown below and in FIG.

[0210] [ka]

[0211] 1 H-NMR (CDCl3, 300MHz): δ (ppm) = 7.68-7.71 (2H, m), 7.32-7.42 (6H, m), 4.73 (2H, m) 3.84 (2H, m), 2.42 (4H, m), 1.33 (4H, m), 0.97 (12H, d).

[0212] [Synthesis Example 4] 9H-fluorene (19.4g; 0.117mol), DMSO (30mL), toluene (30mL), TBAB (0.6g; 0.0019mol), and acrylamide (17.0g; 0.24mol) were charged into a reactor equipped with a magnetic stirrer and a three-way cock, and the atmosphere was replaced with nitrogen. The temperature was raised to 65°C, and complete dissolution was confirmed. 48% by mass KOH aqueous solution (0.56g; 0.0048mol (4.8mmol) in terms of KOH) was added to the obtained solution, and the temperature was raised to 90°C and the solution was heated and stirred for 2 hours. The reaction was terminated when the disappearance of 9H-fluorene was confirmed by HPLC. The obtained reaction solution was cooled to 50°C, and 10% by mass HCl aqueous solution (0.9g; 0.0025mol (2.5mmol) in terms of HCl) and ion-exchanged water (17mL) were added and stirred, and white crystals were gradually precipitated, forming a white suspension. The suspension was filtered and washed with hot water (77.7 mL) and isopropanol (15 mL), obtaining the target product represented by the following formula (1-4) (AAD-FL, 31.8 g; yield 88.4%).

[0213] The melting point of the obtained AAD-FL was 254 to 259°C, and the 5% mass loss temperature was 320°C. 1 The H-NMR results are shown below and in FIG.

[0214] [ka]

[0215] 1 H-NMR (DMSO-d6, 300MHz): δ (ppm) = 7.82-7.84 (2H, m), 7.47-7.49 (2H, m), 7.35-7.40 (4H, m), 6.97 (2H, s), 6.52 (2H, s), 2.24 (4H, m), 1.26 (4H, m).

[0216] [Synthesis Example 5] 9H-fluorene (19.4g; 0.117mol), DMSO (30mL), toluene (30mL), TBAB (0.6g; 0.0019mol), and N-acryloylmorpholine (33.8g; 0.24mol) were charged into a reactor equipped with a magnetic stirrer and a three-way cock, and the atmosphere was replaced with nitrogen. The temperature was then raised to 65°C, and complete dissolution was confirmed. A 48% by mass KOH aqueous solution (0.56g; 0.0048mol (4.8mmol) in terms of KOH) was added to the resulting solution, which was then heated to 90°C and stirred for 2 hours. The reaction was terminated when the disappearance of 9H-fluorene was confirmed by HPLC. The resulting reaction solution was cooled to 50°C, and a 10% by mass HCl aqueous solution (0.9 g; 0.0025 mol (2.5 mmol) in terms of HCl) and ion-exchanged water (17 mL) were added and stirred, whereupon white crystals gradually precipitated, forming a white suspension. The suspension was filtered and washed with hot water (77.7 mL) and isopropanol (15 mL), yielding the target compound (ACMO-FL) represented by the following formula (1-5).

[0217] [ka]

[0218] [Comparative Example 1] 100 parts by mass of CNT and 400 parts by mass of ion-exchanged water were put into a Henschel type mixer (Universe Co., Ltd.) and mixed at room temperature for 5 minutes, and the resulting mixture was granulated at room temperature using an extrusion granulator (Dalton's "Disc Cutter"). The granulated material was dried under reduced pressure at 180°C for 24 hours to prepare an additive (conductive agent) (primary mixing process).

[0219] 6 parts by mass of the obtained conductive agent and 94 parts by mass of PP were kneaded to prepare a resin composition (secondary mixing step).

[0220] [Example 1] A mixed liquid (or dispersion) was prepared by mixing (or dispersing) 50 parts by mass of DEAA-FL prepared in Synthesis Example 1 in 400 parts by mass of ion-exchanged water in a mixer. Except for putting the obtained mixed liquid and 100 parts by mass of CNT into a Henschel type mixer, the mixture was granulated and dried in the same manner as in Comparative Example 1 to prepare a conductive agent (primary mixing step).

[0221] 9 parts by mass of the obtained conductive agent and 91 parts by mass of PP were kneaded to prepare a resin composition (secondary mixing step).

[0222] [Example 2] A mixed liquid (or dispersion) was prepared by mixing (or dispersing) 50 parts by mass of NIPAM-FL prepared in Synthesis Example 3 in 400 parts by mass of ion-exchanged water in a mixer. Except for putting the obtained mixed liquid and 100 parts by mass of CNT into a Henschel type mixer, the mixture was granulated and dried in the same manner as in Comparative Example 1 to prepare a conductive agent (primary mixing step).

[0223] 9 parts by mass of the obtained conductive agent and 91 parts by mass of PP were kneaded to prepare a resin composition (secondary mixing step).

[0224] [Example 3] A mixed liquid (or dispersion) was prepared by mixing (or dispersing) 50 parts by mass of AAD-FL prepared in Synthesis Example 4 in 400 parts by mass of ion-exchanged water in a mixer. Except for putting the obtained mixed liquid and 100 parts by mass of CNT into a Henschel type mixer, the mixture was granulated and dried in the same manner as in Comparative Example 1 to prepare a conductive agent (primary mixing step).

[0225] 9 parts by mass of the obtained conductive agent and 91 parts by mass of PP were kneaded to prepare a resin composition (secondary mixing step).

[0226] [Comparative Example 2] A resin composition was prepared in the same manner as in Comparative Example 1, except that 94 parts by mass of PC was used in place of 94 parts by mass of PP.

[0227] [Example 4] A resin composition was prepared in the same manner as in Example 3, except that 91 parts by mass of PC was used in place of 91 parts by mass of PP.

[0228] Tables 1 and 2 show the evaluation results of the electrical conductivity, Charpy impact strength, and MVR of the resin compositions obtained in Comparative Examples 1 and 2 and Examples 1 to 4. In the tables, the surface resistivity and volume resistivity are shown as values ​​measured at a measurement voltage of 10 V.

[0229] In addition, to measure the electrical conductivity and Charpy impact strength, the obtained resin compositions were injection molded using an injection molding machine (Nissei Plastic Industrial Co., Ltd.'s "Electric High-Performance Injection Molding Machine") under conditions of a cylinder temperature of 230°C, a mold temperature of 70°C, and a filling speed of 20 mm / sec for resin compositions having PP as the base resin, and a cylinder temperature of 290°C, a mold temperature of 90°C, and a filling speed of 20 mm / sec for resin compositions having PC as the base resin. Test pieces were used.

[0230] [Table 1]

[0231] [Table 2]

[0232] As is clear from the results in Tables 1 and 2, all of the resin compositions contain 6% by mass of CNTs relative to the total mass, but the resistivity (surface resistivity and volume resistivity) of the Examples is significantly reduced compared to the Comparative Examples, and the conductivity is improved. In particular, in Example 1, in which DEAA-FL was added, the order of magnitude of the surface resistivity and volume resistivity was 10 times that of Comparative Example 1. 9 10 for 4 ~10 5 Moreover, in Examples 1 to 3, the electrical conductivity could be improved without a significant decrease in impact strength or MVR compared to Comparative Example 1, and in particular in Example 1, the impact strength did not decrease at all.

[0233] [Comparative Example 3] A resin composition was prepared by kneading 6 parts by mass of CNTs and 94 parts by mass of PP all at once without granulating them in advance in a primary mixing step.

[0234] [Example 5] A resin composition was prepared by kneading 6 parts by mass of CNT, 3 parts by mass of DEAA-FL, and 91 parts by mass of PP all at once without granulating them in advance in a primary mixing step.

[0235] Table 3 shows the evaluation results of the electrical conductivity, Charpy impact strength, and MVR of the resin compositions obtained in Comparative Example 3 and Example 5. In the table, the surface resistivity and volume resistivity are shown as values ​​measured under the condition of a measurement voltage of 10 V, and the surface resistivity of Example 5 was measured using "Loresta GP" manufactured by Mitsubishi Chemical Analytical Corporation instead of "Hiresta UP."

[0236] Further, for the measurement of electrical conductivity and Charpy impact strength, test pieces prepared by injection molding under the same conditions as those for the resin compositions having PP as a base resin in Comparative Example 1 and Examples 1 to 3 were used.

[0237] [Table 3]

[0238] As is clear from the results in Table 3, the resistivity (surface resistivity and volume resistivity) was significantly reduced and the conductivity was improved in Example 5 compared to Comparative Example 3. Note that, although the resistivity is lower in Example 5 and Comparative Example 3 compared to Example 1 and Comparative Example 1 which were granulated in the primary mixing step, it is considered possible that the CNTs are partially present as aggregates in the resin composition to form conductive paths, since pellet-shaped CNTs are used. [Industrial Applicability]

[0239] Since the resin composition of the present invention has excellent electrical conductivity, it may be used for various applications such as antistatic applications, etc. For example, it can be effectively used for transport and packaging materials or transport molded articles for semiconductors and electric / electronic parts such as carrier tapes, office automation (OA) equipment, electric / electronic parts such as electromagnetic shielding materials, automobile parts for electrostatic painting, conductive paints, conductive adhesives, etc.

Claims

1. Resin, carbon nanotubes, and a compound represented by the following formula (1) 【Chemistry 1】 [In the formula, R １ represents a hydrocarbon group, k represents 0, R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ indicates a hydrogen atom, R ３ａ and R ３ｂ each independently represents a hydrogen atom or a methyl group, X １ａ and X １ｂ each independently represents the following formula (X1): 【Chemistry 2】 (In the formula, R ４ and R ５ each independently represents a hydrogen atom or a hydrocarbon group, or R ４ and R ５ and are bonded to each other to form a heterocycle together with the adjacent nitrogen atom. It represents a group represented by the following formula: A resin composition comprising a compound represented by the formula:

2. In the formula (1), R ４ and R ５ 2. The resin composition according to claim 1, wherein both of are hydrocarbon groups.

3. In the formula (1), R ４ and R ５ 3. The resin composition according to claim 1, wherein both of said alkyl groups are linear or branched.

4. The resin composition according to any one of claims 1 to 3, wherein the carbon nanotubes are single-walled or multi-walled carbon nanotubes.

5. The resin composition according to any one of claims 1 to 4, wherein the resin comprises at least one selected from the group consisting of polyolefin-based resins and polycarbonate-based resins.

6. The ratio of the compound represented by the formula (1) is 0.1 to 10 parts by mass relative to 100 parts by mass of the resin, The ratio of the carbon nanotubes is 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin, The resin composition according to any one of claims 1 to 5, wherein the ratio of the compound represented by the formula (1) to the carbon nanotubes is the former / latter (mass ratio) = 1 / 0.5 to 1 / 5.

7. A method for improving the electrical conductivity of a resin, comprising adding a compound represented by formula (1) according to claim 1 and carbon nanotubes to the resin.

8. The method according to claim 7, comprising a primary mixing step of mixing the compound represented by formula (1) according to claim 1 and carbon nanotubes, and a secondary mixing step of adding the mixture obtained in the primary mixing step to a resin.

9. 13. A conductive agent which is an additive for improving the electrical conductivity of a resin, comprising a compound represented by formula (1) according to claim 1 and carbon nanotubes.

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