JP7599301B2 - Resin composition and method for improving electrical conductivity - Google Patents

Description

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

Taking advantage of the excellent characteristics based on their 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. US Pat. No. 2,299,948 (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.

U.S. Pat. No. 2,299,948

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.

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 as an additive for improving the electrical conductivity (electrical conductivity) of resins.

Therefore, the object of the present invention is to provide a resin composition that exhibits high electrical conductivity (or low electrical resistance).

As a result of intensive research into achieving the above object, the inventors discovered that adding a fluorene derivative having a specific chemical structure to a resin together with carbon nanotubes can greatly improve electrical conductivity, and thus completed the present invention.

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

[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 represent a hydrogen atom or a substituent;
R ^3a and R ^3b each independently represent a hydrogen atom or a substituent;
X ^1a and X ^1b each independently represent the following formula (X1):

(In the formula, ^R4 and ^R5 each independently represent a hydrogen atom or a hydrocarbon group, or ^R4 and ^R5 are bonded to each other to form a heterocycle together with the adjacent nitrogen atom.)
It represents a group represented by the following formula:
In the formula (1), both R ⁴ and R ⁵ may be a hydrocarbon group. In addition, both R ⁴ and R ⁵ may be a linear or branched alkyl group. The carbon nanotube may be a single-walled or multi-walled carbon nanotube. The resin may include at least one selected from a polyolefin resin and a polycarbonate resin. The ratio of the compound represented by the 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 nanotube 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 the formula (1) to the carbon nanotube may be the former/latter (mass ratio)=about 1/0.5 to 1/5.

The present invention includes a method for improving the electrical conductivity of a resin (a method for reducing resistance or a method for preventing electrostatic charge) by adding a 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.

The present invention also includes an additive that improves the electrical conductivity of a resin, which is a conductive agent (a conductivity improver (or imparting agent), a conductive material, or an antistatic agent) that contains a compound represented by formula (1) and carbon nanotubes.

In addition, the present invention may solve the following problems as a secondary objective:

In other words, another object of the present invention is to provide a resin composition that can achieve both high electrical conductivity and high impact strength.

Yet another object of the present invention is to provide a method for improving the electrical conductivity of a resin, and an additive (conductive agent) that improves the electrical conductivity of a resin.

In this specification and claims, the number of carbon atoms in a substituent may be indicated as _C1 , _C6 , _C10 , etc. For example, an alkyl group having one carbon atom is indicated as a " _C1 alkyl" and an aryl group having 6 to 10 carbon atoms is indicated as a " _C6-10 aryl."

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 surprisingly achieves 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.

FIG. 1 is a ¹ H-NMR spectrum of DEAA-FL obtained in Synthesis Example 1. FIG. 2 is a ¹ H-NMR spectrum of DMAA-FL obtained in Synthesis Example 2. FIG. 3 is a ¹ H-NMR spectrum of NIPAM-FL obtained in Synthesis Example 3. FIG. 4 is a ¹ H-NMR spectrum of AAD-FL obtained in Synthesis Example 4.

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 conductive agent (or conductive material), conductive material, or antistatic agent).

[Fluorene derivatives]

[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 represent a hydrogen atom or a substituent;
R ^3a and R ^3b each independently represent a hydrogen atom or a substituent;
X ^1a and X ^1b each independently represent a group represented by the following formula (X1):

(wherein R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group, or R ⁴ and R ⁵ are bonded to each other to form a heterocycle together with the adjacent nitrogen atom).

In the formula (1), the group R ¹ may be a non-reactive substituent that is inert to 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. Examples of the aryl group include a C _6-10 aryl group such as a phenyl group. Preferred groups R ¹ are a cyano group, a halogen atom, or an alkyl group, and particularly an alkyl group.

Examples of the alkyl group include C _1-12 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group, preferably C _1-8 alkyl groups, and particularly C _1-4 alkyl groups such as methyl group.

In addition, when the number k of substitutions of the group R ¹ is more than one (2 or more), the types of the two or more groups R ¹ substituted on the same benzene ring among the two benzene rings constituting the fluorene ring may be the same or different, and the types of the two or more groups R ¹ substituted on different benzene rings may be the same or different. In addition, the bonding position (substitution position) of the group R ¹ is not particularly limited as long as it is the 1st to 8th positions of the fluorene ring, and examples thereof include the 2nd position, 7th position, and 2,7th positions of the fluorene ring.

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

The substituents represented by R ^2a , R ^2b , R ^2c and R ^2d may be non-reactive substituents that are inactive in the reaction, and examples thereof include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups and aralkyl groups.

Examples of the alkyl group include linear or branched _C1-10 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, and t-butyl groups, and are preferably linear or branched _C1-6 alkyl groups, and more preferably linear or branched _C1-4 alkyl groups.

Examples of the cycloalkyl group include a C _5-10 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.

Examples of the aryl group include C _6-12 aryl groups such as a phenyl group, an alkylphenyl group, a biphenylyl group, a naphthyl group, etc. Examples of the alkylphenyl group include mono- to tri-C _1-4 alkyl-phenyl groups such as a methylphenyl group (or a tolyl group) and a dimethylphenyl group (or a xylyl group).

Examples of the aralkyl group include a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group or a phenethyl group.

Preferred substituents represented by R ^2a , R ^2b , R ^2c and R ^2d include alkyl groups, and preferred alkyl groups are, in the following order, a C _1-6 alkyl group, a C _1-5 alkyl group, a C _1-4 alkyl group and a C _1-3 alkyl group, more preferably a C _1-2 alkyl group, and particularly preferably a methyl group.

Preferred R ^2a , R ^2b , R ^2c , and R ^2d are a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom. It is preferable that at least R ^2c and R ^2d are hydrogen atoms, and in such an embodiment, preferred R ^2a and R ^2b are 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 all hydrogen atoms).

Furthermore, the types of R ^2a , R ^2b , R ^2c and R ^2d may be different from one another, but it is preferable that R ^2a and R ^2b are the same, and R ^2c and R ^2d are the same.

The substituents represented by ^R3a and ^R3b may be non-reactive substituents that are inactive in the reaction, and examples of such substituents include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Examples of such hydrocarbon groups include the same groups as the hydrocarbon groups exemplified as the substituents represented by ^R2a and ^R2b .

Among the substituents represented by R ^3a and R ^3b , preferred substituents are alkyl groups, and preferred alkyl groups are, in the following stepwise order, a C _1-6 alkyl group, a C _1-5 alkyl group, a C _1-4 alkyl group, and a C _1-3 alkyl group, more preferably a C _1-2 alkyl group, and particularly preferably a methyl group.

Moreover, R ^3a and R ^3b are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

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

Examples of the alkyl group include linear or branched C1-12 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, neopentyl group, _hexyl group, octyl group, and decyl group.

Examples of the cycloalkyl group include a C _5-10 cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.

Examples of the aryl group include C _6-12 aryl groups such as a phenyl group, an alkylphenyl group, a biphenylyl group, a naphthyl group, etc. Examples of the alkylphenyl group include mono- to tri-C _1-4 alkyl-phenyl groups such as a methylphenyl group (or a tolyl group) and a dimethylphenyl group (or a xylyl group).

Examples of the aralkyl group include a C _6-10 aryl-C _1-4 alkyl group such as a benzyl group or a phenethyl group.

Of the hydrocarbon groups represented by R ⁴ and R ⁵ , preferred are linear or branched alkyl groups, more preferred are, in the following order, linear or branched C _1-8 alkyl groups, linear or branched C _1-6 alkyl groups, linear or branched C _1-4 alkyl groups, and among these, linear or branched C _1-3 alkyl groups such as methyl, ethyl, and isopropyl groups are preferred, and from the viewpoint of better dispersibility (or compatibility) in the resin, linear or branched C _2-4 alkyl groups are preferred, more preferably linear or branched C _2-3 alkyl groups. When both R ⁴ and R ⁵ are hydrocarbon groups, the types of R ⁴ and R ⁵ may be different from each other, but are preferably the same.

In addition, the heterocycle (N-containing heterocycle) that may be formed by R ⁴ and R ⁵ bonding together with the adjacent nitrogen atom [i.e., the nitrogen atom that bonds with R ⁴ , R ⁵ and the carbonyl group to form an amide group (amide bond or carboxylic acid amide)] 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 be further contained 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. In addition, the heterocycle may be aromatic, but is preferably non-aromatic.

Representative heterocyclic rings include, for example, heterocyclic rings 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 heterocyclic rings containing a nitrogen atom and a heteroatom of a different kind, such as a morpholine ring, and preferably non-aromatic 5- to 7-membered heterocyclic rings containing a nitrogen atom and a heteroatom of a different kind, particularly an oxygen atom, such as a morpholine ring.

In formula (X1), R ⁴ and R ⁵ adjacent to the nitrogen atom 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 bonded to each other to form a heterocycle. That is, the groups [-C(=O)-X ^1a ] and [-C(=O)-X ^1b ] may be unsubstituted amide groups (primary amide groups); monosubstituted amide groups (or N-substituted amide groups); or disubstituted amide groups (or N,N-disubstituted amide groups). The types of X ^1a and X ^1b may be different from each other, but are preferably the same.

From the viewpoint of effectively improving the electrical conductivity, it is preferable that the groups [-C(=O)-X ^1a ] and [-C(=O)-X ^1b ] are mono-substituted amide groups or di-substituted amide groups, and specifically, it is preferable that at least one of R ⁴ and R ⁵ is a hydrocarbon group, and among these, it is preferable that the groups [-C(=O)-X ^1a ] and [-C(=O)-X ^1b ] are di-substituted amide groups, and it is particularly preferable that both R ⁴ and R ⁵ are hydrocarbon groups.

Furthermore, when at least one of R ⁴ or R ⁵ , preferably both, 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, still more preferably a linear or branched C _1-6 alkyl group such as a methyl group, an ethyl group or an isopropyl group, of which a linear or branched C _1-4 alkyl group is preferred, and a linear or branched C _1-3 alkyl group such as an ethyl group is particularly preferred.

The reason why the addition of fluorene derivatives improves electrical conductivity is unclear, but it is speculated that this allows the CNTs to be adequately dispersed in the resin while suppressing their aggregation, and efficiently forms a network structure (conductive paths) in which the CNTs are in contact with or connected to each other.

Representative compounds represented by the formula (1) include, for example, compounds in which R ^2a , R ^2b , R ^2c and R ^2d are hydrogen atoms, R ^3a and R ^3b are hydrogen atoms or methyl groups, and both R ⁴ and R ⁵ are hydrogen ^atoms in the formula (1), specifically, for example, 9,9-bis(2-carbamoyl)C _2-3 alkyl fluorenes such as ^9,9 - ^bis (2- ^{carbamoylethyl )} fluorene and 9,9- ^bis ( ² -carbamoylpropyl)fluorene; Compounds in which one of R 2a , R 2b , R 2c and R 2d are hydrogen atoms, R 3a and R 3b are hydrogen atoms or methyl groups, R 4 and R ⁵ are alkyl groups, specifically, for example, 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, 9,9-bis[ ^2- (N-butylcarbamoyl)ethyl]fluorene and the ^{like ;} Compounds in which ⁵ is an alkyl group, specifically, for example, 9,9-bis[2-(N,N-diC 1-6 alkyl-carbamoyl)C 2-3 alkyl]fluorenes 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; Compounds in which ^3b is a hydrogen atom or a methyl group, and 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, for example, 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, 9,9-bis[2-(homopiperidin-1-yl-carbonyl) _ethyl ]fluorene, and the like, can be mentioned.

These fluorene derivatives can be used alone or in combination of two or more. Among these fluorene derivatives, the following compounds are available: in formula (1), R ^2a , R ^2b , R ^2c and R ^2d are hydrogen atoms, R ^3a and R ^3b are hydrogen atoms or methyl groups, and both R ⁴ and R ⁵ are hydrogen atoms (unsubstituted amide compounds); in formula (1), R ^2a , R ^2b , R ^2c and R ^2d are hydrogen atoms, R ^3a and R ^3b are hydrogen atoms or methyl groups, and one of R ⁴ and R ⁵ is a hydrogen atom and the other is an alkyl group (N-alkyl substituted compounds); in formula (1), R ^2a , R ^2b , R ^2c and R ^2d are hydrogen atoms, R ^3a and R ^3b are hydrogen atoms or methyl groups, and R ⁴ and R A compound in which both of ⁵ 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.

A preferred N-alkyl substituted compound is 9,9-bis[2-(N-C _1-6 alkyl-carbamoyl)C _2-3 alkyl]fluorene, more preferably 9,9-bis[2-(N-C _2-5 alkyl-carbamoyl)C _2-3 alkyl]fluorene, of which 9,9-bis[2-(N-isopropylcarbamoyl)ethyl]fluorene and other 9,9-bis[2-(N-C _2-4 alkyl-carbamoyl)C _2-3 alkyl]fluorenes are preferred.

A preferred N,N-dialkyl substituted compound is 9,9-bis[2-(N,N-diC _1-6 alkyl-carbamoyl)C _2-3 alkyl]fluorene, more preferably 9,9-bis[2-(N,N-diC _1-4 alkyl-carbamoyl)C _2-3 alkyl]fluorene, of which 9,9-bis[2-(N,N-diC 1-3 alkyl-carbamoyl)C _2-3 alkyl]fluorenes such as 9,9-bis[2-(N,N-dimethylcarbamoyl)ethyl]fluorene and _9,9 -bis[2-(N,N-diethylcarbamoyl)ethyl]fluorene are preferred, and 9,9-bis[2-(N,N-dimethylcarbamoyl)ethyl]fluorene is particularly preferred.

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

(In the formula, ^R1 and k are the same as those in the above formula (1) including preferred embodiments).

(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 in the above formula (1) including preferred embodiments).

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

In addition, the compounds represented by the formulae (3a) and (3b) may be either E- or Z-forms depending on the types of R ^2a , R ^2b , R ^2c and R ^2d .

Representative compounds represented by the formulae (3a) and (3b) include, for example, compounds in which R ^2a , R 2b , R ^2c and R ^2d are hydrogen atoms, R ^3a and R ^3b are hydrogen atoms or methyl groups, and both R ⁴ and R ⁵ are hydrogen atoms, specifically (meth)acrylamide, etc.; compounds in which R ^2a , R ^2b , R ^2c and R ^2d are hydrogen atoms, R ^3a and R ^3b are hydrogen atoms or methyl groups, and one of R ⁴ and R ⁵ is a hydrogen atom and the ^other is an alkyl group, specifically N-C _1-6 alkyl-(meth)acrylamide, etc.; compounds in which R ^2a , R ^2b , R ^2c and R ^2d are hydrogen atoms, R ^3a and R ^3b are hydrogen atoms or methyl groups, and R ⁴ and R Compounds in which both R and ^{R 5} are alkyl groups, specifically N,N-diC _1-6 alkyl-(meth)acrylamides such as N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide; compounds in which R ^2a , R ^2b , R ^2c and R ^2d are hydrogen atoms, R ^3a and R ^3b are hydrogen atoms or methyl groups, and 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 nitrogen atoms, oxygen atoms and sulfur atoms in addition to the nitrogen atom constituting the amide group, specifically N-(meth)acryloyl N-containing heterocycles such as N-(meth)acryloylmorpholine. It is preferable that the compounds represented by the formulas (3a) and (3b) are the same compound.

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

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

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

Examples of metal carbonates or bicarbonates include alkali metal carbonates or bicarbonates such as sodium carbonate, potassium carbonate, and sodium bicarbonate.

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

These bases may be used alone or in combination of two or more. Of 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, per 1 mol of the compound represented by formula (2).

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

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

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.

Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene and xylene.

These solvents can be used alone or in combination of two or more. Of 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 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, per 100 g of the total amount of the compounds represented by the formulas (2), (3a), and (3b).

The reaction may be carried out under an inert gas atmosphere, for example, 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.

After the reaction is completed, the reaction mixture may be separated and purified, if necessary, by conventional separation and purification methods, such as neutralization, washing, extraction, filtration, decantation, concentration, dehydration, drying, crystallization, chromatography, or a combination of these methods.

(Characteristics of fluorene derivatives)
The fluorene derivative obtained as described above may be in a crystalline or amorphous form. In the case of a crystalline form, the melting point may be, for example, about 200 to 300°C, preferably 230 to 280°C, more preferably 240 to 270°C, when the group [-C(=O)-X ^1a ], [-C(=O)-X ^1b ] is an unsubstituted amide group, and may be, for example, about 150 to 300°C, preferably 200 to 270°C, more preferably 220 to 250°C, when the group [-C(=O)-X ^1a ], [-C(=O) ^{-X 1b ]} is a monosubstituted amide group, and may be, for example, about 50 to 200°C, preferably 70 to 180°C, more preferably 80 to 160°C, when the group [-C(=O)-X ^1a ], [-C(=O)-X 1b ] is a disubstituted amide group.

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

In addition, fluorene derivatives have excellent solubility in solvents. In particular, compounds in which the groups [--C(=O)-- ^X.sub.1a ] and [--C(=O)-- ^X.sub.1b ] in the formula (1) are disubstituted amide groups appear to be more soluble in a wide variety of solvents.

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

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

Typical 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.

Single-walled or multi-walled carbon nanotubes (i) are hollow carbon materials in which graphite sheets, i.e., carbon atom planes or graphene sheets of a graphite structure, are closed in a tube shape, and their diameter is on the nanometer scale, with a graphite wall structure. Among carbon nanotubes having such a structure, carbon nanotubes having a wall structure closed in a tube shape with a single graphite sheet are called single-walled carbon nanotubes (SWCNTs), and carbon nanotubes having a structure in which multiple graphite sheets are each closed in a tube shape and nested are called multi-walled carbon nanotubes (nested multi-walled carbon nanotubes or MWCNTs). Single-walled carbon nanotubes and multi-walled carbon nanotubes may be used alone or in combination.

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.

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.

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.

Examples of amorphous nanoscale carbon tubes (ii) include nanotubes described in WO00/40509 (Japanese Patent Publication No. 3355442), i.e., 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 shape, and in X-ray diffraction (incident X-rays: CuKα), the planar spacing (d002) of the carbon net plane (002) measured by the 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.

Examples of nanoflake carbon tubes (iii) include carbon nanotubes that are formed by assembling multiple, usually many, flake-shaped graphite sheets in a patchwork or paper mache configuration.

As an example of the iron-carbon composite (iv), there may be mentioned the iron-carbon composite described in JP 2002-338220 A, that is, an iron-carbon composite consisting of (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 iron carbide or iron (b).

Among these carbon nanotubes, 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 because they offer an excellent balance between electrical conductivity and cost-effectiveness, with single-walled or multi-walled carbon nanotubes being particularly preferred and multi-walled carbon nanotubes being even more preferred.

[resin]
Examples of the resin include a curable resin (thermosetting or photosetting resin), a thermoplastic resin, etc. These resins can be used alone or in combination of two or more kinds.

Examples of curable resins 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; and silicone resins. These curable resins can be used alone or in combination of two or more.

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, and thermoplastic elastomers (TPEs). These thermoplastic resins can be used alone or in combination of two or more.

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 graft styrene copolymer. Examples of rubber component-containing styrene resin or rubber graft 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.

Examples of (meth)acrylic resins include homopolymers or copolymers of (meth)acrylic monomers such as polymethyl methacrylate (PMMA) and (meth)acrylic acid-(meth)acrylic acid ester copolymers.

Examples of vinyl acetate resins include polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), and polyvinyl acetal. Examples of polyvinyl acetal include polyvinyl formal (PVF) and polyvinyl butyral (PVB).

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; and the like. Examples of vinylidene chloride resins include vinylidene chloride copolymers such as vinylidene chloride-vinyl chloride copolymers and vinylidene chloride-acrylonitrile copolymers.

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).

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.

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.

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

Examples of polyketone resins include aliphatic polyketone resins.

Examples of polysulfone-based resins include polysulfone resin (PSF) and polyethersulfone (PES).

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

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

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).

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 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.

Furthermore, among the thermoplastic resins, it is preferable to include at least one selected from polyolefin-based resins and polycarbonate-based resins.

(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 the specific fluorene derivative represented by the above formula (1), the dispersion can be made more effective or efficient.

Examples of polyolefin resins include linear olefin resins containing α-olefins as the 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. Of these polyolefin resins, linear olefin resins are preferred.

Examples of the α-olefin that is a polymerization component of the chain olefin resin include α-C 2-20 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, and preferably α-C 2-10 olefins} , and more preferably α-C _2-6 olefins such as ethylene and propylene.

The linear olefin resin may be a homopolymer of the α-olefin or a copolymer. The polymerization components in the copolymer may contain two or more types 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.

Examples of copolymerizable monomers other than the α-olefin include (meth)acrylic monomers, unsaturated carboxylic acids or their anhydrides, vinyl carboxylates, and dienes.

Examples of the (meth)acrylic monomer include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, N-substituted (meth)acrylamides, (meth)acrylonitrile, etc. Examples of the (meth)acrylic acid esters include (meth)acrylic acid alkyl esters and (meth)acrylic acid glycidyl, etc. Examples of the (meth)acrylic acid alkyl esters include (meth)acrylic acid C _1-10 alkyl esters such as methyl (meth)acrylate and ethyl (meth)acrylate, etc. 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, etc.

Examples of unsaturated carboxylic acids or their anhydrides include (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, and their anhydrides (e.g., maleic anhydride).

Examples of vinyl carboxylates include saturated vinyl carboxylates such as vinyl acetate and vinyl propionate.

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.

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 structural 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%.

Representative examples of linear olefin resins include poly α-C _2-6 olefin resins such as polyethylene resins, polypropylene resins, poly 1-butene resins, and poly 4-methyl-1-pentene resins, and 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.

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. Examples of ethylene-(α-C 3-10 olefin} ) copolymers include ethylene-propylene copolymers, ethylene-(1-butene) copolymers, ethylene-propylene-(1-butene) copolymers, ethylene-(4-methyl-1-pentene) copolymers, etc. Examples of modified polyethylenes include maleic anhydride modified polyethylene, etc.

In addition, in copolymers such as ethylene-(α-C _3-10 olefin) copolymer, the proportion of ethylene (or ethylene units) relative to the total polymerization components (monomers) may be, for example, about 60 mol % or more, or may be about 70 to 99.5 mol %.

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.

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 _3-10 olefin) copolymers prepared by a metallocene catalyst are more preferred.

The density of the polyethylene resin may be selected, for example, from the range of about 0.87 to 1 g/cm ³ , and preferred ranges are 0.88 to 0.98 g/cm ³ , 0.885 to 0.95 g/cm ³ , 0.895 to 0.92 g/cm ³ , and 0.9 to 0.91 g/cm ³ in the following stepwise order. Note that in this specification and claims, the density can be measured in accordance with JIS K 7122.

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.

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

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 2-10 olefin such as a propylene-ethylene copolymer, a propylene-(1-butene) copolymer, and a propylene-ethylene-( ₁ -butene) copolymer; maleic anhydride-modified polypropylene; and chlorinated polypropylene.

In copolymers of propylene and other copolymerizable monomers, such as copolymers of propylene and other α-C _2-10 olefins, or modified polypropylenes, the proportion of propylene (or propylene units) relative to the total of the polymerization components (monomers) is, for example, 50 mol % or more, preferably 70 mol % or more, and more preferably 90 mol % or more. The proportion may be, for example, 80 to 99.5 mol %, preferably 85 to 99 mol %, and more preferably 94 to 98 mol %.

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

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. From the viewpoint of stereoregularity, the polypropylene-based resin may be a polypropylene-based resin having stereoregularity such as isotactic polypropylene (IPP) or syndiotactic polypropylene (SPP), 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 using a metallocene catalyst.

These polypropylene-based resins can be used alone or in combination of two or more. Of these polypropylene-based resins, polypropylene (propylene homopolymer) is preferred.

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.

The melt flow rate (MFR) (unit: g/10 min) of polypropylene-based resins may be, for example, about 0.5 to 55, and preferred ranges are as follows: 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 polyethylene-based resins can be measured at test conditions of 230°C in accordance with JIS K 7210.

(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.

Examples of biphenols, which are polymerization components for forming biphenol- 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.

Examples of bis(hydroxyaryl)alkanes include bis(hydroxyphenyl)C 1-6 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; bis(hydroxy-C _1-6 alkyl-phenyl)C _1-6 alkanes such as 2,2-bis(4-hydroxy-3-isopropylphenyl)propane ( _bisphenol G); and bis(hydroxy-phenylphenyl)C _1-6 alkanes such as 2,2-bis(4-hydroxy-3-phenylphenyl)propane.

Examples of bis(hydroxyaryl)-arylalkanes include bis(hydroxyphenyl)-mono- or diphenyl-C 1-6 alkanes such as 1,1-bis(4-hydroxyphenyl)-1-phenylethane (bisphenol AP) and bis( ₄ -hydroxyphenyl)-diphenylmethane (bisphenol BP).

Examples of the bis(hydroxyaryl)cycloalkanes include bis(hydroxyphenyl)C _5-10 cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclopentane and 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z); and bis(hydroxyphenyl)-mono- to tri-C _1-6 alkyl-C _5-10 cycloalkanes such as 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC).

Examples of bis(hydroxyaryl) ethers include bis(hydroxyphenyl) ethers such as bis(4-hydroxyphenyl) ether.

Examples of bis(hydroxyaryl)ketones include bis(hydroxyphenyl)ketones such as bis(4-hydroxyphenyl)ketone.

Examples of bis(hydroxyaryl)sulfides include bis(hydroxyphenyl)sulfides such as bis(4-hydroxyphenyl)sulfide.

Examples of bis(hydroxyaryl)sulfoxides include bis(hydroxyphenyl)sulfoxides such as bis(4-hydroxyphenyl)sulfoxide.

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

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 _1-6 alkyl-phenyl)fluorene such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene; 9,9-bis(hydroxy-mono- or di-C _6-10 arylphenyl)fluorene such as 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene; and 9,9-bis(hydroxynaphthyl)fluorene such as 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene.

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

Examples of alkylene oxide (alkylene carbonate or haloalkanol) adducts of bisphenols or biphenols include _C2-4 alkylene oxide adducts such as ethylene oxide adducts. The number of moles of alkylene oxide (alkylene carbonate or haloalkanol) added may be, for example, about 2 to 20 moles per mole of bisphenols or biphenols.

The bisphenol- or bicarbonate-based resin may be formed by using these bisphenols alone or in combination of two or more. Among these bisphenols, bis(hydroxyaryl)alkanes are preferred, bisphenol F, bisphenol AD, bisphenol A and other bis(hydroxyphenyl)C _1-4 alkanes are more preferred, and bisphenol A is particularly preferred.

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 cyclohexanedicarboxylic 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.

These polycarbonate resins may be used alone or in combination of two or more. Preferred polycarbonate resins are polycarbonate resins having bis(hydroxyphenyl)C _1-6 alkanes as a polymerization component, such as bisphenol A polycarbonate resin.

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. Even if the fluorene derivative has a highly polar amide group, i.e., the group [-C(=O)-X ^1a ] or [-C(=O)-X ^1b ], it seems that the conductivity can be effectively improved, probably because it can be unexpectedly dispersed in a non-polar or low-polar resin (or non-polar polymer) such as a polyolefin resin.

[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).

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, and preferably 3% by mass or less, based on the total resin composition. The proportion may be, for example, about 0.01 to 5% by mass, and preferably 0.1 to 1% by mass.

The other components may be included in the resin composition, or may be included in the conductive agent used to prepare the resin composition (the conductive agent prepared in the primary mixing step described below).

[Preferable ratio in resin composition]
The ratio 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 ratio 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 deteriorated.

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, with preferred ranges being 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 carbon nanotubes is too low, it may not be possible to effectively improve conductivity, and conversely, if it is too high, mechanical properties such as impact strength may be reduced.

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 as follows: 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. 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. 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.

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), effectively improving 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.

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

Mixing (or kneading) may be performed by a conventional method such as dry or wet mixing, or melt kneading. Mixing (or kneading) may be performed using conventional equipment, such as mixers (kneaders or stirrers) such as rolls (mixing rolls), ball mills, tumble mixers, ribbon blenders, Henschel mixers, kneaders, and Banbury mixers, and extruders such as granulating extruders and single-screw or twin-screw extruders. These equipment may be used alone or in combination of two or more.

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, if the resin contains a curable resin, the temperature and time may be such that the curable resin does not completely cure.

In the above method, all the components may be mixed (or kneaded) together to prepare the material. In such a method of mixing all the components together, the resistivity may be further reduced. From the viewpoint of suppressing scattering and improving handling (workability or safety), the method may include a primary mixing step (pre-mixing step or conductive agent preparation step) in which the carbon nanotubes and the fluorene derivative represented by formula (1) are mixed to prepare a mixture (conductive agent), and a secondary mixing step (or conductive agent addition step) in which the mixture obtained in the primary mixing step is mixed with a resin.

(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.

The conductive agent may further contain conventional additives as exemplified in the section on other components, if necessary. 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 relative to the entire conductive agent, and the preferred ranges are 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, i.e., the conductive agent is preferably formed substantially only from the fluorene derivative and the CNT.

The mixing method in the primary mixing step is not particularly limited, and mixing can be performed 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 the fluorene derivative to a temperature equal to or higher than the melting point thereof and melt-knead it. Of these methods, the method of mixing in the presence of a solvent is preferable from the viewpoint of simplicity, etc.

Examples of solvents 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.

These solvents can be used alone or in combination of two or more. Of these solvents, water, alcohols, hydrocarbons, halogenated hydrocarbons, etc. are preferred, and from the standpoint of ease of handling, etc., aqueous solvents such as water and alcohols, especially water, are preferred.

The solvent capable of dissolving the fluorene derivative can be appropriately selected depending on the type of the fluorene derivative, and examples of the solvent 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 and C _1-3 alkanols such as methanol. Among these, aromatic hydrocarbons such as toluene, water, and C _1-2 alkanols such as methanol are preferred, and water is particularly preferred.

The proportion of the solvent can be selected from the range of, for example, about 10 to 10,000 parts by mass per 100 parts by mass of CNT, 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 proportion of the solvent is too high, there is a risk of reduced productivity.

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

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 granulating extruders, and mixers such as mixing rollers, kneaders, Banbury mixers, and Henschel mixers may be used, with the Henschel mixer being preferred.

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, and preferably 50 to 150 m/min. The mixing temperature is not particularly limited and may be room temperature.

The mixture obtained by these methods may be used as a conductive agent as is, but it is preferable to remove the solvent by drying. The drying process may be natural drying, but from the viewpoint of productivity, a method in which heating and/or decompression is applied is preferable.

The heating method can be a conventional method, such as 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.

As a method for reducing the pressure, conventional methods such as a method using an oil pump, an oil-less pump, an aspirator, or a rotary evaporator can be used. The pressure in the reduction method is, for example, 0.00001 to 0.05 MPa, preferably 0.00001 to 0.03 MPa.

If a lump of conductive agent is obtained using a mixer, it may be granulated (or particulated) by grinding or other methods to improve handling.

(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. In addition, when the resin composition contains the other components, the resin composition may be mixed with the conductive agent in the secondary mixing step.

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.

For mixing (or kneading), a conventional device such as a mixer (kneader or stirrer) or 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 single-screw or twin-screw extruders, with single-screw or twin-screw extruders being preferred.

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 using conventional methods.

The form of the resin composition is not particularly limited, and may be a solid form such as pellets, 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, casting molding, or other injection 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.

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

(Characteristics of Resin Composition)
Since the resin composition exhibits high electrical conductivity, the surface resistivity (unit: Ω/□) of the resin composition may be, for example, 1×10 ² to 1×10 ⁸ , preferably 1×10 ⁵ to 1×10 ⁷ , more preferably 5×10 ⁵ to 1×10 ⁶ , more preferably 1×10 ² to 1×10 ⁶ , and particularly 1×10 ³ to 1×10 ^4. The volume resistivity (unit: Ω·cm) of the resin composition may be, for example, 1×10 ¹ to 1×10 ⁶ , preferably 1×10 ⁴ to 1×10 ⁵ , more preferably 3×10 ⁴ to 8×10 ⁴ , more preferably 1×10 ¹ to 1×10 ⁴ , and particularly 1×10 ² to 1×10 ³ .

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

Although high electrical conductivity and high impact strength are usually in a trade-off relationship, 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 ) of the resin composition may be, for example, about 1 to 100 depending on the type of resin, and in particular 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.

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

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

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

The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Details of the evaluation method and the reagents used are provided below.

[Evaluation method]
(HPLC)
The HPLC (high performance or high performance liquid chromatograph) device used was an "LCMS-2020" manufactured by Shimadzu Corporation, and the column used was a "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. Measurements were performed under these conditions.

( ^1H -NMR)
The sample was dissolved in a deuterated solvent (CDCl ₃ ) containing tetramethylsilane as an internal standard substance, and the ¹ H-NMR spectrum was measured using a nuclear magnetic resonance apparatus ("AVANCE III HD" manufactured by BRUKER).

(Melting Point)
The measurement was carried out using a BUCHI "Melting point M-565" under conditions of a temperature rise rate of 0.5°C/min from a temperature of 50°C.

(5% mass loss temperature)
Thermogravimetry - Differential thermal analysis (TG-DTA) (PerkinElmer's "TGA-4000") was used under the conditions of a nitrogen atmosphere, a measurement temperature range of 50 to 400°C, and a heating rate of 10°C/min. The temperature at which the mass of the sample decreased by 5% by mass was measured.

(Conductive)
For the resin compositions obtained in the examples and comparative examples, the surface resistivity [Ω/□] and volume resistivity [Ω·cm] were measured in accordance with JIS K 6911 using a resistivity meter ("Hiresta UP" manufactured by Mitsubishi Chemical Analytical Co., Ltd.) under 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.

(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, Ltd.) in accordance with JIS K 7111, and the average value was taken as the Charpy impact strength [kJ/m ² ]. The notch shape was B, and the hammer was 2.0 J (base resin: PP) or 7.5 J (base resin: PC).

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

[Reagents, etc.]
(Raw materials)
N,N-diethylacrylamide: "DEAA (registered trademark)" manufactured by KJ Chemicals Co., Ltd.
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. (Other)
DMSO: dimethyl sulfoxide, manufactured by Kanto Chemical Co., Ltd. Toluene: manufactured by Kanto Chemical Co., Ltd. TBAB: tetrabutylammonium bromide, manufactured by Tokyo Chemical Industry Co., Ltd. KOH: potassium hydroxide, manufactured by Kanto Chemical Co., Ltd. Isopropanol: manufactured by Kanto Chemical Co., Ltd. (resin)
PP: Polypropylene resin, Prime Polypro (registered trademark) J105G manufactured by Prime Polymer Co., Ltd.
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".

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

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

¹ H-NMR (CDCl ₃ , 300MHz): δ (ppm) = 7.69-7.72 (2H, m), 7.27-7.43 (6H, m), 3.18 (4H, q), 2.7 9 (4H, q), 2.42-2.48 (4H, m), 1.47-1.53 (4H, m), 0.96 (6H, t), 0.76 (6H, t) .

[Synthesis Example 2]
A reactor equipped with a magnetic stirrer and a three-way cock was charged with 9H-fluorene (19.4 g; 0.117 mol), DMSO (30 mL), toluene (30 mL), TBAB (0.6 g; 0.0019 mol), and N,N-dimethylacrylamide (23.8 g; 0.24 mol), and purged with nitrogen. The temperature was raised to 65° C., and complete dissolution was confirmed. A 48% by mass KOH aqueous solution (0.56 g; 0.0048 mol (4.8 mmol) in terms of KOH) was added to the resulting solution, and the temperature was raised to 90° C. and the mixture was heated and stirred for 2 hours. The reaction was terminated when 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 represented by the following formula (1-2) (DMAA-FL, 30.0 g; yield 82.4%).

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

¹ H-NMR (CDCl ₃ , 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).

[Synthesis Example 3]
A reactor equipped with a magnetic stirrer and a three-way cock was charged with 9H-fluorene (19.4 g; 0.117 mol), DMSO (30 mL), toluene (30 mL), TBAB (0.6 g; 0.0019 mol), and N-isopropylacrylamide (27.2 g; 0.24 mol), and the contents were purged with nitrogen, and the temperature was raised to 65° C., and it was confirmed that the contents were completely dissolved. A 48% by mass aqueous solution of KOH (0.56 g; 0.0048 mol (4.8 mmol) in terms of KOH) was added to the resulting solution, and the temperature was raised to 90° C., followed by heating and stirring 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 represented by the following formula (1-3) (NIPAM-FL, 32.8 g; yield 71.4%).

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

¹ H-NMR (CDCl ₃ , 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).

[Synthesis Example 4]
A reactor equipped with a magnetic stirrer and a three-way cock was charged with 9H-fluorene (19.4 g; 0.117 mol), DMSO (30 mL), toluene (30 mL), TBAB (0.6 g; 0.0019 mol), and acrylamide (17.0 g; 0.24 mol), and the contents were purged with nitrogen, and then heated to 65° C. to confirm complete dissolution. A 48% by mass KOH aqueous solution (0.56 g; 0.0048 mol (4.8 mmol) in terms of KOH) was added to the resulting solution, and the temperature was raised to 90° C., followed by heating and stirring for 2 hours. The reaction was terminated when 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, and white crystals gradually precipitated to form a white suspension. The suspension was filtered and washed with hot water (77.7 mL) and isopropanol (15 mL), and the target product represented by the following formula (1-4) (AAD-FL, 31.8 g; yield 88.4%) was obtained.

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

^1H -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).

[Synthesis Example 5]
A reactor equipped with a magnetic stirrer and a three-way cock was charged with 9H-fluorene (19.4 g; 0.117 mol), DMSO (30 mL), toluene (30 mL), TBAB (0.6 g; 0.0019 mol), and N-acryloylmorpholine (33.8 g; 0.24 mol), and purged with nitrogen. The temperature was raised to 65° C., and it was confirmed that the solution was completely dissolved. A 48% by mass KOH aqueous solution (0.56 g; 0.0048 mol (4.8 mmol) in terms of KOH) was added to the resulting solution, and the temperature was raised to 90° C. and the mixture was heated 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 (ACMO-FL) represented by the following formula (1-5).

[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 (manufactured by 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 product was dried under reduced pressure at 180°C for 24 hours to prepare an additive (conductive agent) (primary mixing step).

6 parts by mass of the obtained conductive agent was mixed with 94 parts by mass of PP to prepare a resin composition (secondary mixing process).

[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. A conductive agent was prepared by granulation and drying in the same manner as in Comparative Example 1, except that the obtained mixed liquid and 100 parts by mass of CNT were put into a Henschel type mixer (primary mixing step).

The obtained conductive agent (9 parts by mass) was mixed with 91 parts by mass of PP to prepare a resin composition (secondary mixing process).

[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. A conductive agent was prepared by granulation and drying in the same manner as in Comparative Example 1, except that the obtained mixed liquid and 100 parts by mass of CNT were put into a Henschel type mixer (primary mixing step).

The obtained conductive agent (9 parts by mass) was mixed with 91 parts by mass of PP to prepare a resin composition (secondary mixing process).

[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. A conductive agent was prepared by granulation and drying in the same manner as in Comparative Example 1, except that the obtained mixed liquid and 100 parts by mass of CNT were charged into a Henschel type mixer (primary mixing step).

The obtained conductive agent (9 parts by mass) was mixed with 91 parts by mass of PP to prepare a resin composition (secondary mixing process).

[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 instead of 94 parts by mass of PP.

[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 instead of 91 parts by mass of PP.

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 values measured at a measurement voltage of 10 V.

To measure the electrical conductivity and Charpy impact strength, the obtained resin compositions were injection molded using an injection molding machine (Nissei Plastics 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 with 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 with PC as the base resin.

As is clear from the results in Tables 1 and 2, all of the resin compositions contain 6% by mass of CNT relative to the total mass, but the resistivity (surface resistivity and volume resistivity) of the Examples was significantly reduced and the conductivity was improved compared to the Comparative Examples. In particular, in Example 1, in which DEAA-FL was added, the order of magnitude of the surface resistivity and volume resistivity was significantly reduced to about 10 ⁴ to 10 ⁵ compared to 10 ⁹ in Comparative Example 1. Furthermore, in Examples 1 to 3, the conductivity was 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.

[Comparative Example 3]
A resin composition was prepared by kneading 6 parts by mass of CNT and 94 parts by mass of PP together without prior granulation in a primary mixing step.

[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.

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 values measured at a measurement voltage of 10 V, and the surface resistivity of Example 5 was measured using "Loresta GP" instead of "Hiresta UP" manufactured by Mitsubishi Chemical Analytical Co., Ltd.

In addition, to measure the electrical conductivity and Charpy impact strength, test pieces were used that were prepared by injection molding under the same conditions as the resin compositions using PP as the base resin in Comparative Example 1 and Examples 1 to 3.

As is clear from the results in Table 3, the resistivity (surface resistivity and volume resistivity) of Example 5 was significantly reduced compared to Comparative Example 3, and the conductivity was improved. Note that, although the resistivity of Example 5 and Comparative Example 3 is lower than that of Example 1 and Comparative Example 1, which were granulated by the primary mixing process, it is possible that the CNTs are partially present as aggregates in the resin composition, forming conductive paths, because pellet-shaped CNTs are used.

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

Claims (9)

Resin, carbon nanotubes, and a compound represented by the following formula (1)

[In the formula, R ¹ represents a hydrocarbon group, k represents 0 ,
R ^2a , R ^2b , R ^2c and R ^2d each represent a hydrogen atom ;
R ^3a and R ^3b each independently represent a hydrogen atom or a methyl group;
X ^1a and X ^1b each independently represent the following formula (X1):

(In the formula, ^R4 and ^R5 each independently represent a hydrogen atom or a hydrocarbon group, or ^R4 and ^R5 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: The resin composition according to claim 1, wherein in the formula (1), both R ⁴ and R ⁵ are hydrocarbon groups. The resin composition according to claim 1 or 2, wherein in the formula (1), both of R ⁴ and R ⁵ are linear or branched alkyl groups. The resin composition according to any one of claims 1 to 3, wherein the carbon nanotubes are single-walled or multi-walled carbon nanotubes. The resin composition according to any one of claims 1 to 4, wherein the resin contains at least one selected from a polyolefin-based resin and a polycarbonate-based resin. 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. A method for improving the electrical conductivity of a resin by adding a compound represented by formula (1) according to claim 1 and carbon nanotubes to the resin. 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. An additive for improving the electrical conductivity of a resin, the conductive agent comprising a compound represented by formula (1) according to claim 1 and carbon nanotubes.

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