JP2009256617A - Carbon nanocomposite, dispersion liquid and resin composition each containing the same and method for producing carbon nanocomposite - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbon nanocomposite having excellent dispersibility in a solvent or a resin and excellent heat resistance, and to provide a dispersion liquid and a resin composition each of which contains the carbon nanocomposite. <P>SOLUTION: The carbon nanocomposite contains: a carbon nanostructure; and a vinyl polymer which is adsorbed on the carbon nanostructure and contains an imido group-containing constituent unit (preferably, a maleimide monomer unit). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a carbon nanocomposite and a method for producing the same, and more specifically, a carbon nanocomposite containing a carbon nanostructure and a vinyl polymer containing an imide group-containing structural unit adsorbed thereto, and a method for producing the same About. The present invention also relates to a dispersion and a resin composition containing the carbon nanocomposite.

  Carbon nanostructures typified by carbon nanotubes (CNT) are attracting attention because they are excellent in thermal conductivity, electrical conductivity, mechanical properties, etc., and also have storage stability. For example, electronic device materials, microscope probes Electrode materials such as emitters for field emission displays, negative electrodes for lithium secondary batteries, diffusion materials and separators for fuel cells, medical materials such as field effect transistors and drug delivery system materials, composite materials with resins and ceramics, molecular storage Development for application expansion to materials, etc. is underway. However, carbon nanostructures are likely to aggregate due to van der Waals forces and have poor dispersibility in solvents and resins, so that the above characteristics cannot be fully exhibited.

  Therefore, various methods have been proposed to improve the dispersibility of carbon nanotubes in a solvent. For example, WO 2002/016257 (Patent Document 1) discloses a composition comprising single-walled carbon nanotubes at least partially coated with at least one polymer molecule, and the polymer includes polyvinylpyrrolidone, polystyrene. Examples include sulfonate, dextran, polyvinyl alcohol, polyethylene glycol, polyallylamine, and the like. International Publication No. 2002/076888 (Patent Document 2) discloses a powder in which a polymer is adsorbed on a carbon nanotube. Examples of the polymer include gum arabic, carrageenan, pectin, polygalacturonic acid, alginic acid, chitosan and the like. These hydrophilic polymers are exemplified. However, the composition of Patent Document 1 and the powder of Patent Document 2 are still insufficient in dispersibility, particularly in organic solvents and resins, and inferior in heat resistance.

  Japanese Patent Application Laid-Open No. 2004-2850 (Patent Document 3) discloses a method of solubilizing a nanotube by non-covalently bonding a polymer to the nanotube. As the polymer, poly (arylene ethynylylene) and Poly (3-decylthiophene) is disclosed. However, the nanotubes solubilized by this method have poor solubility of the polymer in the solvent, and the dispersibility of the nanotube in the solvent or resin is still insufficient. Poly (3-decylthiophene) had a low melting point and insufficient heat resistance.

  Further, Petar Petrov et al., CHEM. COMMUN. 2003, p. 2904-2905 (Non-patent Document 1) discloses a composite of a vinyl copolymer containing a pyrenyl group having an affinity for carbon nanotubes and a carbon nanotube. However, although this carbon nanotube composite is well dispersed in the solvent, it is inferior in heat resistance.

  When carbon nanotube composites are used in resin composite materials such as electrical and electronic parts and automobile parts, these resin composite materials are easy to store heat, and heat dissipation characteristics (thermal conductivity) and heat resistance are required. Nanotube composites are mixed with highly heat-resistant high-performance resins such as polyarylene sulfides, liquid crystal polymers, and heat-resistant polyamides. However, in conventional carbon nanotube composites, the coating resin is at the melting temperature of these heat-resistant resins. There is a problem of thermal decomposition and a problem of bleeding out in a high temperature use environment, and it is necessary to improve the heat resistance of the coating resin.

  Japanese Unexamined Patent Application Publication No. 2004-250646 (Patent Document 4) discloses a polyimide composite material in which carbon nanotubes are dispersed in a thermosetting imide oligomer and then thermally cured as a composite material having high heat resistance. Since this polyimide composite material is a composite of carbon nanotubes and thermosetting polyimide, it has excellent heat resistance. However, since polyimide is poorly soluble in solvents, polyimide composite materials tend to be inferior in dispersibility.

  For this reason, conventional carbon nanotube composites are still insufficient in dispersibility and heat resistance in solvents and resins, and carbon nanotube composites that are superior in dispersibility and heat resistance are being demanded.

International Publication No. 2002/016257 Pamphlet International Publication No. 2002/076888 Pamphlet JP 2004-2850 A JP 2004-250646 A

Peter Petrov et al., CHEM. COMMUN. 2003, 2904-2905

  The present invention has been made in view of the above-mentioned problems of the prior art, and has a carbon nanocomposite excellent in dispersibility in a solvent or resin and excellent in heat resistance, a dispersion containing the carbon nanocomposite, and a resin composition And a method for producing the carbon nanocomposite.

  As a result of intensive studies to achieve the above object, the present inventors have made it possible to disperse in a solvent or resin by adsorbing a vinyl polymer containing an imide group-containing structural unit to a carbon nanostructure. The present inventors have found that a carbon nanocomposite excellent in heat resistance and heat resistance can be obtained and completed the present invention.

  That is, the carbon nanocomposite of the present invention is characterized by containing a carbon nanostructure and a vinyl polymer that is adsorbed to the carbon nanostructure and includes an imide group-containing structural unit. In addition, the dispersion and the resin composition of the present invention contain the carbon nanocomposite of the present invention and a solvent or a resin.

  The vinyl polymer preferably further contains a vinyl monomer unit other than the imide group-containing structural unit, and the thermal decomposition temperature is preferably 290 ° C. or higher. The imide group-containing structural unit preferably contains a maleimide monomer unit. The average diameter of the carbon nanostructure is preferably 1 μm or less.

  In the carbon nanocomposite of the present invention, the amount of adsorption of the vinyl polymer is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the carbon nanostructure.

  Further, the method for producing a carbon nanocomposite of the present invention comprises mixing a carbon nanostructure and a vinyl polymer containing an imide group-containing structural unit in a solvent, and mixing the carbon nanostructure with the vinyl polymer. It is a method characterized by adsorbing.

  The reason why the carbon nanocomposite of the present invention is excellent in dispersibility and heat resistance is not necessarily clear, but the present inventors speculate as follows. In other words, since the vinyl polymer according to the present invention contains a ring structure having an imide group having excellent heat resistance, the heat resistance of the carbon nanocomposite of the present invention including this vinyl polymer is increased. Inferred. In the carbon nanocomposite of the present invention, the vinyl polymer according to the present invention has an imide group-containing structural unit that adsorbs to the carbon nanostructure, but the main chain skeleton is a vinyl polymer skeleton. The polarity tends to be lower than that of a polyimide typified by an aromatic polyimide, and the affinity with a solvent or a resin is increased. For this reason, it is surmised that the carbon nanostructure adsorbed by the vinyl polymer is excellent in dispersibility in a solvent or resin.

  On the other hand, a polyimide represented by an aromatic polyimide has an imide bond in the main chain, so that the mobility is completely restricted and the polarity is extremely high. For this reason, it is guessed that the solubility to a solvent and affinity with resin become low, and the dispersibility of the carbon nanostructure which the said polyimide adsorbed also falls.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to obtain the carbon nanocomposite excellent in the dispersibility in a solvent or resin, and excellent in heat resistance, the dispersion liquid containing the carbon nanocomposite, and the resin composition.

The right side is a photograph showing the high concentration carbon nanocomposite colloid obtained in Example A1, and the left side is a photograph showing the high concentration carbon nanostructure colloid obtained in Comparative Example A1.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

<Carbon nanocomposite>
First, the carbon nanocomposite of the present invention will be described. The carbon nanocomposite of the present invention includes a carbon nanostructure, a vinyl polymer that adsorbs to the carbon nanostructure and includes an imide group-containing constituent unit (hereinafter referred to as “imide group-containing vinyl polymer”), It is characterized by containing.

  In the carbon nanocomposite of the present invention, the adsorption of the carbon nanostructure and the imide group-containing vinyl polymer may be due to non-covalent bonding, covalent bonding, or the like. Although it may be a combination, it does not destroy the surface structure of the carbon nanostructure, does not form defects, and has excellent properties such as thermal conductivity, electrical conductivity, and mechanical properties inherent to the carbon nanostructure. It is preferable to include at least adsorption by non-covalent bond in that it tends to be effectively expressed.

  In the present invention, “adsorption by non-covalent bond” means adsorption by an interaction other than a covalent bond generated between the carbon nanostructure and the imide group-containing vinyl polymer. Examples of such non-covalent bonds (interactions other than covalent bonds) include, for example, van der Waals force, charge transfer interaction, hydrophobic interaction, electrostatic attraction, hydrogen bond, π-π interaction, and CH-π. Examples include interaction. It is assumed that van der Waals force and / or charge transfer interaction occurs mainly between the carbon nanostructure and the imide group-containing vinyl polymer. For example, the imide group-containing structural unit is aryl. In the case of containing a group, in addition to the van der Waals force and / or the charge transfer interaction, a π-π interaction between the aryl group and the graphene structure of the carbon nanostructure occurs. When the structural unit contains an alkyl group, it is presumed that a CH-π interaction occurs in addition to the van der Waals force and / or the charge transfer interaction. Among such non-covalent adsorption, those using van der Waals force, charge transfer interaction, π-π interaction, and CH-π interaction are preferable. Further, since the van der Waals force and / or the charge transfer interaction and the π-π interaction are expressed adjacent to each other, the imide group-containing structural unit preferably contains an aryl group. Thereby, the adsorption amount of an imide group containing vinyl polymer increases, and adsorption stability improves. Although the reason why the imide group-containing vinyl polymer is not easily detached by washing or the like even if it is adsorption by a non-covalent bond is not necessarily clear, in the carbon nanocomposite of the present invention, the imide group-containing structural unit This is presumed to be due to the strong effects of van der Waals forces.

  On the other hand, the adsorption by the covalent bond is not particularly limited as long as the carbon nanostructure and the imide group-containing vinyl polymer are adsorbed through the covalent bond. For example, the carbon nanostructure may be acid-treated. Etc. to introduce a carboxyl group, etc., and then introduce a vinyl group or a halogen atom from this carboxyl group as a starting point, and use this vinyl group or halogen atom as a starting point to form a carbon nanostructure by radical polymerization or living radical polymerization. Examples of the carbon nanocomposite adsorbed by the covalent bond include those obtained by grafting an imide group-containing vinyl polymer. In addition, as carbon nanostructure which introduce | transduced the carboxyl group etc., Ctube200 by a CNT company etc. are mentioned, for example. In addition, a carbon nanocomposite adsorbed by the covalent bond may be obtained by introducing an imide group-containing vinyl polymer directly into a carbon nanostructure by radical addition reaction during polymerization, solution processing, or melt processing. it can.

  Such adsorption of the carbon nanostructure and the imide group-containing vinyl polymer can be achieved by dispersing the carbon nanocomposite in a good solvent for the imide group-containing vinyl polymer, Even when washed and filtered, the carbon nanocomposite preferably remains.

(Carbon nanostructure)
The carbon nanostructure used in the present invention is not particularly limited, and carbon nanofiber, carbon nanohorn, carbon nanocone, carbon nanotube, carbon nanocoil, carbon nanowall, fullerene, graphite, carbon flake, nanographene (graphene nanoribbon, etc.) ), And derivatives thereof. From the viewpoint of improving thermal conductivity and mechanical strength, carbon nanofiber, carbon nanohorn, carbon nanocone, carbon nanotube, carbon nanocoil, carbon nanowall, graphite, Anisotropic carbon nanostructures such as nanographene are preferred, carbon nanofibers, carbon nanohorns, carbon nanocones and carbon nanotubes are more preferred Carbon nanofibers and carbon nanotubes are especially preferred. These carbon nanostructures may be used alone or in combination of two or more.

  In the present invention, when carbon nanotubes and / or carbon nanofibers are used as the carbon nanostructure, either single-layer or multi-layer (two or more layers) can be used. You can do it.

  The carbon nanostructure may contain atoms, molecules, and the like other than carbon, and may contain a metal or other nanostructure as necessary.

  The average diameter of such a carbon nanostructure is not particularly limited, but is preferably 1 μm or less, more preferably 800 nm or less, further preferably 500 nm or less, particularly preferably 300 nm or less, and most preferably 200 nm or less. When the average diameter of the carbon nanostructure exceeds the upper limit, when the carbon nanocomposite is mixed with a resin and used as a resin composite, the heat resistance is sufficiently improved with a small amount of addition (the deflection temperature under load increases, The thermal expansion coefficient does not decrease), and mechanical strength such as tensile strength and impact strength tends to be insufficient. In addition, when processing under shearing conditions such as injection molding, the carbon nanocomposite tends to be easily affected by orientation due to shearing force. The lower limit value of the average diameter of the carbon nanostructure is not particularly limited, but is preferably 0.4 nm, and more preferably 0.5 nm.

  In addition, the aspect ratio of the carbon nanostructure is not particularly limited, but when the carbon nanocomposite is mixed with a resin and used as a resin composite, mechanical strength such as tensile strength and impact strength can be improved by adding a small amount. From the viewpoint of reducing thermal linear expansion, and in applications where thermal conductivity is required, 5 or more is preferable, and 10 or more is preferable from the viewpoint of improving the thermal conductivity of a carbon nanocomposite or a resin composite material containing the carbon nanocomposite. Is more preferable, 20 or more is more preferable, 40 or more is particularly preferable, and 80 or more is most preferable.

In the present invention, among the peaks of the Raman spectrum of the carbon nanostructure obtained by measuring with a Raman spectrophotometer, the G band observed in the vicinity of about 1585 cm ⁻¹ due to the displacement vibration of the carbon atom in the graphene structure. The ratio (G / D) of the D band observed in the vicinity of about 1350 cm ⁻¹ , where the graphene structure is observed to have defects such as dangling bonds, is not particularly limited, but high thermal conductivity such as a high thermal conductive resin material. Is preferably 0.1 or more, more preferably 0.5 or more, further preferably 1.0 or more, particularly preferably 3.0 or more, and most preferably 5.0 or more. When G / D is less than the lower limit, thermal conductivity tends not to be sufficiently improved.

  Such a carbon nanostructure can be produced by appropriately selecting a conventionally known production method such as a laser ablation method, an arc synthesis method, a chemical vapor deposition method (CVD method), or a melt spinning method depending on the application. The carbon nanostructures used in the present invention are not limited to those produced by these methods.

(Imide group-containing vinyl polymer)
The imide group-containing vinyl polymer used in the present invention includes an imide group-containing structural unit, and further vinyl-based monomer units other than the imide group-containing structural unit (hereinafter referred to as “other vinyl monomer units”). It is preferable to contain. In the present invention, the “monomer unit” means a structural unit derived from a monomer or a structural unit having the same structure.

  As said imide group containing structural unit, following formula (1):

(In Formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, and R ³ represents a hydrogen atom, or an alkyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group, an amino group, etc. Represents a monovalent organic group of
A maleimide monomer unit represented by the following formula (2):

(In formula (2), R ⁴ and R ⁵ each independently represents a hydrogen atom or an alkyl group, and R ⁶ represents a hydrogen atom, or an alkyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group, an amino group, etc. Represents a monovalent organic group of
And a N-alkenylimide unit and a derivative unit thereof.

  The maleimide monomer is not particularly limited, and examples thereof include maleimide, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-alkylmaleimides such as N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide and Nn-dodecylmaleimide; N-acetyl N-alkynylmaleimides such as rhenylmaleimide and N-propynylmaleimide; N-benzylmaleimide, N-methylbenzylmaleimide, N-phenylethylmaleimide, N-phenylethylmaleimide, N-naphthylmethylmaleimide, N- N-aralkylmaleimides such as butylethylmaleimide; N-unsubstituted cycloalkylmaleimides typified by N-cyclohexylmaleimide, N-cyclododecylmaleimide and N-adamantylmaleimide, N-substituted cycloalkyls represented by N-methylcyclohexylmaleimide N-cycloalkylmaleimide such as alkylmaleimide; N-phenylmaleimide, N-naphthylmaleimide, N-naphthalenylmaleimide, N-perylenylmaleimide, N-pentacenylmaleimide, N-terphenylmaleimide, N-phenane N-unsubstituted arylmaleimides represented by threnylmaleimide, N-tetracenylmaleimide, N-anthracenylmaleimide and N-pyrenylmaleimide, N- (2-methylphenyl) maleimide, N-alkyl-substituted arylmaleimides represented by-(2,6-diethyl) phenylmaleimide, N- (4-dodecylphenyl) maleimide, N-tolylmaleimide and N-xylylmaleimide, N- (4-aminophenyl) N-amino-substituted arylmaleimide represented by maleimide, N-acetylenylphenylmaleimide represented by N-acetylenylphenylmaleimide and N-alkynyl-substituted arylmaleimide represented by N-propynylphenylmaleimide, N-aryl-substituted arylmaleimide represented by N-biphenylmaleimide N-halogen-substituted arylmaleimides represented by N-o-chlorophenylmaleimide, N- (2,4,6-trichlorophenyl) maleimide, N-pentafluorophenylmaleimide and N-tetrafluorophenylmaleimide N-arylmaleimides; substituted with heterocycles such as N-pyridylmaleimide, N-3- (2-phenylpyridyl) maleimide, N-3- (9-alkylcarbazoyl) maleimide and N- (9-acridinyl) maleimide Maleimides; bismaleimides such as N, N′-1,4-phenylenedimaleimide, N, N′-1,3-phenylenedimaleimide and 4,4′-bismaleimide diphenylmethane; N-fluoromaleimide, N-chloro Halogenated maleimides such as maleimide, N-bromomaleimide, and N-iodomaleimide; N-aminomaleimide, N-acetylmaleimide, N-hydroxymaleimide, N-hydroxymethylmaleimide, N-hydroxyethylmaleimide, N-hydroxyphenylmaleimide, -Carboxyphenylmaleimide, N- (2-carboxyethyl) maleimide, 6-maleimidocaproic acid, Nt-butoxycarbonylmaleimide, 3-maleimidopropionic acid N-hydroxysuccinimide, 6-maleimidohexanoic acid N-hydroxysuccinimide, 3 -[2- (2-maleimidoethoxy) ethylcarbamoyl] -2,2,5,5-tetramethyl-1-pyrrolidinyloxy, 3-maleimidobenzoic acid N-hydroxysuccinimide and the like. These maleimide monomers may be used alone or in combination of two or more. Further, these maleimide monomers may have a water-soluble substituent such as a sulfone group or a sulfonimide group or a silyl group such as a trialkoxysilyl group, if necessary. Furthermore, salts of these maleimide monomers can also be used.

  Although there is no restriction | limiting in particular as said glutarimide group, For example, glutarimide, N-methyl glutarimide, N-ethyl glutarimide, Nn-propyl glutarimide, N-isopropyl glutarimide, Nn-butyl glutarimide N-isobutylglutarimide, N-tert-butylglutarimide, Nn-pentylglutarimide, Nn-hexylglutarimide, Nn-heptylglutarimide, Nn-octylglutarimide and Nn N-alkyl glutarimides such as dodecyl glutarimide; N-alkynyl glutarimides such as N-acetylenyl glutarimide and N-propynyl glutarimide; N-aralkyls such as N-benzyl glutarimide and N-methylbenzyl glutarimide Glutarimide; N-cycloalkyl glutarimide such as N-unsubstituted cycloalkyl glutarimide represented by N-cyclohexyl glutarimide and N-substituted cycloalkyl glutarimide represented by N-methylcyclohexyl glutarimide; N-phenyl glutar N-unsubstituted aryl glutarimide, represented by N-naphthyl glutarimide, N-anthracenyl glutarimide and N-pyrenyl glutarimide, N-tolyl glutarimide and N-xylyl glutarimide Alkyl-substituted arylglutarimide, N-aminosubstituted arylglutarimide represented by N- (4-aminophenyl) glutarimide, N-acetylenylphenylglutarimide and N-propynylphenylglutarimide N-alkynyl-substituted aryl glutarimide represented by N, N-aryl-substituted aryl glutarimide represented by N-biphenyl glutarimide, N- (2-chlorophenyl) glutarimide, N- (2-bromophenyl) glutarimide N- (2,6-dichlorophenyl) glutarimide, N- (2,4,6-trichlorophenyl) glutarimide, N- (2,6-dibromophenyl) glutarimide, N- (2,4,6- N-arylglutarimides such as tribromophenyl) glutarimide, N-pentafluorophenylglutarimide and N-halogen-substituted arylglutarimides represented by N-tetrafluorophenylglutarimide; N-fluoroglutarimide, N-chloroglutar Imide, N-bromogluta Halogenated glutarimide such as ruimide and N-iodoglutarimide. These glutarimide groups may be included singly or in combination of two or more. Of these, N-arylglutarimide is preferred.

  Although there is no restriction | limiting in particular as said N-alkenylimide and its derivative (s), For example, N-vinyl succinimide, N-vinyl phthalimide, N-vinyl carbazole, 1-vinyl imidazole, etc. are mentioned. These may be used alone or in combination of two or more.

  In the imide group-containing vinyl polymer according to the present invention, such an imide group-containing structural unit may be contained singly or in combination of two or more. Of these imide group-containing structural units, maleimide monomer units are preferred from the viewpoint of improving dispersibility and heat resistance of the carbon nanostructure, and maleimide monomer units, N-cycloalkylmaleimide monomer units, N At least one of an arylmaleimide monomer unit, a maleimide monomer unit substituted with a heterocyclic ring, and an N-alkylmaleimide monomer unit is more preferable, and an N-arylmaleimide monomer unit is particularly preferable. When an imide group-containing vinyl polymer containing an N-arylmaleimide monomer unit is used, it is assumed that van der Waals force and / or charge transfer interaction and π-π interaction are expressed. Adsorption amount and adsorption stability are improved.

  Other vinyl monomers according to the present invention include unsaturated carboxylic acid ester monomers in terms of improving the solubility in various solvents such as organic solvents and water of the imide group-containing polymer and the affinity with various resins, Vinyl cyanide monomer, aromatic vinyl monomer, unsaturated carboxylic acid monomer, acid anhydride and derivative thereof, epoxy group-containing vinyl monomer, oxazoline group-containing vinyl monomer, amino group-containing vinyl monomer, amide group-containing Vinyl monomers, hydroxyl group-containing vinyl monomers, polyalkylene glycol group-containing vinyl monomers, siloxane structure-containing vinyl monomers, silyl group-containing vinyl monomers, cationic vinyl monomers and anionic vinyl monomers are preferred. Among them, for example, in view of improving the dispersibility of the carbon nanocomposite when mixing the carbon nanocomposite of the present invention with a resin such as polyarylene sulfide such as polyphenylene sulfide, polyester or polyamide, an unsaturated carboxylic acid monomer , Its acid anhydrides and derivatives thereof, epoxy group-containing vinyl monomers, and oxazoline group-containing vinyl monomers are more preferable. From the viewpoint of improving the dispersibility of carbon nanocomposites in nonpolar solvents such as alkanes and ethers, siloxane Structure-containing vinyl monomers and silyl group-containing vinyl monomers are more preferred. Further, from the viewpoint of highly dispersing the carbon nanocomposite in a highly polar solvent such as water or alcohol, unsaturated carboxylic acid monomers, acid anhydrides and derivatives thereof, amino group-containing vinyl monomers, amide group-containing vinyls. More preferred are monomer based monomers, hydroxyl group-containing vinyl monomers, polyalkylene glycol group-containing vinyl monomers, cationic vinyl monomers, anionic vinyl monomers and the like. These other vinyl monomers may be used alone or in combination of two or more.

  In the present invention, in addition to the other vinyl monomers, for example, vinyl monomers such as olefin monomers, vinyl halide monomers, carboxylic acid unsaturated ester monomers, and vinyl ether monomers can be used. These vinyl monomers may be used alone or in combination of two or more.

  The unsaturated carboxylic acid ester monomer is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, ( (Meth) acrylic acid halogens represented by (meth) acrylic acid alkyl esters such as n-hexyl (meth) acrylate and cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate and 2-chloroethyl (meth) acrylate Alkylated esters and the like.

  The vinyl cyanide monomer is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like. Although there is no restriction | limiting in particular as said aromatic vinyl type monomer, For example, styrene, alpha-methyl styrene, vinyl toluene, o-ethyl styrene, pt-butyl styrene, p-methyl styrene, styrene sulfonic acid, styrene sulfonic acid Examples include sodium, chlorostyrene, and bromostyrene.

  The unsaturated carboxylic acid monomer is not particularly limited. For example, unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid and crotonic acid, maleic acid, fumaric acid, itaconic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, Citraconic acid, glutaconic acid, tetrahydrophthalic acid, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid, methyl-1,2,3,6-tetrahydrophthalic acid, 5-norbornene- And unsaturated dicarboxylic acids such as 2,3-dicarboxylic acid and methyl-5-norbornene-2,3-dicarboxylic acid, and monoalkyl esters of unsaturated dicarboxylic acids represented by monomethyl maleate and monoethyl maleate . The acid anhydride is not particularly limited. For example, maleic anhydride, fumaric anhydride, itaconic anhydride, crotonic acid, methyl maleic anhydride, methyl fumaric anhydride, mesaconic anhydride, citraconic anhydride, anhydrous Glutaconic acid, tetrahydrophthalic anhydride, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, methyl-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene -2,3-dicarboxylic acid anhydride, and unsaturated dicarboxylic acid anhydrides such as methyl-5-norbornene-2,3-dicarboxylic acid anhydride. Furthermore, the derivative is not particularly limited, and examples thereof include metal salts of unsaturated carboxylic acid monomers, t-butyl (meth) acrylate, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, (meth ) 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl (meth) acrylate, ethylaminopropyl (meth) acrylate, 2-dibutylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, Examples include alkyl ester derivatives of (meth) acrylic acid such as 3-diethylaminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, and cyclohexylaminoethyl (meth) acrylate.

  The epoxy group-containing vinyl monomer is not particularly limited. For example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl maleate, glycidyl fumarate, glycidyl itaconate, glycidyl crotonate, glycidyl citraconic acid, glutaconate Examples thereof include glycidyl esters of unsaturated carboxylic acids such as glycidyl acid, p-glycidyl styrene, allyl glycidyl ether, and styrene-p-glycidyl ether.

  The oxazoline group-containing vinyl monomer is not particularly limited, and examples thereof include 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 5-methyl-2-vinyl-oxazoline, 2-isopropenyl-oxazoline, 2- Examples include acroyl-oxazoline, 2-styryl-oxazoline, 4,4-dimethyl-2-vinyl-oxazoline, and 4,4-dimethyl-2-isopropenyl-oxazoline.

  The amino group-containing vinyl monomer is not particularly limited, and examples thereof include vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, and allylamine derivatives represented by allylamine, methallylamine and N-methylallylamine. And aminostyrenes represented by p-aminostyrene.

  The amide group-containing vinyl monomer is not particularly limited, and examples thereof include (meth) acrylamide, N-methyl (meth) acrylamide, butoxymethyl (meth) acrylamide, N-propyl (meth) acrylamide and N-phenyl (meth) ) Acrylamides such as acrylamide. Also, an amide group-containing vinyl monomer analog such as N-vinyl-2-pyrrolidone can be used.

  The hydroxyl group-containing vinyl monomer is not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5, (meth) acrylate (Meth) acrylic acid hydroxyalkyl esters such as 6-pentahydroxyhexyl, (meth) acrylic acid 2,3,4,5-tetrahydroxypentyl, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis- 4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene and And hydroxyalkenes such as 4-dihydroxy-2-butene. Although there is no restriction | limiting in particular as said polyalkylene glycol group containing vinyl-type monomer, For example, polyethyleneglycol (meth) acrylate etc. are mentioned.

  The siloxane structure-containing vinyl monomer is not particularly limited, and examples thereof include α-methyl-ω- (3-methacryloxypropyl) polydimethylsiloxane and α-ethyl-ω- (3-methacryloxypropyl) polydimethylsiloxane. , Α-propyl-ω- (3-methacryloxypropyl) polydimethylsiloxane, α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane, α-methoxy-ω- (3-methacryloxypropyl) polydimethyl Examples include siloxane and (meth) acryloxy group-containing organopolysiloxanes such as α-ethoxy-ω- (3-methacryloxypropyl) polydimethylsiloxane.

  The silyl group-containing vinyl monomer is not particularly limited. For example, trimethoxysilylpropyl (meth) acrylate, triethoxysilylpropyl (meth) acrylate, methyldiethoxysilylpropyl (meth) acrylate, (meth ) Alkoxysilyl group-containing (meth) acrylates such as methyldiethoxysilylpropyl acrylate and methyldiethoxysilylpropyl (meth) acrylate; trimethoxysilylstyrene, vinyltrimethoxysilane, vinyltriethoxysilane and p-styryl Examples include an alkoxysilyl group-containing vinyl monomer such as trimethoxysilane; a silane compound containing a vinyl group typified by vinyltrichlorosilane and not containing an oxygen atom.

  Examples of the olefin monomer include ethylene, propylene, butene, isobutene, 2-methyl-1-butene, 2-methyl-2-butene, 2-ethyl-1-butene, 2-ethyl-2-butene and 2-methyl- 1-pentene, 2-methyl-2-pentene, 2-ethyl-1-pentene, 2-ethyl-2-pentene, 2-methyl-1-hexene, 2-methyl-2-hexene, 2-ethyl-1- Examples include hexene, 1-methyl-1-heptene, isooctene, 2-methyl-1-octene, isoprene, neoprene, butadiene, dicyclopentadiene, ethylidene norbornene, and cyclic olefin. The vinyl halide monomer is vinyl chloride. Etc. Examples of the carboxylic acid unsaturated ester monomer include vinyl acetate and isopropenyl acetate, and examples of the vinyl ether monomer include vinyl methyl ether and vinyl ethyl ether. Examples of the cationic vinyl monomer include diallyldimethylammonium hydrochloride, allylimine hydrochloride, and allylamine hydrochloride. Examples of the anionic vinyl monomer include styrene sulfonic acid, sodium styrene sulfonate, and lithium styrene sulfonate. It is done.

  The number average molecular weight of the imide group-containing vinyl polymer used in the present invention is not particularly limited, but preferably 10,000 or more, from the viewpoint of improving the adsorption amount and adsorption stability on the carbon nanostructure surface, More than 30,000 is more preferable, and 5,000 or more is particularly preferable. The number average molecular weight of the imide group-containing vinyl polymer is preferably 5 million or less, more preferably 1 million or less, and particularly preferably 500,000 or less. When the number average molecular weight of the imide group-containing vinyl polymer exceeds the upper limit, the fluidity tends to be lowered. Furthermore, the molecular weight distribution (weight average molecular weight / number average molecular weight) of the imide group-containing vinyl polymer is not particularly limited, and may be monodispersed or multimodal. In view of improving heat resistance, a value close to 1 is preferable.

In the present invention, the content of the imide group-containing structural unit in the imide group-containing vinyl polymer is not particularly limited and may be 100% by mass, but is preferably 99% by mass or less from the viewpoint of improving the solubility in a solvent. 95 mass% or less is more preferable, and 90 mass% or less is still more preferable. The content of the imide group-containing structural unit is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, particularly preferably 2% by mass or more, and 5% by mass or more. Is most preferred. If the content of the imide group-containing structural unit is less than the lower limit, the amount of non-covalent bonds (adsorption amount) to the carbon nanostructure tends to decrease or the non-covalent bond stability (adsorption stability) tends to decrease. In addition, the heat resistance of the obtained carbon nanocomposite and the resin composite material containing the carbon nanocomposite tends to decrease. Incidentally, an imido group-containing vinyl polymer of imide group ratio of containing structural units ^{1 H-NMR} imide group-containing vinyl used in the present invention can be determined by measuring polymer affinity with solvent and carbon The carbon nanocomposites are excellent in both affinity with the nanostructures, adsorbing with the carbon nanostructures, particularly adsorbing stability, and the resulting carbon nanocomposites are excellent in dispersibility.

  Although there is no restriction | limiting in particular as a manufacturing method of the said imide group containing vinyl polymer, The following method is mentioned. For example, when the imide group-containing vinyl polymer contains a maleimide monomer unit, a method of (co) polymerizing maleimide monomers and other vinyl monomers as required; α, β-unsaturated carboxylic anhydride Product, α, β-unsaturated carboxylic acid and α, β-unsaturated carboxylic acid ester (co) polymerize at least one monomer, and then obtain (co) polymer, ammonia, methylamine, Primary amines such as ethylamine, n-propylamine, isopropylamine, n-butylamine, t-butylamine, aniline, 9- (aminomethyl) anthracene, 2-aminomethylanthracene, 1-pyreneamine and 1-pyrenemethylamine; And a method of imidizing a maleic anhydride group.

  When the imide group-containing vinyl polymer contains a glutarimide group-containing constitutional unit, for example, the method described in JP-B No. 64-2603, JP-B No. 4-61007, Japanese Patent No. 2561043, etc. Can be manufactured. When the imide group-containing vinyl polymer contains an alkenylimide unit, it can be produced, for example, by (co) polymerizing N-alkenylimide.

  Although there is no restriction | limiting in particular as a transmission medium of the reaction chain in these (co) polymerization, A radical and an ion are mentioned. Living polymerisation is also preferred from the viewpoint of obtaining an imide group-containing vinyl polymer having a narrow molecular weight distribution. Of these, radical polymerization or living radical polymerization is more preferable, and radical polymerization is particularly preferable from the industrial viewpoint.

  The polymerization method in radical polymerization or ionic polymerization is not particularly limited, and for example, known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and dispersion polymerization may be used alone or in combination of two or more. Either a batch type or a continuous type polymerization method may be used. In the case of producing a polymer containing a maleimide monomer unit by imidizing a maleic anhydride group, for example, a maleic anhydride group-containing polymer was prepared by bulk polymerization, solution polymerization or bulk suspension polymerization. Thereafter, the target polymer can be obtained by imidizing maleic anhydride groups in a bulk state, a solution state or a suspension state.

  In the production of the imide group-containing vinyl polymer, conventionally known polymerization initiators, chain transfer agents, catalysts, dispersion stabilizers, solvents and the like can be used.

  When the imide group-containing vinyl polymer according to the present invention is a copolymer, the sequence of the copolymer is not particularly limited, and examples thereof include dendritics such as random, block, alternating, graft, hyperbranch, and the like. Any branched one such as a star polymer may be used, but from the viewpoint of dispersibility, at least one of random, block, alternating, and graft is preferable, and a random sequence is more preferable.

(Characteristics of carbon nanocomposites)
The carbon nanocomposite of the present invention is obtained by adsorbing the imide group-containing vinyl polymer on the carbon nanostructure. Conventionally, carbon nanostructures with an average diameter of 1 μm or less are prone to agglomerate and are difficult to disperse in a solvent or resin. The tendency is stronger as the average diameter is smaller, but carbon nanostructures with an average diameter of 1 μm or less By adsorbing the imide group-containing vinyl polymer to the nanostructure, it can be uniformly dispersed in a solvent or a resin. Conventionally, carbon nanostructures having a large aspect ratio also tend to aggregate and have been difficult to disperse in a solvent or resin. However, the imide group-containing vinyl-based carbon nanostructure has a large aspect ratio. By adsorbing the polymer, it can be uniformly dispersed in a solvent or a resin.

  Carbon nanocomposites are essentially neutral in terms of charge and have low dispersibility in solvents and resins. However, as the G / D value increases, carbon nanostructures have defects in graphene structure. In the past, carbon nanostructures with a large G / D value should be well dispersed in the solvent or resin because the polarity tends to decrease and the dispersibility in the solvent or resin tends to decrease. Was difficult. Further, even when attempts were made to disperse the carbon nanostructure in a solvent or resin using a known dispersant, the carbon nanostructure having a large G / D value was adsorbed because the graphene structure was almost complete. There was a tendency for the dispersant to be easily detached. On the other hand, when the imide group-containing vinyl polymer is used, the imide group-containing vinyl polymer is adsorbed on the carbon nanostructure having a large G / D value regardless of the presence or absence of defects in the chemical modification and the graphene structure. The carbon nanocomposite can be uniformly dispersed in a solvent or resin.

  In the carbon nanocomposite of the present invention, the amount of adsorption of the imide group-containing vinyl polymer is not particularly limited, but from the viewpoint of improving the dispersibility and flowability (molding processability) of the carbon nanocomposite, the carbon nanostructure 0.1 mass part or more is preferable with respect to 100 mass parts of a body, 0.5 mass part or more is more preferable, 1.0 mass part or more is further more preferable, 2.0 mass part or more is especially preferable, 3.0 mass part Part or more is most preferable. When the adsorption amount of the imide group-containing vinyl polymer is less than the lower limit, the dispersibility and fluidity (molding processability) of the carbon nanocomposite tend to be lowered. Further, the adsorption amount of the imide group-containing vinyl polymer is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and the rigidity of the resin composition containing the carbon nanocomposite with respect to 100 parts by mass of the carbon nanostructure. Or 95 parts by mass or less is more preferable, 90 parts by mass or less is particularly preferable, and 80 parts by mass or less is most preferable.

  In the carbon nanocomposite of the present invention, the adsorption stability of the imide group-containing vinyl polymer is not particularly limited, but is preferably 1% or more, more preferably 10% or more, further preferably 30% or more, 50 % Or more is particularly preferable, and 60% or more is most preferable. In addition, adsorption stability means that the dispersion liquid containing the carbon nanocomposite is subjected to ultrasonic treatment for 30 minutes (for example, an oscillation frequency of 45 kHz) and then the dispersion liquid is three times as much solvent as the solvent contained therein. It is defined by the rate of change in the amount of adsorption of the imide group-containing vinyl polymer before and after the washing / suction filtration operation.

<Method for producing carbon nanocomposite>
The method for producing the carbon nanocomposite of the present invention is not particularly limited as long as it is a method capable of adsorbing the imide group-containing vinyl polymer on the carbon nanostructure. Can be mentioned.
(I) A method of mixing the carbon nanostructure and the imide group-containing vinyl polymer in a solvent.
(Ii) A method of mixing the carbon nanostructure and the imide group-containing vinyl polymer without using a solvent.
(Iii) A method of mixing the carbon nanostructure and the melted imide group-containing vinyl polymer.
(Iv) A method of melting the imide group-containing vinyl polymer after mixing the carbon nanostructure and the imide group-containing vinyl polymer without using a solvent.
(V) A method in which the imide group-containing vinyl polymer is polymerized (including the case where the maleic anhydride group is imidized) using a solvent as necessary in the presence of the carbon nanostructure.

  These production methods may be carried out alone or in combination of two or more. In the production method of the present invention, at the time of the mixing or after the polymerization, at least one of ultrasonic treatment, vibration, stirring, external field application (for example, electric field application, magnetic field application, etc.), melt kneading, etc. It is preferable to apply, and it is more preferable to perform ultrasonic treatment. Among these mixing methods, the production method (i) is particularly preferable, and it is most preferable to perform ultrasonic treatment. The ultrasonic treatment is not particularly limited, and examples thereof include a method using an ultrasonic cleaner and a method using an ultrasonic homogenizer.

  In the production method of the present invention, the method for mixing the carbon nanostructure and the imide group-containing vinyl polymer is not particularly limited, and may be mixed all at once or divided and mixed. As for the order, the imide group-containing vinyl polymer may be added to the carbon nanostructure, or the carbon nanostructure may be added to the imide group-containing vinyl polymer. The carbon nanostructure and the imide group-containing vinyl polymer may be added simultaneously, or may be added alternately, but at least a part of the imide group-containing vinyl polymer is dissolved first or It is particularly preferable to melt and then add the carbon nanostructure from the viewpoint of increasing the adsorption amount of the imide group-containing vinyl polymer to the carbon nanostructure and improving the adsorption stability.

  In the production method of the present invention, another resin or additive may be added when the carbon nanostructure and the imide group-containing vinyl polymer are mixed. These resins and additives may be mixed together or divided and mixed. Moreover, there is no restriction | limiting in particular also about the order.

  When mixing by melt-kneading, the carbon nanostructure, the imide group-containing vinyl polymer, and if necessary, resin and / or additive in pellets, powders or strips, respectively Can be uniformly kneaded by a stirrer, a drive lender, hand mixing, or the like, and then melt kneaded using an extruder, a rubber roll machine, a Banbury mixer, or the like having a uniaxial or multiaxial vent.

  The mixing ratio of the carbon nanostructure and the imide group-containing vinyl polymer is not particularly limited, but the addition amount of the imide group-containing vinyl polymer is 0.1 with respect to 100 parts by mass of the carbon nanostructure. It is preferably at least 0.5 parts by mass, more preferably at least 1.0 part by mass, particularly preferably at least 2.0 parts by mass, and most preferably at least 3.0 parts by mass. When the addition amount of the imide group-containing vinyl polymer is less than the lower limit, the dispersibility and heat resistance of the carbon nanocomposite tend to be lowered. In addition, the amount of the imide group-containing vinyl polymer added is preferably 100000 parts by mass or less, more preferably 500 parts by mass or less, with respect to 100 parts by mass of the carbon nanostructure, and the resin composition containing the carbon nanocomposite. From the viewpoint of improving thermal conductivity in applications where fluidity (molding processability) and thermal conductivity are required, it is more preferably 100 parts by mass or less, particularly preferably 95 parts by mass or less, and most preferably 90 parts by mass or less.

  The temperature at the time of mixing is not particularly limited and may be less than 0 ° C., but is preferably 0 ° C. or higher, more preferably room temperature (23 ° C.) or higher, further preferably 30 ° C. or higher, particularly preferably 35 ° C. or higher, and 40 ° C. or higher. Is most preferred. If the mixing temperature is less than the lower limit, the amount of adsorption and the adsorption stability tend not to be sufficiently improved. Further, from the viewpoint of improving the solubility of the imide group-containing vinyl polymer and improving the adsorptivity, it is preferable that the temperature at the time of mixing is high, and the imide group-containing vinyl polymer is excellent in heat resistance. The temperature can be selected, but the upper limit is preferably 500 ° C, more preferably 450 ° C, and particularly preferably 400 ° C.

  Although there is no restriction | limiting in particular as a solvent used in the manufacturing method of said (i) or (v), An organic solvent and water are mentioned, These may be used independently or may be used in mixture. Examples of the organic solvent include chloroform, dichloromethane, carbon tetrachloride, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, and isopentyl acetate. , Amyl acetate, tetrahydrofuran, N-methyl-2-pyrrolidone, dimethylformaldehyde, dimethylacetamide, dimethyl sulfoxide, acetonitrile, methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol, hexafluoroisopropanol, ethylene glycol, propylene glycol, tetra Methylene glycol, tetraethylene glycol, hexamethylene glycol, diethylene Recall, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, chlorophenol, dichlorobenzene, phenol, tetrahydrofuran, sulfolane, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, N-dimethylpyrrolidone, pentane Hexane, neopentane, cyclohexane, heptane, octane, isooctane, nonane, decane, diethyl ether and the like. These organic solvents may be used alone or in combination of two or more. Moreover, in this invention, raw materials, such as the main ingredient of hardening resin, such as an epoxy resin, and a crosslinking agent, can also be used as a solvent.

  In the production method of (i) or (v), when producing a carbon nanocomposite in a solvent, the lower limit of the amount of carbon nanostructure added is not particularly limited, but with respect to 100 parts by mass of the solvent. 0.0001 mass part is preferable, 0.001 mass part is more preferable, 0.005 mass part is further more preferable, and 0.1 mass part is especially preferable. The upper limit of the amount of carbon nanostructure added is not particularly limited, but is preferably 1 part by weight, more preferably 0.1 part by weight, still more preferably 0.09 part by weight, based on 100 parts by weight of the solvent. 08 parts by mass is particularly preferable. When the added amount of the carbon nanostructure is less than the lower limit, the productivity of the carbon nanocomposite tends to decrease. On the other hand, when the above upper limit is exceeded, the dispersibility of the carbon nanostructures tends to be reduced and aggregation easily occurs, the amount of adsorption of the imide group-containing vinyl polymer tends to decrease, and the adsorption stability tends to decrease, Even when the preferred upper limit is exceeded, a good-quality dispersion can be obtained, for example, by collecting a portion (for example, a supernatant) in which there is no aggregation or precipitation in the dispersion.

  In addition, after the imide group-containing vinyl polymer is adsorbed to the carbon nanostructure by the production method of (i) or (v), filtration, combination of centrifugation and filtration, reprecipitation, solvent removal The carbon nanocomposite can be obtained by (such as drying), melt-kneading while containing the solvent, sampling of the carbon nanocomposite, and the like.

  Furthermore, when the imide group-containing vinyl polymer is adsorbed to the carbon nanostructure by the production method of (i) or (v), the mixed dispersion is filtered as necessary. The solvent and the unadsorbed polymer dissolved in the solvent can be removed, and the carbon nanocomposite can be recovered. The removed unadsorbed polymer can be recovered and reused. Moreover, a carbon nanocomposite can also be collect | recovered by reprecipitating with the poor solvent with respect to the said imide group containing vinyl polymer.

<Dispersion and resin composition containing carbon nanocomposite>
The dispersion of the present invention contains the carbon nanocomposite of the present invention and a solvent. Examples of the solvent include those exemplified in the mixing method. In the present invention, the carbon nanocomposite can be prepared in a solvent and used as a dispersion as it is. However, since the carbon nanocomposite of the present invention is excellent in redispersibility, the carbon nanocomposite is used as a solvent. A dispersion liquid can also be produced by adding to the mixture and subjecting it to ultrasonic treatment.

  The resin composition of the present invention contains the carbon nanocomposite of the present invention and a resin. The content of the carbon nanocomposite is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more with respect to 100% by mass of the resin composition. 0.2 mass% or more is particularly preferable, 90 mass% or less is preferable, 50 mass% or less is more preferable, 10 mass% or less is further preferable, and 5 mass% or less is particularly preferable. When the content of the carbon nanocomposite is less than the lower limit, the thermal conductivity and mechanical strength of the resin composite obtained by molding the resin composition of the present invention tend to be lowered, and on the other hand, exceeds the upper limit. And the fluidity of the resin composition tends to decrease. The melt viscosity of the resin composition of the present invention is not particularly limited, but is preferably 0.05 to 500 g / (10 minutes, load 2.16 kg) as MFR at a molding temperature, and is preferably 0.1 to 200 g / ( More preferably, the load is 10 minutes and the load is 2.16 kg).

  The resin is not particularly limited, but epoxy resin, phenol resin, melamine resin, thermosetting imide resin, thermosetting polyamideimide, thermosetting silicone resin, urea resin, unsaturated polyester resin, urea resin, benzoguanamine resin , Alkyd resin, and urethane resin; polystyrene, ABS (acrylonitrile-butadiene-styrene) resin, AS (acrylonitrile-styrene) resin, methyl methacrylate-acrylonitrile-styrene resin, methyl methacrylate-acrylonitrile-butadiene -Styrene resins and aromatic vinyl resins such as styrene-butadiene-styrene resins, polymethyl methacrylate, polymethyl acrylate, polymethacrylic acid, copolymers thereof, and acrylic rubber Vinyl cyanide resins such as acrylic resins, polyacrylonitrile, acrylonitrile-methyl acrylate resins, and acrylonitrile-butadiene resins, imide group-containing vinyl resins, polyethylene, polypropylene, polyisoprene, polybutadiene, ethylene propylene diene monomer rubber, and ethylene Polyolefin resin such as propylene rubber, acid or acid anhydride modified polyolefin resin, epoxy modified polyolefin resin, acid or acid anhydride modified acrylic elastomer, epoxy modified acrylic elastomer, silicone rubber, fluoro rubber, natural rubber, polycarbonate, cyclic polyolefin , Polyamide, polyethylene terephthalate, polybutylene terephthalate, poly 1,4-cyclohexanedimethyl terephthalate Tartrate, polyarylate, liquid crystal polyester, polyphenylene ether, polyarylene sulfide, polysulfone, polyether sulfone, polyoxymethylene, polytetrafluoroethylene, fluorinated ethylene propylene, polychlorotrifluoroethylene, polyvinylidene fluoride and polyvinyl fluoride Examples thereof include thermoplastic resins such as fluorine resin, polylactic acid, polyvinyl chloride, thermoplastic polyimide, thermoplastic polyamideimide, polyetherimide, polyetheretherketone, polyetherketoneketone, and polyetheramide. These resins may be used alone or in combination of two or more.

  Among these resins, thermoplastic resins are preferable, and among them, crystalline resins (for example, polyethylene, polypropylene, polyisoprene, polybutadiene, ethylene propylene diene monomer rubber, ethylene propylene rubber, etc.) from the viewpoint of thermal conductivity and mechanical strength. Polyolefin resin, acid or acid anhydride modified polyolefin resin, epoxy modified polyolefin resin, polyamide, polyethylene terephthalate, polybutylene terephthalate, poly 1,4-cyclohexanedimethyl terephthalate, liquid crystal polyester, polyarylene sulfide, polyoxymethylene, polytetra Fluorine-based resins such as fluoroethylene, fluorinated ethylene propylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride Polylactic acid, polyetheretherketone, polyetherketoneketone, polyetheramide, etc.) are more preferred, crystalline resins requiring a processing temperature of 280 ° C. or higher are more preferred, and crystals requiring a processing temperature of 290 ° C. or higher are preferred. Resin (for example, liquid crystal polyester, polyarylene sulfide, polyetheretherketone, fluororesin, and polyamide that requires a processing temperature of 290 ° C. or higher) are particularly preferable. From the viewpoint of heat resistance and molding processability, polyarylene sulfide and Liquid crystal polyester is most preferred. Since the imide group-containing vinyl polymer according to the present invention is excellent in heat resistance, the carbon nanocomposite of the present invention is well dispersed in, for example, a crystalline resin that requires a high processing temperature of 290 ° C. or higher. It is possible to make it.

  In the resin composition of this invention, various additives can be mix | blended in the range which does not impair the effect of invention. There are no particular restrictions on such additives, but examples include flame retardants, antioxidants, UV absorbers, antistatic agents, lubricants, mold release agents, crystal nucleating agents, viscosity modifiers, colorants, silane couplings. Surface treatment agents such as agents, clay minerals such as talc and montmorillonite, layered silicates represented by mica minerals and kaolin minerals, glass fibers, carbon fibers, fillers such as silica and thermally conductive fillers, elastomers, etc. Can be mentioned.

  The heat conductive filler is not particularly limited, and examples thereof include alumina, boron nitride, aluminum nitride, silicon carbide, diamond, and zinc oxide. These thermally conductive fillers may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as thermal conductivity of this heat conductive filler, 0.5 W / mK or more is preferable, 1 W / mK or more is more preferable, 5 W / mK or more is further more preferable, 10 W / mK or more is especially preferable, Most preferable is 20 W / mK or more. The content of the heat conductive filler in the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 90% by mass, more preferably 0.1 to 80% by mass with respect to 100% by mass of the resin composition, 0.1-70 mass% is further more preferable, and 0.1-50 mass% is especially preferable. If the content of the heat conductive filler is less than the lower limit, the thermal conductivity of the resin composite obtained tends not to be sufficiently improved, and if it exceeds the upper limit, the fluidity of the resin composition tends to decrease.

  There is no restriction | limiting in particular as a manufacturing method of the resin composition of this invention, The conventionally well-known mixing method employ | adopted when disperse | distributing a filler in resin is mentioned. For example, a resin, a method of mixing the resin with the carbon nanocomposite of the present invention and various additives as necessary, an extruder having a uniaxial or multiaxial vent, a rubber roll machine, or a Banbury mixer. And a method of melt-kneading the carbon nanocomposite of the present invention and various additives as required. Moreover, when using a low-viscosity thermosetting resin as resin, it is also possible to mix by performing a compounding process using a self-revolving mixer.

  In addition to mixing the carbon nanocomposite and the resin, the resin composition of the present invention may be prepared by mixing the carbon nanostructure and the imide group-containing vinyl polymer in the resin to add the imide group to the carbon nanostructure. It can also be produced by adsorbing the vinyl-containing polymer. Examples of the mixing method include a mixing method by melt kneading, ultrasonic treatment in a solvent, stirring treatment, and the like. Furthermore, there is no restriction | limiting in particular about the method of mixing resin, the carbon nanocomposite of this invention, and various additives, You may mix in a lump or may be divided and mixed. Also, the order is not particularly limited, and after the specific components are premixed, the remaining components may be mixed.

  The carbon nanocomposite used in preparing the resin composition of the present invention may be subjected to a drying treatment or may contain a solvent (an organic solvent and / or water). Although there is no restriction | limiting in particular about the temperature of a drying process, It is preferable to freeze-dry from a viewpoint of preventing aggregation at the time of drying. Further, when the carbon nanocomposite is aggregated, the carbon nanocomposite is rapidly dispersed in the resin even if it is used as it is, but it is preferable that the carbon nanocomposite is pulverized in advance by pulverization or freeze pulverization.

  In the present invention, in order to improve the dispersibility of the carbon nanocomposite, it is preferable that a part of the resin and / or various additives are preliminarily mixed with the carbon nanocomposite in advance. Examples of the premixing method include, for example, a method of mixing in a solvent, a method of mixing a molten resin and a carbon nanocomposite, a method of mixing by a stirrer, a drive renderer or hand mixing, and the production of a carbon nanocomposite. A method of mixing at least a part of the resin and / or various additives is sometimes used. Among them, a method of mixing in a solvent is preferable, and at least a part of the resin and / or various additives are dissolved and / or dispersed (without dissolution) in the solvent, and the carbon nanocomposite of the present invention is added thereto. A method of adding and mixing, or a method of adding and mixing at least part of the resin and / or various additives to the dispersion containing the carbon nanocomposite of the present invention is more preferable. In addition, the shape of the resin at the time of premixing is not particularly limited, and examples thereof include powder, pellets, granules, tablets, and fibers.

  In the resin composition of the present invention, injection molding, press molding, extrusion molding, blow molding, compression molding, gas assist molding, insert molding, two-color molding, molding using an external field (for example, magnetic field molding, electric field is used) A resin composite material can be obtained by performing a conventionally known molding process such as molding. Although there is no restriction | limiting in particular about molding temperature, Since the carbon nanocomposite of this invention is excellent in heat resistance (The thermal decomposition temperature of an imide group containing vinyl polymer is high), for example, 290 degreeC or more, 300 degreeC or more, or 310 Molding at a high temperature of ℃ or higher is also possible.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. Various physical properties of the vinyl polymer and the carbon nanocomposite were measured by the following methods.

(1) Method for measuring number average molecular weight of vinyl polymer 2 mg of vinyl polymer was dissolved in 2 ml of chloroform, and gel permeation chromatograph (hereinafter abbreviated as “GPC”. “Shodex GPC-” manufactured by Showa Denko K.K. 101 ”, pump:“ DU-H7000 ”manufactured by Showa Denko Co., Ltd., column:“ K-805L ”manufactured by Showa Denko Co., Ltd. connected in series, and vinyl system under the condition of a column temperature of 40 ° C. The number average molecular weight of the polymer was measured. As the detector, an ultraviolet detector (“RI-71S” manufactured by Showa Denko KK) was used. The number average molecular weight and molecular weight distribution were determined as converted values by standard polystyrene (measured at 9 points in the range of molecular weight 1310 to molecular weight 2210000).

(2) Method for analyzing composition of vinyl polymer by ¹ H-NMR Dissolving the vinyl polymer in deuterated dimethyl sulfoxide, conducting ¹ H-NMR measurement under conditions of 30 ° C. and 400 MHz, each obtained The integral value of the proton of the structural unit was determined, and from these ratios, the molar ratio of each structural unit in the vinyl polymer was determined and converted into a mass ratio. Table 1 shows an example of chemical shifts for protons of each structural unit.

(3) Evaluation method of redispersibility of carbon nanocomposite 2 mg of carbon nanocomposite was added to 50 g of the solvent shown in Table 4, and this was subjected to ultrasonic treatment (BRANSON's desktop ultrasonic cleaner “BRANSONIC B-220”. And the oscillation frequency of 45 kHz) was applied for 30 minutes to redisperse the carbon nanocomposite. The dispersion was centrifuged immediately after sonication (1 hour at a relative centrifugal acceleration of 1000 G), and then allowed to stand for 20 hours. A UV-visible light absorption spectrum of the supernatant after standing was measured, and redispersibility (precipitation resistance) was evaluated by absorbance at 650 nm. In addition, the larger the absorbance value, the more the carbon nanocomposite is dispersed in the solvent even after centrifugation, which means that the redispersibility (precipitation resistance) is excellent.

(4) Adsorption amount of vinyl polymer and measurement method of thermal decomposition temperature First, carbon nanostructure and vinyl polymer are vacuum dried to remove volatile components such as residual solvent, and then thermogravimetric analysis is performed for each. Carbon nanostructures were subjected to thermogravimetric analysis (TGA) by heating from room temperature to 500 ° C at a temperature increase rate of 20 ° C / min using a device ("Thermo plus TG8120" manufactured by Rigaku Corporation). The thermal decomposition start temperature and thermal decomposition end temperature of the polymer and vinyl polymer were measured. Normally, the temperature at the start of mass reduction is the pyrolysis start temperature and the temperature at the end of mass reduction is the pyrolysis end temperature, but when the mass reduction has not ended at 500 ° C. Was further heated until the mass reduction was completed, and the thermal decomposition end temperature was measured. Further, the temperature at which the mass reduction was 5% by mass in the thermogravimetric analysis was defined as the thermal decomposition temperature of the vinyl polymer.

  Next, the carbon nanocomposite is vacuum-dried to remove volatile components such as residual solvent, and then heated at a rate of temperature in a nitrogen atmosphere using a thermogravimetric analyzer (“Thermo plus TG8120” manufactured by Rigaku Corporation). Thermogravimetric analysis was carried out by heating from room temperature to 500 ° C. at 20 ° C./min (to the thermal decomposition end temperature if the vinyl polymer contained in the carbon nanocomposite is 500 ° C. or higher). . Of the mass reduction of the carbon nanocomposite, the amount derived from the vinyl polymer was taken as the amount of adsorption of the vinyl polymer to the carbon nanocomposite, and expressed in the amount [part by mass] relative to 100 parts by mass of the carbon nanostructure. . Further, in the thermogravimetric analysis, the temperature at which a mass reduction of 5% by mass with respect to the adsorption amount of the vinyl polymer was observed was defined as the thermal decomposition temperature of the vinyl polymer adsorbed on the carbon nanocomposite. For example, in the case of a carbon nanocomposite in which 20 parts by mass of a vinyl polymer is adsorbed with respect to 100 parts by mass of the carbon nanostructure, the temperature at which 1 mass part weight loss is observed in the thermogravimetric analysis is expressed as vinyl. It was set as the thermal decomposition temperature of the polymer.

(5) Evaluation method of adsorption stability 0.05 part by mass of carbon nanocomposite was added to 100 parts by mass of the solvent shown in Table 4, and this was subjected to ultrasonic treatment (BRANSON's tabletop ultrasonic cleaner “BRANSONIC B- 220 "and an oscillation frequency of 45 kHz) was applied for 30 minutes to obtain a dispersion containing a carbon nanocomposite. Subsequently, the Kiriyama funnel (filter: omnipore membrane filter, pore size 1.0 μm) was used, and the dispersion was subjected to suction filtration while being washed with 300 parts by mass of chloroform. Thereafter, the filter cake was vacuum-dried, and the solvent was completely distilled off to recover the carbon nanocomposite.

The recovered carbon nanocomposite was subjected to thermogravimetric analysis in the same manner as the measurement method of (4) above, and the amount of adsorption of the vinyl polymer to 100 parts by mass of the carbon nanostructure was determined [parts by mass]. formula:
Adsorption stability [%] = Adsorption amount of vinyl polymer after washing / suction filtration operation /
Adsorption amount of vinyl polymer before washing / suction filtration operation × 100
The adsorption stability was evaluated based on the value obtained from the above.

Moreover, the following were used as the carbon nanostructure. The G / D value of the carbon nanostructure was measured by using a laser Raman spectroscopy system (“NRS-3300” manufactured by JASCO Corporation) and measuring a Raman spectrum at an excitation laser wavelength of 532 nm, about 1585 cm ⁻¹ . It was determined from the peak intensity of the Raman spectrum of the G band observed and the D band observed around 1350 cm ⁻¹ .
Carbon nanostructure (A-1):
Multi-walled carbon nanotube (“Ctube100” manufactured by CNT, average diameter 10-40
nm, aspect ratio of 100 or more, G / D value: 0.9, thermal decomposition temperature under nitrogen atmosphere exceeds 600 ° C.).
Carbon nanostructure (A-2):
Multi-walled carbon nanotubes (“MWNT-7” manufactured by Nanocarbon Technologies, Inc.)
The average diameter is 40 to 90 nm, the aspect ratio is 100 or more, the G / D value is 8.0, and the thermal decomposition temperature in a nitrogen atmosphere exceeds 600 ° C.).
Carbon nanostructure (A-3):
Carbon nanofiber (“VGCF” manufactured by Showa Denko KK, average diameter 150 nm, aspect ratio 60, G / D value 9.6, thermal decomposition temperature in a nitrogen atmosphere exceeds 600 ° C.).
Carbon nanostructure (A-4):
Single-walled carbon nanotube (manufactured by CNI, average diameter 0.8 to 1.2 nm, aspect ratio 83 or more, G / D value: 16.0, thermal decomposition temperature under nitrogen atmosphere exceeds 600 ° C.).

(Preparation Example 1)
Preparation of imide group-containing vinyl polymer (B-1):
A reaction vessel equipped with a stirrer and a reflux tube was charged with 30 parts by mass of styrene and 50 parts by mass of methyl ethyl ketone, and the system was replaced with nitrogen gas while stirring this solution. Next, 40 parts by mass of N-phenylmaleimide, 30 parts by mass of styrene, 0.05 part by mass of t-dodecyl mercaptan and 0.1 part by mass of 2,2′-azobisisobutyronitrile are dissolved in 140 parts by mass of methyl ethyl ketone. The solution thus obtained was added at a constant rate at 80 ° C. over 4 hours with stirring, and further aged at 80 ° C. for 1 hour to complete the polymerization. After cooling, the solution was poured into an excess amount of methanol and purified by reprecipitation. The precipitate was dried in vacuo and the solvent was completely distilled off to obtain an imide group-containing vinyl polymer (B-1).

The number average molecular weight of this imide group-containing vinyl polymer (B-1) measured using GPC was 108,000, and the molecular weight distribution was 4.0. Further, ¹ H-NMR measurement was performed on the imide group-containing vinyl polymer (B-1), and the proportion of each structural unit was determined. As a result, the N-phenylmaleimide unit was 45% by mass and the styrene unit was 55% by mass. %Met.

(Preparation Example 2)
Preparation of imide group-containing vinyl polymer (B-2):
A reaction vessel equipped with a stirrer and a reflux tube was charged with 100 parts by mass of N-phenylmaleimide, 0.4 parts by mass of 2,2′-azobisisobutyronitrile and 500 parts by mass of methyl ethyl ketone, and the solution was stirred. After replacing the system with nitrogen gas, the temperature was raised to 80 ° C. Then, it hold | maintained at 80 degreeC for 4 hours, and superposition | polymerization was complete | finished. After cooling, the solution was poured into an excess amount of methanol and purified by reprecipitation. The precipitate was dried in vacuo and the solvent was completely distilled off to obtain an imide group-containing vinyl polymer (B-2). The number average molecular weight of this imide group-containing vinyl polymer (B-2) measured using GPC was 17,000, and the molecular weight distribution was 3.4.

(Preparation Example 3)
Preparation of imide group-containing vinyl polymer (B-3):
Instead of N-phenylmaleimide, 13 parts by mass of N-pyrenylmaleimide and 87 parts by mass of styrene were used, 1750 parts by mass of chloroform was used in place of methyl ethyl ketone, and the amount of 2,2′-azobisisobutyronitrile was changed to 0.1. The imide group-containing vinyl polymer (B-3) was prepared in the same manner as in Preparation Example 2 except that the polymerization temperature was changed to 3 parts by mass, the polymerization temperature was changed to 60 ° C., and the polymerization time (retention time) was changed to 8 hours. Got.

The number average molecular weight of this imide group-containing vinyl polymer (B-3) measured using GPC was 10,000, and the molecular weight distribution was 2.2. Further, ¹ H-NMR measurement was performed on the imide group-containing vinyl polymer (B-3), and the proportion of each structural unit was determined. As a result, the N-pyrenylmaleimide unit was 20% by mass and the styrene unit was 80%. It was mass%.

(Preparation Example 4)
Preparation of imide group-containing vinyl polymer (B-4):
An imide group-containing vinyl polymer (B-4) was obtained in the same manner as in Preparation Example 2, except that 55 parts by mass of N-methylmaleimide and 45 parts by mass of methyl methacrylate were used instead of N-phenylmaleimide.

The number average molecular weight of this imide group-containing vinyl polymer (B-4) measured using GPC was 25,000, and the molecular weight distribution was 6.7. Further, ¹ H-NMR measurement was performed on the imide group-containing vinyl polymer (B-4), and the proportion of each structural unit was determined. As a result, the N-methylmaleimide unit was 45% by mass, and the methyl methacrylate unit was It was 55% by mass.

(Preparation Example 5)
Preparation of imide group-containing vinyl polymer (B-5):
Instead of 100 parts by mass of N-phenylmaleimide, 13 parts by mass of N-phenylmaleimide and 87 parts by mass of 2-dimethylaminoethyl methacrylate were used, 0.4 part by mass of 2,2′-azobisisobutyronitrile and 500 of methyl ethyl ketone. An imide group-containing vinyl polymer (B-5) was obtained in the same manner as in Preparation Example 2, except that 0.1 parts by mass of n-dodecyl mercaptan was used in addition to the parts by mass.

The number average molecular weight of this imide group-containing vinyl polymer (B-5) measured using GPC was 9000, and the molecular weight distribution was 2.8. Further, ¹ H-NMR measurement was performed on this imide group-containing vinyl polymer (B-5), and the proportion of each structural unit was determined. As a result, the N-phenylmaleimide unit was 10% by mass, and 2-dimethyl methacrylate. The aminoethyl unit was 90% by mass. Further, this imide group-containing vinyl polymer (B-5) was dissolved in chloroform and tetrahydrofuran well and also in ion-exchanged water, so that it was confirmed to be amphiphilic.

(Preparation Example 6)
Preparation of 1-pyrenylmethyl methacrylate:
1-Pyrenemethanol 5.0 g and triethylamine 4.34 g were dissolved in 100 ml of tetrahydrofuran, and 2.25 g of methacryloyl chloride was added dropwise at 0 ° C., followed by stirring at room temperature for 1 hour. The precipitate was filtered while washing with ethyl acetate, the filtrate and the washing solution were mixed and dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, hexane: ethyl acetate = 10: 1) and dried in vacuo to give 1-pyrenylmethyl methacrylate.

(Preparation Example 7)
Preparation of polymethyl methacrylate:
A reaction vessel equipped with a stirrer was charged with 100 parts by weight of methyl methacrylate, 0.4 parts by weight of 2,2′-azobisisobutyronitrile, and 500 parts by weight of methyl ethyl ketone, and the system was stirred while stirring the solution. After replacing with nitrogen gas, the temperature was raised to 80 ° C. Then, it hold | maintained at 80 degreeC for 4 hours, and superposition | polymerization was complete | finished. After cooling, the solution was poured into an excess amount of methanol and purified by reprecipitation. The precipitate was vacuum-dried and the solvent was completely distilled off to obtain polymethyl methacrylate. The number average molecular weight of this polymethyl methacrylate measured using GPC was 10,000, and the molecular weight distribution was 2.3.

(Preparation Example 8)
Preparation of methyl methacrylate / 1-pyrenylmethyl methacrylate copolymer (C-1):
Preparation Example 7 except that 70 parts by weight of methyl methacrylate and 30 parts by weight of 1-pyrenylmethyl methacrylate obtained in Preparation Example 6 were used instead of 100 parts by weight of methyl methacrylate, and 550 parts by weight of toluene was used instead of methyl ethyl ketone. Similarly, a methyl methacrylate / 1-pyrenylmethyl methacrylate copolymer (C-1) was obtained.

The number average molecular weight of this methyl methacrylate / methacrylic acid 1-pyrenylmethyl copolymer (C-1) measured using GPC was 10,000, and the molecular weight distribution was 2.4. Further, ¹ H-NMR measurement was carried out on this methyl methacrylate / methacrylic acid 1-pyrenylmethyl copolymer (C-1), and the proportion of each structural unit was determined. The acid 1-pyrenylmethyl unit was 20% by mass.

(Example A1)
(1) Dispersibility of low-concentration dispersion liquid 1.6 mg of an imide group-containing vinyl polymer (B-1) and 2 mg of carbon nanostructure (A-1) are added to 50 g of chloroform, and ultrasonic treatment ( A BRANSON tabletop ultrasonic cleaner “BRANSONIC B-220” (oscillation frequency 45 kHz) was applied for 1 hour to obtain a low concentration dispersion. The dispersion immediately after ultrasonication was centrifuged (relative centrifugal acceleration of 1000 G for 1 hour), and then allowed to stand for 20 hours. The UV-visible light absorption spectrum was measured for the supernatant after standing, and the dispersibility (precipitation resistance) was evaluated by the absorbance at 650 nm. The results are shown in Table 2. The larger the absorbance value, the more the carbon nanocomposite is dispersed in the solvent even after centrifugation, which means that the dispersibility (precipitation resistance) is excellent.

(2) Dispersibility of high concentration dispersion liquid 6.4 mg of imide group-containing vinyl polymer (B-1), 8 mg of carbon nanostructure (A-2) and 12 g of chloroform are placed in a screw tube, and ultrasonic waves are added thereto. A high-concentration dispersion was obtained by applying a treatment (using a table type ultrasonic cleaner “BRANSONIC B-220” manufactured by BRANSON, oscillation frequency 45 kHz) for 1 hour. After allowing this dispersion to stand for 1 minute, the screw tube bottle was tilted, the dispersion state of the dispersion near the gas-liquid interface was visually observed, and judged according to the following criteria. The results are shown in Table 2. FIG. 1 (right) shows a photograph of the high-concentration dispersion (colloid) after standing.
A: Aggregation is not observed and is uniformly dispersed.
B: Aggregation was observed, but uniformly dispersed.
C: Aggregation was not solved and was dispersed non-uniformly (a part separated into an aggregate and a solvent was observed).

(Example A2)
The dispersibility of (1) the low concentration dispersion and (2) the high concentration dispersion was evaluated in the same manner as in Example A1, except that 50 g or 12 g of tetrahydrofuran (THF) was used instead of chloroform. The results are shown in Table 2.

(Example A3)
The dispersibility of (1) the low concentration dispersion and (2) the high concentration dispersion was evaluated in the same manner as in Example A1, except that 50 g or 12 g of N-methyl-2-pyrrolidone (NMP) was used instead of chloroform. . The results are shown in Table 2.

(Example A4)
(1) Low in the same manner as in Example A1 except that 1.6 mg or 6.4 mg of the imide group-containing vinyl polymer (B-2) was used instead of the imide group-containing vinyl polymer (B-1). The dispersibility of the concentration dispersion and (2) the high concentration dispersion was evaluated. The results are shown in Table 2.

(Example A5)
(1) Low in the same manner as in Example A1 except that 1.6 mg or 6.4 mg of the imide group-containing vinyl polymer (B-3) was used instead of the imide group-containing vinyl polymer (B-1). The dispersibility of the concentration dispersion and (2) the high concentration dispersion was evaluated. The results are shown in Table 2.

(Example A6)
(1) Low in the same manner as in Example A1 except that 1.6 mg or 6.4 mg of the imide group-containing vinyl polymer (B-4) was used instead of the imide group-containing vinyl polymer (B-1). The dispersibility of the concentration dispersion and (2) the high concentration dispersion was evaluated. The results are shown in Table 2.

(Example A7)
(1) Low in the same manner as in Example A1 except that 1.6 mg or 6.4 mg of the imide group-containing vinyl polymer (B-5) was used instead of the imide group-containing vinyl polymer (B-1). The dispersibility of the concentration dispersion and (2) the high concentration dispersion was evaluated. The results are shown in Table 2.

(Comparative Example A1)
Without using the imide group-containing vinyl polymer (B-1), 2 mg of carbon nanostructure (A-1) is dispersed in 50 g of chloroform, or 8 mg of carbon nanostructure (A-2) is dispersed in 12 g of chloroform. Except for the above, the dispersibility of (1) the low concentration dispersion and (2) the high concentration dispersion was evaluated in the same manner as in Example A1. The results are shown in Table 2. FIG. 1 (left) shows a photograph of a highly concentrated dispersion (colloid) after standing for 1 minute.

(Comparative Example A2)
(1) Low concentration in the same manner as in Example A1, except that 1.6 mg or 6.4 mg of styrene (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of the imide group-containing vinyl polymer (B-1) Dispersibility of the dispersion and (2) high concentration dispersion was evaluated. The results are shown in Table 2.

(Comparative Example A3)
(1) Except that 1.6 mg or 6.4 mg of N-phenylmaleimide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of the imide group-containing vinyl polymer (B-1) (1 The dispersibility of the low-concentration dispersion and (2) the high-concentration dispersion was evaluated. The results are shown in Table 2.

(Comparative Example A4)
(1) Low concentration in the same manner as in Example A1, except that 1.6 mg or 6.4 mg of 1-pyrenylmethyl methacrylate obtained in Preparation Example 6 was used instead of the imide group-containing vinyl polymer (B-1). Dispersibility of the dispersion and (2) high concentration dispersion was evaluated. The results are shown in Table 2.

(Comparative Example A5)
Except for using 1.6 mg or 6.4 mg of polystyrene (manufactured by Polymer Source, number average molecular weight 107000, weight average molecular weight / number average molecular weight: 1.51) in place of the imide group-containing vinyl polymer (B-1). In the same manner as in Example A1, the dispersibility of (1) the low concentration dispersion and (2) the high concentration dispersion was evaluated. The results are shown in Table 2.

(Comparative Example A6)
Implemented except that 1.6 mg or 6.4 mg of styrene / acrylonitrile / oxazoline copolymer (“Epocross RAS-1005” manufactured by Nippon Shokubai Co., Ltd.) was used instead of the imide group-containing vinyl polymer (B-1). The dispersibility of (1) the low concentration dispersion and (2) the high concentration dispersion was evaluated in the same manner as in Example A1. The results are shown in Table 2.

(Comparative Example A7)
When an NMP solution of polyamideimide (“Comporacene AI1301” manufactured by Arakawa Chemical Industries, Ltd., solid content: 19.8% by mass) was poured into chloroform, polyamideimide was precipitated, so NMP was used as a solvent.

  NMP, the NMP solution of the polyamide, and the carbon nanostructure (A-1) are added so that 1.6 mg of polyamideimide and 2 mg of carbon nanostructure (A-1) are contained per 50 g of NMP. A low-concentration dispersion is prepared by mixing, and NMP, the NMP solution of polyamide and carbon so that 6.4 mg of polyamideimide and 8 mg of carbon nanostructure (A-2) are contained in 12 g of NMP. The dispersibility of (1) the low concentration dispersion and (2) the high concentration dispersion was evaluated in the same manner as in Example A1, except that the high concentration dispersion was prepared by mixing the nanostructure (A-2). . The results are shown in Table 2.

(Comparative Example A8)
Except for using 1.6 mg or 6.4 mg of polyvinylpyrrolidone (“Polyvinylpyrrolidone K30” manufactured by Wako Pure Chemical Industries, Ltd.) instead of the imide group-containing vinyl polymer (B-1), the same as Example A1 was used. (1) The dispersibility of the low concentration dispersion and (2) the high concentration dispersion was evaluated. The results are shown in Table 2.

(Comparative Example A9)
(1) Low concentration dispersion in the same manner as in Example A1 except that 1.6 mg or 6.4 mg of polymethyl methacrylate obtained in Preparation Example 7 was used instead of the imide group-containing vinyl polymer (B-1). The dispersibility of the liquid and (2) the high-concentration dispersion was evaluated. The results are shown in Table 2.

(Comparative Example A10)
The same procedure as in Example A1 was conducted except that 1.6 mg or 6.4 mg of methyl methacrylate / 1-pyrenylmethyl methacrylate copolymer (C-1) was used instead of the imide group-containing vinyl polymer (B-1). (1) The dispersibility of the low concentration dispersion and (2) the high concentration dispersion was evaluated. The results are shown in Table 2.

(Comparative Example A11)
The same procedure as in Example A1 was repeated except that 1.6 mg or 6.4 mg of sodium polystyrene sulfonate (Aldrich, weight average molecular weight 70000) was used instead of the imide group-containing vinyl polymer (B-1) (1 The dispersibility of the low-concentration dispersion and (2) the high-concentration dispersion was evaluated. The results are shown in Table 2. In addition, sodium polystyrene sulfonate was insoluble in chloroform.

  As is clear from the results shown in Table 2, when the carbon nanocomposite was prepared in chloroform or NMP using the imide group-containing vinyl polymer according to the present invention (Examples A1, A3 to A7). Is the same type of solvent when a carbon nanostructure is dispersed in the same type of solvent (Comparative Example A1) or by using a low molecular weight compound or other polymer in place of the imide group-containing vinyl polymer according to the present invention. It was confirmed that both the low-concentration dispersion and the high-concentration dispersion exhibited excellent dispersibility as compared with the case where the carbon nanocomposite was prepared (Comparative Examples A2 to A11).

  Further, when polyamideimide is used as a polymer containing an imide group (Comparative Example A7), since polyamideimide is dissolved only in a limited solvent such as NMP, the usable solvent is limited. When the imide group-containing vinyl polymer according to the invention was used (Examples A1 to A3), it was confirmed that the carbon nanocomposite was well dispersed in any solvent of chloroform, THF, and NMP.

(Example B1)
3.2 mg of imide group-containing vinyl polymer (B-5) and 4 mg of carbon nanostructure (A-1) were added to 50 g of ion-exchanged water, and this was subjected to ultrasonic treatment (desktop ultrasonic cleaner made by BRANSON) After using “BRANSONIC B-220” (oscillation frequency 45 kHz) for 1 hour, the dispersion was centrifuged (relative centrifugal acceleration 1000 G for 1 hour) and then allowed to stand for 20 hours. The UV-visible light absorption spectrum was measured for the supernatant after standing, and the dispersibility (precipitation resistance) was evaluated by the absorbance at 650 nm. The results are shown in Table 3. The larger the absorbance value, the more the carbon nanocomposite is dispersed in the solvent even after centrifugation, which means that the dispersibility (precipitation resistance) is excellent.

(Comparative Example B1)
4 mg of carbon nanostructure (A-1) is added to 50 g of ion-exchanged water, and then subjected to ultrasonic treatment (using a BRANSON desktop ultrasonic cleaner “BRANSONIC B-220”, oscillation frequency 45 kHz) for 1 hour. A dispersion was prepared in the same manner as in Example B1 except that it was applied, and the dispersibility was evaluated by absorbance. The results are shown in Table 3.

(Comparative Example B2)
A dispersion was prepared in the same manner as in Example B1, except that 3.2 mg of sodium polystyrene sulfonate (manufactured by Aldrich, weight average molecular weight 70000) was used instead of the imide group-containing vinyl polymer (B-5). Evaluation of dispersibility by absorbance was performed. The results are shown in Table 3.

(Comparative Example B3)
A dispersion was prepared in the same manner as in Example B1, except that 3.2 mg of polyvinylpyrrolidone (“Polyvinylpyrrolidone K30” manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of the imide group-containing vinyl polymer (B-5). Prepared and evaluated dispersibility by absorbance. The results are shown in Table 3.

  As is apparent from the results shown in Table 3, the dispersion containing the carbon nanocomposite (Example B1) according to the present invention uses conventional polystyrene sodium sulfonate or polyvinylpyrrolidone (comparison). Compared to Examples B2 to B3), the supernatant has a higher absorbance and the highest concentration, and the carbon nanocomposite of the present invention can be well dispersed not only in an organic solvent but also in ion-exchanged water. confirmed.

(Example C1)
First, 0.04 part by mass of an imide group-containing vinyl polymer (B-1) is added to 100 parts by mass of chloroform, and then 0.05 part by mass of the carbon nanostructure (A-1) is added. Ultrasonic treatment (using a BRANSON desktop ultrasonic cleaner “BRANSONIC B-220”, oscillation frequency 45 kHz) was applied for 1 hour to obtain a dispersion containing a carbon nanocomposite. Subsequently, the Kiriyama funnel (filter: omnipore membrane filter, pore size 1.0 μm) was used, and the dispersion was subjected to suction filtration while being washed with 300 parts by mass of chloroform. Then, the filter cake was vacuum-dried, the solvent was distilled off completely, and the carbon nanocomposite which the imide group containing vinyl polymer (B-1) adsorb | sucked to the carbon nanostructure (A-1) was obtained.

  The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Example C2)
An imide group was added to the carbon nanostructure (A-2) in the same manner as in Example C1, except that 0.05 part by mass of the carbon nanostructure (A-2) was used instead of the carbon nanostructure (A-1). A carbon nanocomposite on which the vinyl-containing polymer (B-1) was adsorbed was obtained. The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Example C3)
An imide group was added to the carbon nanostructure (A-3) in the same manner as in Example C1, except that 0.05 part by mass of the carbon nanostructure (A-3) was used instead of the carbon nanostructure (A-1). A carbon nanocomposite on which the vinyl-containing polymer (B-1) was adsorbed was obtained. The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Example C4)
An imide group was added to the carbon nanostructure (A-4) in the same manner as in Example C1, except that 0.05 part by mass of the carbon nanostructure (A-4) was used instead of the carbon nanostructure (A-1). A carbon nanocomposite on which the vinyl-containing polymer (B-1) was adsorbed was obtained. The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Example C5)
A carbon nanocomposite in which an imide group-containing vinyl polymer (B-1) was adsorbed to a carbon nanostructure (A-2) was obtained in the same manner as in Example C2, except that 100 parts by mass of NMP was used instead of chloroform. Obtained. The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Example C6)
A carbon nanostructure (A) in the same manner as in Example C2, except that 0.04 part by mass of the imide group-containing vinyl polymer (B-2) was used instead of the imide group-containing vinyl polymer (B-1). -2) to obtain a carbon nanocomposite in which the imide group-containing vinyl polymer (B-2) was adsorbed. The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Example C7)
A carbon nanostructure (A) in the same manner as in Example C2, except that 0.04 parts by mass of the imide group-containing vinyl polymer (B-3) was used instead of the imide group-containing vinyl polymer (B-1). -2) to obtain a carbon nanocomposite in which the imide group-containing vinyl polymer (B-3) was adsorbed. The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Example C8)
A carbon nanostructure (A) in the same manner as in Example C2, except that 0.04 parts by mass of the imide group-containing vinyl polymer (B-4) was used instead of the imide group-containing vinyl polymer (B-1). -2) to obtain a carbon nanocomposite in which the imide group-containing vinyl polymer (B-4) was adsorbed. The redispersibility, adsorption amount, adsorption stability and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Example C9)
A carbon nanostructure (A) in the same manner as in Example C2, except that 0.04 parts by mass of the imide group-containing vinyl polymer (B-5) was used instead of the imide group-containing vinyl polymer (B-1). -2) to obtain a carbon nanocomposite in which the imide group-containing vinyl polymer (B-5) was adsorbed. The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Comparative Example C1)
Carbon nanostructure in the same manner as in Example C1, except that 0.04 parts by mass of N-phenylmaleimide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of the imide group-containing vinyl polymer (B-1). A carbon nanocomposite in which N-phenylmaleimide was adsorbed on (A-1) was obtained. The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Comparative Example C2)
A carbon nanostructure (A-) was prepared in the same manner as in Example C2, except that 0.04 parts by mass of 1-pyrenylmethyl methacrylate obtained in Preparation Example 6 was used instead of the imide group-containing vinyl polymer (B-1). In 2), an attempt was made to prepare a carbon nanocomposite in which 1-pyrenylmethyl methacrylate was adsorbed, and the amount of adsorbed 1-pyrenylmethyl methacrylate was measured by the same method as the measurement method in (4) above. However, it was confirmed that 1-pyrenylmethyl methacrylate was not adsorbed on the carbon nanostructure (A-2).

  In addition, about the obtained sample, ie, carbon nanostructure (A-2), redispersibility was evaluated by the method similar to the evaluation method of said (3). The results are shown in Table 4.

(Comparative Example C3)
Implemented except that 0.04 parts by mass of polystyrene (manufactured by Polymer Source, number average molecular weight 107000, weight average molecular weight / number average molecular weight: 1.51) was used instead of the imide group-containing vinyl polymer (B-1). In the same manner as in Example C2, an attempt was made to prepare a carbon nanocomposite in which polystyrene was adsorbed on the carbon nanostructure (A-2). When the amount of polystyrene adsorbed on the obtained sample was measured by the above method, carbon nanocomposite was measured. It was confirmed that polystyrene was not adsorbed to the structure (A-2).

  In addition, about the obtained sample, ie, carbon nanostructure (A-2), redispersibility was evaluated by the method similar to the evaluation method of said (3). The results are shown in Table 4.

(Comparative Example C4)
Example C1 except that 0.04 parts by mass of a styrene / acrylonitrile / oxazoline copolymer (“Epocross RAS-1005” manufactured by Nippon Shokubai Co., Ltd.) was used in place of the imide group-containing vinyl polymer (B-1). In the same manner as described above, an attempt was made to prepare a carbon nanocomposite in which a styrene / acrylonitrile / oxazoline copolymer was adsorbed on the carbon nanostructure (A-1), but the styrene / acrylonitrile / oxazoline copolymer was obtained from the above method. When the adsorption amount of the polymer was measured, it was confirmed that the styrene / acrylonitrile / oxazoline copolymer was not adsorbed on the carbon nanostructure (A-1).

  In addition, about the obtained sample, ie, carbon nanostructure (A-1), redispersibility was evaluated by the method similar to the evaluation method of said (3). The results are shown in Table 4.

(Comparative Example C5)
NMP solution of NMP and polyamideimide (Arakawa Chemical Industries) so that 0.04 parts by mass of polyamideimide and 0.05 parts by mass of carbon nanostructure (A-2) are contained with respect to 100 parts by mass of NMP. The carbon nanostructure (A-2) was prepared in the same manner as in Example C5 except that “Comporacene AI1301” manufactured by Co., Ltd., solid content 19.8 mass%) and the carbon nanostructure (A-2) were mixed. A carbon nanocomposite adsorbed with polyamideimide was obtained. The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Comparative Example C6)
Carbon was prepared in the same manner as in Example C2, except that 0.04 parts by mass of polyvinylpyrrolidone (“Polyvinylpyrrolidone K30” manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of the imide group-containing vinyl polymer (B-1). A carbon nanocomposite in which polyvinylpyrrolidone was adsorbed to the nanostructure (A-2) was obtained. The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Comparative Example C7)
A carbon nanostructure (A-1) was prepared in the same manner as in Example C1, except that 0.04 parts by mass of polymethyl methacrylate obtained in Preparation Example 7 was used instead of the imide group-containing vinyl polymer (B-1). ) Was attempted to prepare a carbon nanocomposite in which polymethyl methacrylate was adsorbed. When the amount of polymethyl methacrylate adsorbed was measured by the above method for the obtained sample, the carbon nanostructure (A-1) was obtained. It was confirmed that polymethyl methacrylate was not adsorbed.

  In addition, about the obtained sample, ie, carbon nanostructure (A-1), redispersibility was evaluated by the method similar to the evaluation method of said (3). The results are shown in Table 4.

(Comparative Example C8)
Carbon was prepared in the same manner as in Example C1, except that 0.04 part by mass of methyl methacrylate / 1-pyrenylmethyl methacrylate copolymer (C-1) was used instead of the imide group-containing vinyl polymer (B-1). A carbon nanocomposite was obtained in which the methyl methacrylate / methyl methacrylate 1-pyrenylmethyl copolymer (C-1) was adsorbed to the nanostructure (A-1). The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

(Comparative Example C9)
Carbon in the same manner as in Example C2, except that 0.04 parts by mass of methyl methacrylate / 1-pyrenylmethyl methacrylate copolymer (C-1) was used instead of the imide group-containing vinyl polymer (B-1). A carbon nanocomposite was obtained in which methyl methacrylate / methyl 1-pyrenylmethyl methacrylate (C-1) was adsorbed to the nanostructure (A-2). The redispersibility, adsorption amount, adsorption stability, and thermal decomposition temperature of this carbon nanocomposite were evaluated by the methods (3) to (5). The results are shown in Table 4.

  As is apparent from the results shown in Table 4, when the imide group-containing vinyl polymer according to the present invention was used (Examples C1 to C9), the carbon nanocomposite of the present invention was excellent in the solvent. It was confirmed that it was dispersible.

  On the other hand, when a low molecular weight compound is used instead of the imide group-containing vinyl polymer according to the present invention (Comparative Examples C1 to C2) or when a polymer other than the imide group-containing vinyl polymer is used (Comparative Example C3). ~ C7), it is difficult to disperse the carbon nanostructure in the solvent without agglomeration, because the adsorption of the low molecular weight compound or polymer is not confirmed on the carbon nanostructure or the adsorption amount is small. there were. On the other hand, when a vinyl polymer containing a pyrenyl group is used (Comparative Examples C8 to C9), the carbon nanocomposite is compared with a polymer other than the low molecular weight compound or the imide group-containing vinyl polymer. Could be dispersed in the solvent.

  Further, the carbon nanocomposites of the present invention (Examples C1 to C9) adsorbed with the imide group-containing vinyl polymer were carbon nanocomposites (Comparative Example C5, It was confirmed that the adsorption stability of the polymer was superior to that of C8 and C9).

  Furthermore, the carbon nanocomposites (Examples C1 to C9) of the present invention in which the imide group-containing vinyl polymer was adsorbed were combined with the carbon nanocomposites (Comparative Examples C8 to C9) in which the pyrenyl group-containing vinyl polymer was adsorbed. It was confirmed that the polymer had a high thermal decomposition temperature and excellent heat resistance.

(Example D1)
700 cm ³ of a mixture containing 1.053% by volume of the carbon nanocomposite obtained in Example C2 and 98.947% by volume of polyphenylene sulfide resin (polyphenylene sulfide manufactured by Aldrich, melt viscosity of 275 poise (310 ° C.)) was dry-blended. Prepared. Here, the compounding amount of the carbon nanocomposite takes into account the amount of the imide group-containing vinyl polymer adsorbed to the carbon nanostructure, and the capacity of the carbon nanostructure contained in 100% by volume of the mixture. The mixture was prepared so that the remainder excluding the carbon nanocomposite was a polyphenylene sulfide resin. This mixture was melt-kneaded using a twin-screw extruder equipped with a vent (manufactured by Technobell, screw diameter 15 mm, L / D = 60) at a cylinder setting temperature of 300 ° C. and a screw rotation speed of 100 rpm. The discharged kneaded product was extruded into a strand shape, cooled and then cut with a cutter to obtain a pellet-shaped resin composition. This pellet was obtained by uniformly dispersing the carbon nanocomposite, and the appearance was good. Moreover, adhesion of decomposition | disassembly volatilization products of an imide group containing vinyl polymer, etc. to the looking glass of a vent was not confirmed.

The obtained pellets were vacuum-dried at 130 ° C. for 6 hours, and then injection molded under conditions of a molding temperature of 300 ° C. and a mold temperature of 130 ° C. to obtain a molded product having a thickness of 2 mm. A 25 mm × 25 mm × 2 mm sample was cut out from this molded product, and a steady-state thermal conductivity measuring device (manufactured by ULVAC-RIKO, Inc. “
GH-1 "), and the thermal conductivity in the thickness direction (perpendicular to the flow direction) was measured at 40 ° C (upper and lower temperature difference of 24 ° C). The thermal conductivity was 0.36 W / mK.

(Comparative Example D1)
Pellets were obtained in the same manner as in Example D1, except that 1% by volume of carbon nanostructure (A-2) was used instead of the carbon nanocomposite obtained in Example C2, and the amount of polyphenylene sulfide resin was changed to 99% by volume. A shaped resin composition was prepared. In this pellet, the carbon nanostructure (A-2) was not uniformly dispersed, and the appearance of the pellet was inferior to that of Example D1. Moreover, it was 0.32 W / mK when the molded article was produced using the obtained pellet like Example D1, and the heat conductivity was measured.

(Comparative Example D2)
A pellet was prepared by melting and kneading 700 cm ³ of a polyphenylene sulfide resin (polyphenylene sulfide manufactured by Aldrich, melt viscosity 275 poise (310 ° C.)) in the same manner as in Example D1 except that the carbon nanocomposite was not used. A product was prepared and its thermal conductivity was measured and found to be 0.24 W / mK.

  As is clear from the results shown in Example D1 and Comparative Examples D1 to D2, the polyphenylene sulfide resin composition (Example D1) in which the carbon nanocomposite of the present invention was blended was blended with the carbon nanostructure ( Compared with Comparative Example D1), the dispersibility of the carbon nanocomposite and the thermal conductivity of the molded product were improved. Thus, it was confirmed that the addition of a small amount of carbon nanocomposite can efficiently improve the thermal conductivity while suppressing the thickening of the system.

  As described above, according to the present invention, a carbon nanocomposite excellent in dispersibility in a solvent or resin can be obtained. In addition, since the carbon nanocomposite of the present invention is excellent in heat resistance, it can be used at a high temperature such as being added to a high heat resistant resin that requires a high temperature during production, and can be uniformly dispersed.

  Therefore, the carbon nanocomposite of the present invention is required for applications that make use of the characteristics inherent to the carbon nanostructure, such as applications that require mechanical properties, applications that require electromagnetic shielding, applications that require heat resistance, and dimensionality. Can be used for various applications such as applications where thermal conductivity is required, applications where thermal conductivity is required, applications where electrical conductivity is required, and resin molded bodies, resin sheets, It can be suitably used for a resin film or the like.

  Further, in the present invention, expensive raw materials and manufacturing processes are unnecessary, and the production cost of carbon nanocomposites, dispersions, and resin compositions can be reduced.

Claims (9)

  A carbon nanocomposite comprising a carbon nanostructure and a vinyl polymer that adsorbs to the carbon nanostructure and includes an imide group-containing structural unit.   The carbon nanocomposite according to claim 1, wherein the vinyl polymer further contains a vinyl monomer unit other than the imide group-containing structural unit.   The carbon nanocomposite according to claim 1, wherein the imide group-containing structural unit includes a maleimide monomer unit.   The carbon nanostructure according to any one of claims 1 to 3, wherein an adsorption amount of the vinyl polymer is 0.1 parts by mass or more with respect to 100 parts by mass of the carbon nanostructure. Complex.   The carbon nanocomposite according to any one of claims 1 to 4, wherein a thermal decomposition temperature of the vinyl polymer is 290 ° C or higher.   The carbon nanocomposite according to any one of claims 1 to 5, wherein an average diameter of the carbon nanostructure is 1 µm or less.   A dispersion comprising the carbon nanocomposite according to any one of claims 1 to 6 and a solvent.   A resin composition comprising the carbon nanocomposite according to any one of claims 1 to 6 and a resin.   Production of a carbon nanocomposite characterized in that a carbon nanostructure and a vinyl polymer containing an imide group-containing structural unit are mixed in a solvent to adsorb the vinyl polymer to the carbon nanostructure. Method.