JP5146371B2 - Carbon nanocomposite, dispersion and resin composition containing the same, and method for producing carbon nanocomposite - Google Patents

Description

  The present invention relates to a carbon nanocomposite, a dispersion and a resin composition containing the carbon nanocomposite, and a method for producing the carbon nanocomposite.

  Carbon nanostructures typified by carbon nanotubes (CNT) are excellent in thermal conductivity, electrical conductivity, mechanical properties, and storage properties. For example, electronic device materials, microscope probes, field emission displays Developments are being made and are attracting attention for use in emitters, negative electrodes for lithium secondary batteries, field effect transistors, materials for drug delivery systems, composite materials with resins and ceramics, and molecular storage materials. However, since the carbon nanostructure is easily aggregated by van der Waals force and has extremely low dispersibility in a solvent, a resin, a metal, and ceramics, there is a problem that the above characteristics cannot be sufficiently 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 carbon nanotubes at least partially coated with at least one polymer, and the polymer includes polyvinylpyrrolidone, polystyrene sulfonate, polyethylene Examples include glycols and the like, and WO 2002/076888 (Patent Document 2) discloses a powder in which a hydrophilic polymer is adsorbed on a carbon nanotube. Examples of the polymer include gum arabic, carrageenan, and pectin. Is illustrated. However, when such a polymer as described in Patent Documents 1 and 2 is used, the dispersibility of the carbon nanotubes is not sufficient particularly in an organic solvent or a resin.

  In addition, in pages 2904 to 2905 (Non-patent Document 1) of “CHEM. COMMUN.” Issued in 2003, a composite composed of a polymer containing a pyrenyl group showing affinity for carbon nanotubes and carbon nanotubes. The body is disclosed. By adsorbing the polymer to the carbon nanotube, the dispersibility of the carbon nanotube in the solvent tends to be improved. However, further improvement in dispersibility has been demanded in order to further develop the properties inherent to carbon nanostructures such as carbon nanotubes such as thermal conductivity, electrical conductivity, and mechanical properties.

  Japanese Patent Application Laid-Open No. 2006-265035 (Patent Document 3) discloses a dispersion containing polyphenylene vinylene or polythiophene and carbon nanotubes, and a thin film prepared from a supernatant obtained by centrifuging this dispersion. Yes. However, the concentration of carbon nanotubes in the supernatant is sufficient to further develop the properties inherent to carbon nanotubes such as thermal conductivity, electrical conductivity, and mechanical properties in applications such as vehicle parts and electrical / electronic equipment parts. It wasn't. In addition, when a composition containing polyphenylene vinylene or polythiophene and carbon nanotubes is blended in a resin suitable for vehicle parts represented by engineering plastics and super engineering plastics, the affinity between these resins and polyphenylene vinylene, polythiophene is low, The dispersibility in the resin and the fluidity (workability) of the resin composition were not sufficient.

International Publication No. 2002/016257 Pamphlet International Publication No. 2002/076888 Pamphlet JP 2006-265035 A

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

  The present invention has been made in view of the above problems of the prior art, a carbon nanocomposite excellent in dispersibility and fluidity in a solvent or resin, a dispersion and a resin composition containing the same, and It aims at providing the manufacturing method of the carbon nanocomposite.

  As a result of intensive studies to achieve the above object, the present inventors have a carbon nanostructure, a main chain composed of a vinyl polymer, and a side chain composed of a polymer chain. And a graft-type vinyl polymer having a molecular weight of 300 or more and adsorbing to the carbon nanostructure, the structural unit comprising one and the vinyl monomer unit in the main chain to which the polymer chain is bonded. It has been found that the dispersibility and fluidity in a solvent or resin are sufficiently improved by the carbon nanocomposite, and the present invention has been completed.

That is, the carbon nanocomposite of the present invention includes a carbon nanostructure,
A main chain comprising a vinyl polymer and a side chain comprising at least one polymer chain of vinyl polymer, polysiloxane and polyoxyalkylene , wherein one of the polymer chains and the polymer chain are A structural unit having a molecular weight of 300 or more consisting of a vinyl monomer unit in the main chain to be bonded, and a polycyclic aromatic group-containing vinyl monomer unit represented by the general formula (3) described later (wherein R ¹ Represents a divalent organic group having 1 to 20 carbon atoms, R ² represents a monovalent polycyclic aromatic group, R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom and 1 to carbon atoms. 20 represents a monovalent organic group of 20) and a maleimide monomer unit represented by the following general formula (4) (wherein R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group). represents any one of, R ⁸ is a hydrogen atom, a Kill group, an alkynyl group, an aralkyl group, a cycloalkyl group, adsorbed on at least one contains a structural unit and said carbon nanostructure of the represent.) Any of the aryl group and an amino group A graft-type vinyl polymer,
It is characterized by providing.

In the carbon nanocomposite of the present invention, the molecular weight of a structural unit composed of one of the polymer chains and a vinyl monomer unit in the main chain to which the polymer chain is bonded is 400 or more. preferable.

  Furthermore, in the carbon nanocomposite of the present invention, the carbon nanostructure preferably has a diameter of 1 μm or less.

  The dispersion of the present invention contains the carbon nanocomposite of the present invention and a solvent.

  The resin composition of the present invention is characterized by containing the carbon nanocomposite of the present invention and a resin.

Further, the method for producing the carbon nanocomposite of the present invention comprises a carbon nanostructure,
A main chain composed of a vinyl polymer and a side chain composed of at least one polymer chain of vinyl polymer, polysiloxane and polyoxyalkylene, and one of the polymer chains and the polymer chain are A structural unit having a molecular weight of 300 or more consisting of a vinyl monomer unit in the main chain to be bonded, and a polycyclic aromatic group-containing vinyl monomer unit represented by the general formula (3) described later (wherein R ¹ Represents a divalent organic group having 1 to 20 carbon atoms, R ² represents a monovalent polycyclic aromatic group, R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom and 1 to carbon atoms. 20 represents a monovalent organic group of 20) and a maleimide monomer unit represented by the following general formula (4) (wherein R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group). It represents any one of, R ⁸ is a hydrogen atom, Alkyl group, and an alkynyl group, an aralkyl group, a cycloalkyl group, any of the aryl group and an amino group.) Grafted vinyl polymer and at least one kind of structural units of,
In a solvent to adsorb the graft type vinyl polymer to the carbon nanostructure to obtain a carbon nanocomposite.

  The reason why the carbon nanocomposite of the present invention is excellent in dispersibility and fluidity in a solvent or resin is not necessarily clear, but the present inventors speculate as follows. That is, in the present invention, the graft-type vinyl polymer adsorbed on the carbon nanostructure has a main chain composed of a vinyl polymer and a side chain composed of a polymer chain, The molecular weight of a structural unit composed of one and the vinyl monomer unit in the main chain to which the polymer chain is bonded is 300 or more. Since such a graft-type vinyl polymer has a bulky polymer chain in the side chain, the steric repulsion between the carbon nanocomposites is increased by the adsorption thereof. Due to such steric repulsion, the dispersibility of the carbon nanocomposite in the solvent and in the resin is sufficiently improved. Further, since the cohesive energy between the carbon nanocomposites decreases due to the increase in steric repulsion between the carbon nanocomposites, the carbon nanocomposite of the present invention adsorbs the graft-type vinyl polymer. It is assumed that the fluidity is sufficiently improved as compared with the case where it is not. In the carbon nanocomposite of the present invention, by changing the type of the polymer chain of the side chain (for example, the type of macromonomer when the graft type vinyl polymer is produced by the macromonomer method), It becomes possible to improve dispersibility in various solvents and resins and to impart various functionalities.

  According to the present invention, it is possible to provide a carbon nanocomposite excellent in dispersibility and fluidity in a solvent or a resin, a dispersion and a resin composition containing the carbon nanocomposite, and a method for producing the carbon nanocomposite. It becomes possible.

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

[Carbon nanocomposite]
The carbon nanocomposite of the present invention includes a carbon nanostructure,
Molecular weight of a structural unit having a main chain composed of a vinyl polymer and a side chain composed of a polymer chain, and comprising one of the polymer chains and a vinyl monomer unit in the main chain to which the polymer chain is bonded Is a graft type vinyl polymer adsorbed to the carbon nanostructure, and is 300 or more,
It is characterized by providing.

(Carbon nanostructure)
First, the carbon nanostructure according to the present invention will be described. Such carbon nanostructures are not particularly limited. For example, carbon nanofiber, carbon nanohorn, carbon nanocone, carbon nanotube, carbon nanocoil, carbon microcoil, nanographene (graphene nanoribbon, etc.), carbon nanowall, fullerene , Graphite, carbon flakes, and derivatives thereof (for example, those in which some or all of the carbon atoms are replaced with boron or nitrogen). From the viewpoint of improving thermal conductivity and mechanical properties when using such carbon nanostructures, carbon nanofibers, carbon nanohorns, carbon nanocones, carbon nanotubes, carbon nanocoils, graphite, nanographene and carbon At least one selected from anisotropic carbon nanostructures such as nanowalls is more preferable, and carbon nanofibers and / or carbon nanotubes are more preferable. The carbon nanostructure may be a single trunk or a dendritic structure in which a large number of carbon nanostructures grow outward like branches, but the thermal conductivity, electrical conductivity From the viewpoint of mechanical strength and the like, it is preferably a single trunk.

  In addition, the upper limit of the diameter of such carbon nanostructure is not particularly limited, but from the viewpoint of improving thermal conductivity and electrical conductivity, heat resistance can be achieved by adding a small amount of carbon nanocomposite when used as a resin composition. From the viewpoint of improving (increasing the deflection temperature under load, decreasing the thermal expansion coefficient), and from the viewpoint of improving the mechanical strength such as tensile strength and impact strength by adding a small amount of carbon nanocomposite to the resin. It is preferably 1 μm or less, more preferably 800 nm or less, still more preferably 500 nm or less, particularly preferably 300 nm or less, and most preferably 200 nm or less. The lower limit of the diameter of such a carbon nanostructure is not particularly limited, and is preferably, for example, 0.4 nm or more, and more preferably 0.5 nm or more.

  Further, the aspect ratio of the carbon nanostructure is not particularly limited, but when the carbon nanocomposite is mixed with a resin to produce the resin composition of the present invention, a small amount is added, and tensile strength, impact strength, etc. 5 or more from the viewpoint of improving the thermal conductivity of the carbon nanostructure and its resin composition in the case of applications where the mechanical strength is improved, the thermal linear expansion is reduced, and the thermal conductivity is required. Preferably, it is 10 or more, more preferably 20 or more, particularly preferably 40 or more, and most preferably 80 or more. Moreover, the carbon nanostructure according to the present invention may contain atoms, molecules, etc. other than carbon in the structure, and may include, for example, a metal or another structure as necessary.

When the carbon nanocomposite of the present invention is used in applications where high thermal conductivity is required, for example, a high thermal conductive resin, the carbon nanostructure is a peak of a Raman spectrum obtained by measuring with the Raman spectrophotometer. Among these, 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, and the vicinity of about 1350 cm ⁻¹ observed to have defects such as dangling bonds in the graphene structure. The D band ratio and G / D value to be confirmed are not particularly limited, but are preferably 0.1 or more, more preferably 0.5 or more, from the viewpoint of improving thermal conductivity. Preferably it is 1.0 or more, Especially preferably, it is 3.0 or more, Most preferably, it is 5.0 or more.

  Moreover, when a carbon nanostructure contains either a carbon nanotube or a carbon nanofiber, these can use any of a single layer and a multilayer, and can be used properly or used together according to a use. Here, a multilayer means a thing of two or more layers.

  Furthermore, the carbon nanostructure production method is not particularly limited, but a conventionally known production method can be suitably selected according to the application, for example, chemical vapor phase such as laser ablation method, arc synthesis method, HiPco process, etc. Examples thereof include a growth method (CVD method) and a melt spinning method. The carbon nanostructures used in the present invention are not limited to those produced by these methods.

(Graft type vinyl polymer)
Next, the graft type vinyl polymer according to the present invention will be described. Such a graft-type vinyl polymer has a main chain composed of a vinyl polymer and a side chain composed of a polymer chain, and one of the polymer chains is bonded to the polymer chain in the main chain. The structural unit composed of vinyl monomer units has a molecular weight of 300 or more. In the following, “a structural unit comprising one of the polymer chains and a vinyl monomer unit in the main chain to which the polymer chain is bonded” is referred to as “structural unit (I)”.

  Here, the “structural unit (I)” will be described with an example. The graft-type vinyl polymer has a structure in which at least one atom in the vinyl monomer is substituted with a polymer chain. When the macromonomer is produced by a graft polymerization method (macromonomer method), the structural unit formed by the macromonomer (the structural unit derived from the macromonomer: the macromonomer unit) is the structural unit (I). The graft-type vinyl polymer is produced by a method of adding a polymer compound to a side chain of a vinyl polymer obtained by polymerizing a vinyl monomer, and vinyl. When the polymer is produced by a method of growing a polymer chain on a side chain of a vinyl polymer obtained by polymerizing a monomer, Of the units formed from one of the nil-based monomers, a part excluding the side chain part to which the polymer compound is added or the side chain part for growing the polymer chain, and the part introduced into the part A structural unit composed of one polymer chain (part derived from the polymer compound) corresponds to the structural unit (I). To explain with a more specific example, the following general formula (1):

(In the formula, P represents a polymer chain.)
When the graft-type vinyl polymer is produced using the macromonomer method using the macromonomer represented by the structure, the structure formed from the macromonomer in the graft-type vinyl polymer The unit is the following general formula (2):

(In the formula, P represents a polymer chain.)
The structural unit represented by the general formula (2) corresponds to the structural unit (I).

The vinyl monomer unit is a partial structure of the structural unit (I) having a polymer chain as a side chain, and only the polymer chain bonded to the side difference from the structural unit (I). (Excluding the polymer chain portion bonded to the side difference among the units formed from one vinyl monomer). For example, when the structural unit (I) is a structural unit represented by the above general formula (2), a portion excluding the polymer chain portion represented by P in the general formula (2) (formula (2 The portion represented by — (CH ₃ ) CH—C (CH ₃ ) —)) corresponds to the vinyl monomer unit.

  Such vinyl monomer units are not particularly limited as long as they are derived from vinyl monomers (including vinyl macromonomers), and are formed using known vinyl monomers as appropriate. What you let me do. That is, examples of such vinyl monomer units include unsaturated carboxylic acid ester monomer units, vinyl cyanide monomer units, unsaturated carboxylic acid monomer units, acid anhydride units or derivative units thereof, and epoxy group-containing vinyls. Monomer unit, oxazoline group-containing vinyl monomer unit, amino group-containing vinyl monomer unit, amide group-containing vinyl monomer unit, hydroxyl group-containing vinyl monomer unit, olefin monomer unit, halogenated vinyl monomer unit, carboxylic acid Examples thereof include unsaturated ester monomer units, cationic vinyl monomer units, maleimide monomer units, and the like.

  Such maleimide monomers are not particularly limited, and examples thereof include maleimide, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, and N-isobutyl. N-alkylmaleimides such as maleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide and Nn-dodecylmaleimide; N N-alkynylmaleimides such as acetylenylmaleimide and N-propynylmaleimide; N-aralkylmaleimides such as N-benzylmaleimide and N-methylbenzylmaleimide; N-unsubstituted silanes represented by N-cyclohexylmaleimide N-cycloalkylmaleimides such as N-phenylmaleimide, N-methylcyclohexylmaleimide, N-substituted maleylimides such as N-substituted cycloalkylmaleimide; N-phenylmaleimide, N-naphthylmaleimide, N-anthracenylmaleimide and N-pyrenylmaleimide N-unsubstituted arylmaleimide, N-tolylmaleimide and alkyl-substituted arylmaleimide represented by N-xylylmaleimide, N-amino-substituted arylmaleimide represented by N- (4-aminophenyl) maleimide, N- N-alkynyl-substituted arylmaleimide represented by acetylenylphenylmaleimide and N-propynylphenylmaleimide, N-aryl-substituted arylmaleimide represented by N-biphenylmaleimide, N-o-chloro N-arylmaleimides such as phenylmaleimide, N- (2,4,6-trichlorophenyl) maleimide, N-pentafluorophenylmaleimide and N-halogen-substituted arylmaleimides represented by N-tetrafluorophenylmaleimide; N-pyridylmaleimide , N-3- (9-alkylcarbazoyl) maleimide and N- (9-acridinyl) maleimide substituted maleimides; N, N′-1,4-phenylenedimaleimide, N, N′-1 , 3-phenylene dimaleimide and 4,4′-bismaleimide diphenylmethane bismaleimide; N-fluoromaleimide, N-chloromaleimide, N-bromomaleimide, and halogenated maleimide such as N-iodomaleimide; N-aminomale And N-acetylmaleimide, N-hydroxymaleimide, N-hydroxyphenylmaleimide, p-carboxyphenylmaleimide, N- (2-carboxyethyl) maleimide and the like. These maleimide monomers may be used alone or in combination of two or more. Moreover, these maleimide monomers may have a water-soluble substituent such as a sulfone group or a sulfonimide group, if necessary.

  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 isobutyl, (meth) acrylic acid tert-butyl, (meth) acrylic acid n-hexyl, and (meth) acrylic acid cyclohexyl, (meth) acrylic acid n-pentyl, (meth) acrylic acid isopentyl, (meta ) Neopentyl acrylate, isoamyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Acid n-nonyl, isononyl (meth) acrylate, (meth) acrylic acid n-de , Alkyl (meth) acrylates such as isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, chloromethyl (meth) acrylate and (meth) acrylic Examples include (meth) acrylic acid halogenated alkyl esters represented by 2-chloroethyl acid.

  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. Further, the derivative is not particularly limited, and examples thereof include a metal salt of an unsaturated carboxylic acid monomer.

  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, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylamino (meth) acrylate Ethyl, ethyl aminopropyl (meth) acrylate, 2-dibutylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, phenylameth (meth) acrylate Aminoethyl, and the like (meth) amino group-containing (meth) acrylic acid esters of (meth) acrylic acid such as cyclohexyl acrylate aminoethyl.

  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 oxide group containing vinyl-type monomer, For example, polyethyleneglycol (meth) acrylate etc. are mentioned.

  The olefin monomer is not particularly limited, and examples thereof include ethylene, propylene, isoprene, neoprene, butene, isobutene, butadiene, dicyclopentadiene, ethylidene norbornene, and cyclic olefin. Examples of the vinyl halide monomer Although there is no particular limitation, for example, vinyl chloride, vinyl fluoride, ethylene trifluoride chloride, tetrafluoroethylene, perfluoroethylene and the like can be mentioned. The carboxylic acid unsaturated ester monomer is not particularly limited, and examples thereof include vinyl acetate and isopropenyl acetate. The cationic vinyl monomer is not particularly limited, and examples thereof include diallyldimethylammonium hydrochloride, allylimine hydrochloride, and allylamine hydrochloride, and the anionic vinyl monomer is not particularly limited. Styrene sulfonic acid, sodium styrene sulfonate, lithium styrene sulfonate and the like.

  Further, the vinyl monomer unit (the portion obtained by removing the polymer chain from the structural unit (I)) preferably has a molecular weight of 27 to 150, more preferably 71 to 140. If the molecular weight is less than the lower limit, the solubility of the graft-type vinyl polymer in the solvent tends to decrease. It tends to decrease.

  Further, the “polymer chain” contained in the structural unit (I) means a structure including a structure constituted by repeating at least one monomer unit in the structure. Such a polymer chain preferably has a molecular weight of 200 or more, more preferably 250 to 5000000, and still more preferably 300 to 1000000. If the molecular weight of such a polymer chain is less than the lower limit, the resulting carbon nanocomposite tends to have insufficient dispersibility. If the upper limit is exceeded, the graft type vinyl polymer dissolves in the solvent. Tend to decrease.

  The type of polymer chain contained in the structural unit (I) is not particularly limited, and examples thereof include vinyl polymers, polyimides, polyether imides, polyester imides, polyether ether ketones, and polyether amides. Polyesters such as poly ε-caprolactone, polyamides such as poly ε-caprolactam, polyamideimide, polypyrrole, polyaniline, polylactone, polycarbonate, polyethylene terephthalate, polyethylene 2,6-naphthalate and polybutylene terephthalate, etc., liquid crystal polyester, polyarylate , Polyarylene ether, polyarylene sulfide, polyethersulfone, polyoxyalkylene, polysiloxane, polylactic acid, polyphenol, polyurethane, polysulfone At least one of polyisocyanates such as poly (n-hexyl isocyanate), polytetrahydrofuran, poly (vinylidene fluoride), polyethylenimine, poly (N-methylglycine), and the like. , Vinyl polymers, polyoxyalkylenes, polysiloxanes, and polylactones are more preferable from the viewpoint of improving the solubility of the graft-type vinyl polymer in various solvents and the dispersibility of the resulting carbon nanocomposite in various solvents. From the viewpoints of dispersibility and fluidity in an organic solvent and resin, at least one selected from vinyl polymers, polysiloxanes, and polylactones is more preferable, and vinyl polymers and / or polysiloxanes are particularly preferable. Most preferably, it is a vinyl polymer. On the other hand, when dispersion in a highly polar solvent such as water or alcohol is required, polyoxyalkylene is preferably used as the type of polymer chain contained in the structural unit (I). Here, polyoxyalkylene can also be referred to as polyalkylene glycol and polyalkylene oxide. The shape of the polymer chain contained in the structural unit (I) is not particularly limited, and may be linear or branched. Examples of the branched shape include a graft shape, a hyperbranched shape, and a star polymer. Although it may be a shape, a dendrimer shape or a shape containing a cross-linked portion, it is preferably a straight chain.

  Further, when the polymer chain contained in the structural unit (I) is a vinyl polymer, the type of vinyl monomer used to form such a polymer chain is not particularly limited, For example, unsaturated carboxylic acid ester monomer, vinyl cyanide monomer, aromatic vinyl monomer, unsaturated carboxylic acid monomer, acid anhydride or derivative thereof, epoxy group-containing vinyl monomer, oxazoline group-containing vinyl monomer, amino Group-containing vinyl monomers, amide group-containing vinyl monomers, hydroxyl group-containing vinyl monomers, polyalkylene oxide group-containing vinyl monomers, olefin monomers, halogenated vinyl monomers, carboxylic acid unsaturated ester monomers, cationic vinyl monomers Monomer, anionic vinyl monomer, male It can be preferably exemplified de monomer. Moreover, as such a vinyl-type monomer, the thing similar to what was demonstrated as a monomer used when forming the above-mentioned vinyl-type monomer unit can be used.

  Further, as specific examples when the polymer chain contained in the structural unit (I) is a vinyl polymer, polyethylene, polypropylene, polyisoprene, polyneoprene, hydrogenated polyisoprene, Polybutene, polyisobutene, hydrogenated polyisobutene, polybutadiene, hydrogenated polybutadiene, ethylene-propylene copolymer, ethylene-propyne-dicyclopentadiene copolymer, ethylene-propylene-diene copolymer, cyclic polyolefin, polystyrene, styrene-acrylonitrile copolymer Polymer, styrene-methacrylic acid ester copolymer, styrene-methacrylic acid ester / acrylonitrile copolymer, poly (meth) acrylic acid, poly (meth) acrylic acid methyl ester, poly (meth) acrylic acid ethyl ester, poly (meth) A Poly (meth) acrylates such as propyl laurate, poly (meth) acrylate n-butyl, poly (meth) acrylate isobutyl and poly (meth) acrylate t-butyl, poly (meth) acrylate 2-hydroxy Poly (meth) acrylamide such as ethyl, poly (meth) acrylamide, poly (N, N-dimethylacrylamide), poly (dialkylaminoalkyl) such as poly (dimethylaminoethyl), poly such as poly (2-ethyloxazoline) Examples thereof include oxazoline, poly (N-acylalkylenimine) and acid-modified products thereof, acid anhydride-modified products, epoxy-modified products, and oxazoline-modified products. The modification method for obtaining the modified product is not particularly limited, and may be copolymerization of (meth) acrylic acid, acid anhydride, grafting, or chemical reaction. In addition, the terminal group of these polymer chain portions is not particularly limited, and is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, methoxy, ethoxy, In addition to groups introduced during the production of linear or branched alkoxy groups having 1 to 20 carbon atoms such as propoxy and butoxy, linear or branched alkyl mercapto groups having 1 to 20 carbon atoms, benzyl groups, etc. It may be a reactive substituent such as a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a maleic anhydride group, or an oxazoline group.

  In addition, when the polymer chain contained in the structural unit (I) contains polyoxyalkylene, the graft-type vinyl polymer is soluble in water and alcohol, which is a highly polar solvent, and the resulting carbon nanocomposite is Good dispersion is possible in these solvents. Such polyoxyalkylene is not particularly limited. For example, polyethylene glycol, polymethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, poly (ethylene glycol-propylene glycol) Poly (ethylene glycol-tetramethylene glycol), poly (propylene glycol-tetramethylene glycol) and the like can be preferably mentioned.

  When the polymer chain contained in the structural unit (I) contains polysiloxane, the polysiloxane-containing macromonomer used to form the polymer chain containing such polysiloxane is not particularly limited, For example, α-methyl-ω- (3-methacryloxypropyl) polydimethylsiloxane, α-ethyl-ω- (3-methacryloxypropyl) polydimethylsiloxane, α-propyl-ω- (3-methacryloxypropyl) poly Dimethylsiloxane, α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane, α-methoxy-ω- (3-methacryloxypropyl) polydimethylsiloxane and α-ethoxy-ω- (3-methacryloxypropyl) Organopolysiloxanes such as polydimethylsiloxane, (meth) acrylic acid Methoxysilylpropyl, (meth) acrylic acid triethoxysilylpropyl, (meth) acrylic acid methyldimethoxysilylpropyl, (meth) acrylic acid methyldiethoxysilylpropyl, trimethoxysilylstyrene, vinyltrimethoxysilane, vinyltriethoxysilane and Preferable examples include those obtained by treating alkoxysilane such as p-styryltrimethoxysilane with alkoxysilane to form polysiloxane.

  Moreover, as the macromonomer having a polymer chain, a desired macromonomer may be produced and used by various production methods including conventionally known production methods, or commercially available ones may be used. Examples of such commercially available macromonomers include α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane (trade name: Silaplane FM-0711 (number average molecular weight 1000), manufactured by Chisso Corporation, Silaplane FM-0721 (number average molecular weight 5000), trade name Silaplane FM-0725 (number average molecular weight 10000)), Toa Gosei Co., Ltd. single-end methacryloylated polystyrene (trade name AS-6), Toa Gosei (stock) ) One-end methacryloylated polymethyl methacrylate (trade names AA-6, AA-714S), Toa Gosei Co., Ltd. One-end methacryloylated styrene-acrylonitrile copolymer (trade name AN-6), Toa Gosei Co., Ltd. ) One-end methacryloylated polydimethylsiloxane (trade name AK-32), Toa Gosei ( Specific examples of methacryloylated poly (n-butyl acrylate) (trade name AB-6) and polyethylene glycol monoalkyl ether (meth) acrylate ester manufactured by Shin-Nakamura Chemical Co., Ltd. Methacrylate (trade name NK ester M90G), Shin Nakamura Chemical Co., Ltd. methoxypolyethylene glycol monomethacrylate (trade name NK ester M230G), Kyoeisha Chemical Co., Ltd. methoxypolyethylene glycol methacrylate (trade name Light Ester 130MA, Light Ester 041MA) , Light ester 130A), hydroxyl group-terminated polyethylene glycol mono (meth) acrylate (trade name Blemmer PE series, Blemmer AE series) manufactured by NOF Corporation, polypropylene grease manufactured by NOF Corporation Mono- (meth) acrylate (trade names Blemmer PP series, Blemmer AP series), polyethylene glycol-polypropylene glycol mono (meth) acrylates (trade names Blemmer PEP series, Blemmer AEP series) manufactured by NOF Corporation, NOF Corporation Poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate (trade name: Blemmer PET series, Blemmer AET series), NOF Corporation poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate (trade name) Blemmer PPT series, Blemmer APT series), NOF Corporation octoxypolyethylene glycol-polypropylene glycol mono (meth) acrylate (trade name Blemmer 50POEP-800 B, Blemmer 50AOEP-800B), Lauroxy polyethylene glycol mono (meth) acrylate (trade name Blemmer PLE series, Blemmer ALE series) manufactured by NOF Corporation, Stearoxy polyethylene glycol mono (meth) acrylate manufactured by NOF Corporation (Blenmer PSE Series, Blenmer ASEP Series), Nonyl Buenoxy Polyethylene Glycol Mono (meth) acrylate Blemmer (trade name ANE Series, Blenmer PNEP Series) manufactured by NOF Corporation, Nonyl manufactured by NOF Corporation Phenoxypolypropylene glycol-polyethylene glycol mono (meth) acrylate (Blenmer PNPE series, Blenmer ANEP series), O- [N- (6-maleimidohexanoyl) aminoethyl] -O '-( -Carboxyethyl) polyethylene glycol 3000 (manufactured by Aldrich), O- [N- (6-maleimidohexanoyl) aminoethyl] -O '-[(3-succinimidyloxy) -3-oxopropyl] polyethylene glycol 3000 (Manufactured by Aldrich) or ε-caprolactone macromonomer, ε-caprolactone-modified hydroxyalkyl vinyl monomer (trade names PlaccelFA-1, Placcel FA-4, Placcel FM-1, Placcel FM-) manufactured by Daicel Chemical Industries, Ltd. 4) and ε-caprolactone-modified hydroxyalkyl vinyl monomers (trade names: TONE M-100, TONE M-201) manufactured by UCC.

  Further, the production method of the macromonomer is not particularly limited. For example, when the vinyl monomer unit portion of the macromonomer is a maleimide monomer unit, the N-polymer is reacted with the maleic anhydride and the amino group-containing polymer. Introduce polymer chains by methods of synthesizing substituted maleimides or by chemical conversion of carboxyl groups or hydroxyl groups of carboxyl group maleimides or hydroxyl group-containing maleimides (reaction with polymers, or vinyl polymerization after introduction of vinyl groups or halogens) You may utilize the method to do. When the vinyl monomer unit portion of the macromonomer is a methacrylic acid unit, that is, a methacryloxy group, and the polymer chain contains polystyrene, as a standard method for the synthesis, for example, Y. The method described in Yamashita, “Chemistry and Industry of Macromonomers”, Hutting un Wepf (1993) can be used, and the vinyl monomer unit portion of the macromonomer is a styrene unit, that is, a styryl group, and the polymer chain portion is polystyrene. In the case of α-benzyl-ω-vinylbenzyl polystyrene, for example, polystyrene and parachloro synthesized by living anionic polymerization using benzyllithium (n-butyllithium / toluene / tetramethylethylenediamine complex) as an initiator. It can be synthesized by reacting with methylstyrene (Tsukahara, Y et al., Polym. J., 1994, 26, 1013 (reference)). Furthermore, when the polymer chain portion of the macromonomer contains polyethylene glycol, for example, end group conversion of ethylene glycol monoether can be mentioned, and as a reference for such a synthesis method, Macromolecules, 1991. , 24, 2348-2354, Polymer Journal, 1985, Vol 17, No. 7, pages 827-839. Further, in the case of a vinyl polymer macromonomer, for example, a radical chain transfer reaction method using a chain transfer agent having a vinyl group at the time of polymerization or a polymerization initiator having an ethylenically unsaturated double bond attached to one end. It is also possible to use a method of performing polymerization using

  In addition to the structural unit (I), the graft-type vinyl polymer having the structural unit (I) can contain other structural units as necessary. By including such other structural units, the solubility of the graft type vinyl polymer in the solvent and the adsorptivity of the graft type vinyl polymer to the carbon nanostructure tend to be improved. Such other structural units are not particularly limited, and are structural units derived from vinyl monomers (hereinafter simply referred to as “other vinyl monomer units”. "Monomer unit" includes all side chains.), For example, unsaturated carboxylic acid ester monomer unit, vinyl cyanide monomer unit, unsaturated carboxylic acid monomer unit, acid anhydride unit thereof or the like Derivative unit, epoxy group-containing vinyl monomer unit, oxazoline group-containing vinyl monomer unit, amino group-containing vinyl monomer unit, amide group-containing vinyl monomer unit, hydroxyl group-containing vinyl monomer unit, olefin monomer unit, halogenated Vinyl monomer unit, carboxylic acid unsaturated ester monomer unit, cationic Nyl monomer units, anionic vinyl monomer units, polyoxyalkylene group-containing vinyl monomer units having a molecular weight of less than 300, silyl group-containing vinyl monomer units, polysiloxane group-containing vinyl monomer units having a molecular weight of less than 300, polycyclic aromatic Preferred examples include group-containing vinyl monomer units, imide group-containing structural units, and the like. One of these other structural units may be included alone, or two or more thereof may be included.

  Among these other structural units, a polycyclic aromatic group-containing vinyl-based monomer unit is preferable from the viewpoint of increasing the adsorptivity to the carbon nanostructure, and the adsorptivity to the carbon nanostructure and the adsorption stability are preferred. From the viewpoint of improving the properties, glass transition temperature and thermal decomposition temperature, an imide group-containing structural unit is preferred. The other structural units include unsaturated carboxylic acid ester monomer units, vinyl cyanide monomer units, aromatic vinyl monomer units from the viewpoint of improving the solubility of the graft vinyl polymer in the solvent. Unsaturated carboxylic acid monomer units, acid anhydride units and derivative units thereof, epoxy group-containing vinyl monomer units, oxazoline group-containing vinyl monomer units, amino group-containing vinyl monomer units, amide group-containing vinyl monomer units, Hydroxyl group-containing vinyl monomer units are preferred. Furthermore, as the other structural unit, from the viewpoint of improving the dispersibility of the carbon nanocomposite when mixed with the resin, the unsaturated carboxylic acid monomer unit, its acid anhydride unit and its derivative unit, epoxy group Preferred are vinyl-containing monomer units and oxazoline group-containing vinyl monomer units.

  The polycyclic aromatic group-containing vinyl monomer unit that can be contained as the other structural unit is not particularly limited, and the aromatic vinyl monomer unit has a polycyclic aromatic group directly or a divalent organic group. Examples thereof include those bonded through a group, and those in which a polycyclic aromatic group is bonded directly or via a divalent organic group to the amide group-containing vinyl monomer unit. :

The thing represented by these is preferable. In the above formula (3), ^{R 1} represents a divalent organic group having 1 to 20 carbon atoms, ^{R 2} represents a monovalent polycyclic aromatic-containing ^group, R 3, ^{R 4} and ^{R 5} each Independently represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms.

R ¹ is preferably a divalent organic group having 1 to 20 carbon atoms, and methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, and one or more hydrogen atoms thereof as other atoms. Substituted substituents are more preferable, and butylene is particularly preferable from the viewpoints of adsorptivity and adsorption stability to the carbon nanostructure and polymerization reactivity at the time of copolymerization with a macromonomer. R ² is preferably naphthyl, naphthalenyl, anthracenyl, pyrenyl, terphenyl, perylene, phenanthrene, tetracene, pentacene, or a substituted product in which one or more hydrogen atoms thereof are substituted with other atoms. Pyrenyl is particularly preferred from the viewpoint of adsorptivity to the structure and adsorption stability. As R ³ and R ⁴ , a hydrogen atom, an alkyl ester group and a carboxyl group are preferable, and a hydrogen atom is particularly preferable. As R ⁵ , a hydrogen atom, a methyl group, an alkyl ester group and a carboxyl group are preferable, and a hydrogen atom and a methyl group are particularly preferable. In the present invention, such polycyclic aromatic group-containing vinyl monomer units may be contained singly or in combination of two or more.

  Moreover, as said imide group containing structural unit, following formula (4):

(In formula (4), R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group, and R ⁸ 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 (5):

(In Formula (5), R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group, and R ¹¹ 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 glutarimide group-containing structural unit represented by:
N-alkenylimide units and derivative units thereof may be mentioned.

  The maleimide monomer used for forming such an imide group-containing structural unit is not particularly limited, and examples thereof include maleimide, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, and N-isopropyl. Maleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide and N N-alkylmaleimides such as n-dodecylmaleimide; N-alkynylmaleimides such as N-acetylenylmaleimide and N-propynylmaleimide; N-benzylmaleimide, N-methylbenzylmaleimide, N-phenylethylmaleimide, N-phenyl N-aralkylmaleimide such as tilmaleimide, N-naphthylmethylmaleimide, N-naphthylethylmaleimide; N-unsubstituted cycloalkylmaleimide represented by N-cyclohexylmaleimide, N-substituted cycloalkyl represented by N-methylcyclohexylmaleimide N-cycloalkylmaleimide such as maleimide; N-phenylmaleimide, N-naphthylmaleimide, N-naphthalenylmaleimide, N-perylenylmaleimide, N-pentacenylmaleimide, N-terphenylmaleimide, N-phenanthre N-unsubstituted arylmaleimides, N-tolylmaleimides and N-xylylmaleimides represented by nilmaleimide, N-tetracenylmaleimide, N-anthracenylmaleimide and N-pyrenylmaleimide Representative alkyl-substituted arylmaleimides, N-amino-substituted arylmaleimides represented by N- (4-aminophenyl) maleimide, N-acetylenylphenylmaleimides and N-alkynyl-substituted aryls represented by N-propynylphenylmaleimide N-aryl substituted arylmaleimide represented by maleimide, N-biphenylmaleimide, N-o-chlorophenylmaleimide, N- (2,4,6-trichlorophenyl) maleimide, N-pentafluorophenylmaleimide and N-tetrafluorophenyl N-arylmaleimides such as N-halogen substituted arylmaleimides typified by maleimide; N-pyridylmaleimide, N-3- (9-alkylcarbazoyl) maleimide and N- (9-acridinyl) maleimi B-maleimides such as N, N′-1,4-phenylene dimaleimide, N, N′-1,3-phenylene dimaleimide and 4,4′-bismaleimide diphenylmethane; N— Halogenated maleimides such as fluoromaleimide, N-chloromaleimide, N-bromomaleimide, and N-iodomaleimide; N-aminomaleimide, N-acetylmaleimide, N-hydroxymaleimide, N-hydroxyphenylmaleimide, p-carboxyphenylmaleimide, N- (2-carboxyethyl) maleimide, 3-maleimidopropionic acid N-hydroxysuccinimide, 6-maleimidohexanoic acid N-hydroxysuccinimide, 3- [2- (2-maleimidoethoxy) ethylcarbamoyl] -2, , 5,5-tetramethyl-1-Pirorijinirokishi, 3 maleimido benzoic acid N- hydroxysuccinimide and the like. These maleimide monomers may be used alone or in combination of two or more. In addition, these maleimide monomers may have a water-soluble substituent such as a sulfone group or a sulfonimide group as necessary, or may be a salt of a maleimide monomer.

  Although there is no restriction | limiting in particular as said glutarimide group used in order to form the said imide group containing structural unit, For example, glutarimide, N-methyl glutarimide, N-ethyl glutarimide, Nn-propyl glutarimide, N-isopropyl glutarimide, Nn-butyl glutarimide, N-isobutyl glutarimide, N-tert-butyl glutarimide, Nn-pentyl glutarimide, Nn-hexyl glutarimide, Nn-heptyl glutar N-alkyl glutarimides such as imide, Nn-octyl glutarimide and Nn-dodecyl glutarimide; N-alkynyl glutarimides such as N-acetylenyl glutarimide and N-propynyl glutarimide; N-benzyl glutarimide and N N-aralkyl glutarimide such as methylbenzyl glutarimide; N-cyclo such as N-unsubstituted cycloalkyl glutarimide represented by N-cyclohexyl glutarimide and N-substituted cycloalkyl glutarimide represented by N-methylcyclohexyl glutarimide Alkyl glutarimide; N-unsubstituted aryl glutarimide, N-tolyl glutarimide, N-phenyl glutarimide, N-naphthyl glutarimide, N-anthracenyl glutarimide and N-pyrenyl glutarimide, N-tolyl glutarimide and N- Alkyl substituted aryl glutarimide represented by xylyl glutarimide, N-amino substituted aryl glutarimide represented by N- (4-aminophenyl) glutarimide, N-acetylenyl phenyl group Taruimido and N- propynyl phenyl glutaric N- alkynyl-substituted aryl glutarimide represented by Tal imides, such as N- aryl glutarimide such N- aryl-substituted aryl glutarimide represented by N- biphenyl glutarimide and the like. These glutarimide groups may be contained singly or in combination of two or more.

  Further, the N-alkenylimide and derivatives thereof used for forming the imide group-containing structural unit are not particularly limited. For example, N-vinylsuccinimide, N-vinylphthalimide, 1-vinylimidazole, and N -Vinylcarbazole and the like. These may be used alone or in combination of two or more.

  In the graft-type vinyl polymer according to the present invention, such imide group-containing constitutional units 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 and an N-alkylmaleimide monomer unit is more preferable, and an N-arylmaleimide monomer unit is particularly preferable. Further, when the graft-type vinyl polymer contains a rigid imide group-containing constitutional unit as another vinyl monomer unit, the rigidity is further strengthened by increasing the content of the imide group-containing constitutional unit. Thus, for example, even if the carbon nanostructure has an average diameter of 30 nm or less, the dispersibility tends to be sufficiently improved.

  Further, the unsaturated carboxylic acid ester monomer used for forming the other vinyl monomer unit is not particularly limited, and examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) (Meth) acrylic alkyl esters such as n-propyl acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, and cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate and (meth) And (meth) acrylic acid halogenated alkyl ester represented by 2-chloroethyl acrylate.

  Further, the vinyl cyanide monomer used for forming the other vinyl monomer units 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 used to form the other vinyl monomer unit is not particularly limited, and examples thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, maleic acid, and fumaric acid. , Itaconic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid, methyl-1, Representative of unsaturated dicarboxylic acids such as 2,3,6-tetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, and methyl-5-norbornene-2,3-dicarboxylic acid, and monomethyl maleate and monoethyl maleate And monoalkyl esters of unsaturated dicarboxylic acids It is. 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 used to form the other vinyl monomer units is not particularly limited, and examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl maleate, and glycidyl fumarate. And glycidyl esters of unsaturated carboxylic acids such as glycidyl itaconate, glycidyl crotonate, glycidyl citraconic acid, glycidyl glutaconate, p-glycidyl styrene, allyl glycidyl ether, and styrene-p-glycidyl ether.

  The oxazoline group-containing vinyl monomer used to form the other vinyl monomer unit is not particularly limited, and examples thereof include 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 5-methyl-2- Vinyl-oxazoline, 2-isopropenyl-oxazoline, 2-acryloyl-oxazoline, 2-styryl-oxazoline, 4,4-dimethyl-2-vinyl-oxazoline, 4,4-dimethyl-2-isopropenyl-oxazoline, etc. Is mentioned.

  The amino group-containing vinyl monomer used to form the other vinyl monomer units is not particularly limited, and examples thereof include vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, Examples include allylamine derivatives represented by allylamine and N-methylallylamine, and aminostyrenes represented by p-aminostyrene.

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

  The hydroxyl group-containing vinyl monomer used to form the other vinyl monomer unit is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate. (Meth) acrylic acid 2,3,4,5,6-pentahydroxyhexyl, (meth) acrylic acid 2,3,4,5-tetrahydroxypentyl (meth) acrylic acid hydroxyalkyl ester, 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 4-dihydroxy-2-butene Such as hydroxy alkene Tsu, and the like. Although there is no restriction | limiting in particular as said polyalkylene oxide group containing vinyl-type monomer, For example, polyethyleneglycol (meth) acrylate etc. are mentioned.

  Examples of the olefin monomers used to form the other vinyl monomer units include ethylene, propylene, butene, isobutene, 2-methyl-1-butene, 2-methyl-2-butene, and 2-ethyl-1-butene. 2-ethyl-2-butene, 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-hexene, 1-methyl-1-heptene, isooctene, 2-methyl-1-octene, isoprene, neoprene, butadiene, dicyclopentadiene, ethylidene norbornene and cyclic olefin Examples of the vinyl halide monomer include vinyl chloride. 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.

  In the present invention, the molecular weight of the structural unit (I) composed of one of the polymer chains and the vinyl monomer unit in the main chain to which the polymer chain is bonded depends on the dispersibility and flow of the carbon nanocomposite. From the viewpoint of improving the property, it is necessary to be 300 or more per one, preferably 400 or more, more preferably 500 or more, further preferably 600 or more, particularly preferably 700 or more, most Preferably it is 800 or more. The upper limit of the molecular weight of the structural unit (I) is not particularly limited, but is preferably 5000000 or less, more preferably from the viewpoint of improving the solubility of the graft type vinyl polymer in a solvent. Is 1000000 or less, more preferably 500000 or less, particularly preferably 300000 or less, and most preferably 250,000 or less.

Moreover, the value measured as follows is employ | adopted for the molecular weight of the structural unit (I) in this invention. That is, first, when the graft-type vinyl polymer is produced by polymerizing a macromonomer (macromonomer method) or addition reaction of a macromonomer to a vinyl polymer (radical addition of a macromonomer to a polymer, etc.) In this case, the number average molecular weight of the macromonomer used is measured by gel permeation chromatography, and the measured value is adopted as the molecular weight of the structural unit (I). As such a gel permeation chromatograph, 2 mg of the macromonomer used was dissolved in 2 ml of chloroform, and a gel permeation chromatograph (Shodex GPC-101, pump: DU-H7000, manufactured by Showa Denko KK, column: K A method of measuring the number average molecular weight of the macromonomer using -805L, manufactured by Showa Denko Co., Ltd. (three in series) is employed. Moreover, in the measurement by such a gel permeation chromatograph, column temperature shall be 40 degreeC, and the detector used the ultraviolet detector (RI-71S, Showa Denko Co., Ltd. product), Furthermore, the number average molecular weight is If the polymer chain in the macromonomer is polyethylene glycol, use the polyethylene glycol standard as the standard reagent. If the polymer chain of the macromonomer polymer chain is other than polyethylene glycol, use the polystyrene standard as the standard reagent. Calculate by conversion. In addition, when a macromonomer does not melt | dissolve in chloroform, it shall measure using hexafluoroisopropanol as a solvent. In addition, when a graft-type vinyl polymer is produced by a polymer addition reaction to a vinyl monomer unit in the polymer (excluding the above-mentioned method of adding a macromonomer), the polymer used Structure obtained by adding the value measured by gel permeation chromatograph to the number average molecular weight and the molecular weight of the vinyl monomer unit determined by the type of monomer used to form the vinyl polymer Adopted as the molecular weight of the unit (I). Furthermore, when a graft-type vinyl polymer is produced by polymer chain growth from a vinyl-type monomer unit in the polymer, the number average molecular weight of the graft-type vinyl polymer is measured by gel permeation chromatography. Then, the ratio of the structural unit (I) formed in the graft-type vinyl polymer is determined by ¹ H-NMR measurement, and the number of the structural units (I) contained in the graft-type vinyl polymer is thereby determined. And the following formula:
[Mn (I)] = [Mn (P)] × ([R] / [N])
(In the formula, Mn (I) represents the number average molecular weight of the structural unit (I), Mn (P) represents the number average molecular weight of the graft-type vinyl polymer, and R represents the portion of the structural unit (I). (N represents the number of structural units (I).)
To calculate the number average molecular weight of the structural unit (I), and adopt the calculated value as the molecular weight of the structural unit (I).

The composition of the graft-type vinyl polymer according to the present invention can be determined from the ratio of the integral values of protons of each unit by performing ¹ H-NMR (400 MHz) measurement at 30 ° C. in deuterated chloroform. it can. For example, when the graft type vinyl polymer contains a dimethylsiloxane group, the proton of the methyl group of the dimethylsiloxane group is observed near 0 ppm, and the proton of the methylene group of —CH ₂ —Si— is 0.50 to Observed in the range of 0.80 ppm. Further, when the graft type vinyl polymer contains a methyl methacrylate unit, the methyl group proton of the methyl ester group is observed in the vicinity of 3.5 ppm. When the graft type vinyl polymer contains a 1-pyrenylpropyl methacrylate unit, the proton of the pyrene group is observed in the range of 7.55 to 8.30 ppm. When the styrene unit is contained in the graft type vinyl polymer, protons are observed in the chemical shift range of 7.10 to 7.45 ppm. When the N-methylmaleimide unit is contained in the graft type vinyl polymer, the proton of the methyl group is observed around 3.0 ppm. When the graft-type vinyl polymer contains an N-phenylmaleimide unit, the proton at the meta position of the phenyl group is observed in the range of 7.46 to 7.50 ppm. When the graft type vinyl polymer contains a methyl methacrylate unit, the proton of the methyl group of the methyl ester is observed at about 3.5 ppm. When the graft type vinyl polymer contains a methoxypolyethylene glycol methacrylate unit, the ethylene proton of polyethylene glycol is in the range of 3.64 to 3.67 ppm, and the proton of the terminal methyl group is 3.8 to 3.9 ppm. The methylene proton adjacent to the ester of the methacryloxy group is observed in the range of 4.2 to 4.4 ppm. When the graft type vinyl polymer is not dissolved in deuterated chloroform, the composition is determined by measuring using deuterated hexafluoroisopropanol as the deuterated solvent.

  The lower limit of the content of the structural unit (I) of the graft-type vinyl polymer is not particularly limited, but is preferably 0.01 mol% or more, and more preferably from the viewpoint of improving dispersibility. 05 mol% or more, more preferably 0.1 mol% or more, particularly preferably 0.5 mol% or more, and most preferably 1 mol% or more. The upper limit of the content of the structural unit (I) is not particularly limited and may be 100 mol%. However, from the viewpoint of increasing the adsorptivity of the graft-type vinyl polymer to the carbon nanostructure, it is 99.9 mol% or less. Preferably, it is 99 mol% or less, more preferably 90 mol% or less, particularly preferably 80 mol% or less, and most preferably 70 mol% or less.

  Further, the number average molecular weight of the graft-type vinyl polymer is not particularly limited, but from the viewpoint of improving the binding stability by improving the amount of adsorption to the surface of the carbon nanostructure and suppressing reaggregation of the carbon nanostructure by steric repulsion. It is preferably 3000 or more, more preferably 5000 or more, still more preferably 7000 or more, particularly preferably 10,000 or more, and most preferably 20000 or more. The upper limit of the number average molecular weight of such a graft-type vinyl polymer is not particularly limited, but is preferably 10000000 or less, more preferably 5000000 or less, and further preferably 1000000 from the viewpoint of fluidity. Or less, particularly preferably 500,000 or less, and most preferably 300,000 or less. Further, the number average molecular weight of the graft-type vinyl polymer determined by the weight average molecular weight / number average molecular weight is not particularly limited, but the lower limit thereof may be as close as 1 to the value.

  Further, the method for producing such a graft-type vinyl polymer is not particularly limited, and a known method can be appropriately employed. For example, a method using vinyl polymerization of a macromonomer as described above (macromonomer Method), a method in which a polymer compound is added to the side chain of the vinyl polymer to introduce a polymer chain into the side chain of the vinyl polymer, and a method in which the polymer chain is grown on the side chain of the vinyl polymer And a method of grafting a macromonomer to a vinyl polymer using a radical initiator or the like. Among such methods for producing a graft-type vinyl polymer, a polymer chain having a clear molecular weight can be easily and reliably introduced, and therefore, it is preferably produced by vinyl polymerization of a macromonomer. In addition, there is no restriction | limiting in particular as a transmission medium of the reaction chain which can be used when manufacturing the said graft-type vinyl polymer by carrying out vinyl polymerization of the monomer component containing the said macromonomer, A radical and ion are mentioned. In the case of adopting a method of vinyl polymerizing a monomer component containing the macromonomer, a polymerization reaction that can be used is not particularly limited, and a known polymerization reaction can be appropriately employed, but a narrow molecular weight distribution can be achieved. From the viewpoint, it is preferable to employ living polymerization. Among various polymerization reactions, it is preferable to use radical polymerization or living radical polymerization, and from the viewpoint of industrial properties, it is particularly preferable to use radical polymerization. Also, there is no particular limitation on the polymerization method, and for example, a known polymerization method by radical polymerization can be used, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization and a combination of these polymerization methods are suitably employed. Either a batch type or a continuous type can be suitably employed. Further, conventionally known polymerization initiators, chain transfer agents, catalysts, dispersion stabilizers, solvents and the like can be suitably used. The sequence of the graft-type vinyl polymer is not particularly limited, and examples thereof include at least one of random, block, alternating, dendritic such as graft, hyperbranch, and branched such as star polymer. Among these, from the viewpoint of dispersibility, at least one of random, block, alternating, and graft is preferable, and random is more preferable.

(Carbon nanocomposite)
The carbon nanocomposite of the present invention comprises the carbon nanostructure and a graft-type vinyl polymer adsorbed on the carbon nanostructure. The “adsorption” referred to here may be non-covalent bond, covalent bond, or a combination thereof. In addition, as such a carbon nanocomposite, the surface structure of the carbon nanostructure is non-destructive (no defect is formed), and the carbon nanostructure has inherent thermal conductivity and electrical conductivity. From the standpoint of effectively exhibiting excellent properties such as property and mechanical properties, it is preferable that at least the graft-type vinyl polymer includes a non-covalent bond adsorbed to the carbon nanostructure. .

  In the present invention, “adsorption by non-covalent bond” means adsorption by an interaction other than the covalent bond generated between the graft-type vinyl polymer and the carbon nanostructure. In addition, non-covalent adsorption of the graft-type vinyl polymer to the carbon nanostructure can be performed by, for example, combining a polycyclic aromatic-containing unit such as an anthracenyl group or a pyrenyl group or an imide group-containing structural unit with a graft-type vinyl-based polymer. Carbon nanostructures and π-π interactions and / or van der Waals forces with the graphene structure of carbon nanostructures by introducing them into the coalescence, and the hydrophobic part of the graft-type vinyl polymer in water And the like utilizing the affinity with the body.

  On the other hand, the above-mentioned “adsorption by covalent bond” is not particularly limited. For example, a carboxyl group or the like is introduced into the carbon nanostructure by acid treatment or the like, and this is used as a reaction starting point to react the graft-type vinyl polymer. Introducing a graft type vinyl polymer into a carbon nanostructure by deriving from the reaction starting point to a halide which is the starting point of a vinyl group or a living radical initiator and polymerizing by radical polymerization or living radical polymerization, etc. In addition to the method of graft introduction, a graft-type vinyl polymer can also be directly introduced by radical addition during polymerization, solution processing, or melt processing.

  Moreover, it is preferable that the carbon nanocomposite of the present invention remains in an adsorbed state even when the dispersion washing operation of dispersion / washing filtration with a good solvent of the vinyl polymer is repeated a plurality of times.

  Furthermore, in the carbon nanocomposite of the present invention, the amount of the graft vinyl polymer adsorbed on the carbon nanostructure is not particularly limited, but the lower limit is 100% by mass with respect to the carbon nanostructure. From the viewpoint of dispersibility and heat resistance, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and particularly preferably 2.% by mass. It is 0 mass% or more, Most preferably, it is 3.0 mass% or more. On the other hand, the upper limit of the adsorption amount is not particularly limited, but is preferably 500% by mass or less, more preferably 200% by mass or less with respect to 100% by mass of the carbon nanostructure. From the viewpoint of fluidity (molding processability) when used, and in the case of applications where thermal conductivity is required, from the viewpoint of increasing thermal conductivity, it is 100% by mass or less with respect to 100% by mass of the carbon nanostructure. More preferably, it is 95 mass% or less, Most preferably, it is 90 mass% or less.

  The following method is adopted as a method for measuring the adsorption amount of the graft-type vinyl polymer to the carbon nanostructure. That is, first, the carbon nanostructure and the graft-type vinyl polymer in the carbon nanocomposite are respectively taken out, vacuum-dried to remove volatile components such as residual solvent, and then a thermogravimetric analyzer for each. (Thermoplus TG8120 manufactured by Rigaku Denki Co., Ltd.) was used to perform thermogravimetric analysis (TGA) by heating from room temperature to 500 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere. The thermal decomposition start temperature and thermal decomposition end temperature of the polymer and the graft-type vinyl polymer are 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 mass reduction has not ended at 500 ° C. The temperature is further increased until the mass reduction is completed, and the thermal decomposition end temperature is measured. Next, with respect to the carbon nanocomposite, a thermogravimetric analyzer (“Thermo plus TG8120” manufactured by Rigaku Denki Co., Ltd.) was used to increase the temperature from room temperature to 500 ° C. at a temperature rising rate of 20 ° C./min. When the thermal decomposition end temperature of the graft-type vinyl polymer contained in the body is 500 ° C. or higher, the thermogravimetric analysis is performed. Then, after measuring the amount of carbon nanocomposite derived from the grafted vinyl polymer as the amount of adsorption of the grafted vinyl polymer onto the carbon nanocomposite, based on this measured value Then, an amount (parts by mass) with respect to 100 parts by mass of the carbon nanostructure is calculated, and the obtained value is taken as an adsorption amount.

  Further, the lower limit of the absorbance of the dispersion liquid when the carbon nanocomposite of the present invention is dispersed in chloroform is not particularly limited, but the absorbance value at a wavelength of 650 nm is preferably 0.3 or more, more preferably It is 0.6 or more, more preferably 0.8 or more, particularly preferably 0.9 or more, and most preferably 1.0 or more. Further, the absorbance after redispersion of the carbon nanocomposite of the present invention is not particularly limited, but the absorbance value at a wavelength of 650 nm is preferably 0.3 or more, more preferably 0.5 or more, More preferably, it is 0.7 or more, particularly preferably 0.8 or more, and most preferably 0.9 or more.

  As a method for measuring the absorbance of the dispersion, the following method is employed. That is, first, 2 mg of the graft-type vinyl polymer and 2 mg of the carbon nanostructure were weighed, put into 20 ml of chloroform, and subjected to ultrasonic treatment for 1 hour (desktop ultrasonic cleaner BRANSONIC B- manufactured by BRANSON). 220, the chloroform dispersion of the carbon nanocomposite immediately after being manufactured at an oscillation frequency of 45 kHz) is subjected to centrifugation (1 hour at a relative centrifugal acceleration of 1000 G). Next, a UV-visible light spectrum is measured for the supernatant thus obtained. The measured absorbance value at 650 nm is defined as the absorbance. Moreover, the following method is employ | adopted as a measuring method of the light absorbency after the said re-dispersion. That is, first, 2 mg of the carbon nanocomposite is weighed and put into 20 ml of chloroform, and then subjected to ultrasonic treatment for 15 minutes (BRANSON Benchsonic BRANSONIC B-220, oscillation frequency 45 kHz). Subsequently, the chloroform dispersion of the carbon nanocomposite thus obtained is centrifuged (relative centrifugal acceleration at 1000 G for 1 hour). Next, a UV-visible light spectrum is measured for the obtained supernatant. The measured absorbance value at 650 nm is taken as the absorbance after the redispersion.

  In the present invention, the fluidity (torque ratio) of the resin composition comprising the carbon nanocomposite and the polyphenylene sulfide resin is not particularly limited, but is preferably in the range of 1-1.16. More preferably, it is in the range of 10. As a method for measuring such fluidity, the following method is adopted. That is, first, 7 cc of a carbon nanocomposite and a polyphenylene sulfide resin (manufactured by Aldrich, polyphenylene sulfide, melt viscosity 275 poise (310 ° C.)) of 100% by volume is prepared. Here, the compounding amount of the carbon nanocomposite takes into account the amount of adsorption of the graft-type vinyl polymer in the carbon nanostructure, and the capacity of the carbon nanostructure contained in 100% by volume of the mixture. The amount is determined so as to be 1% by volume, and the remainder excluding the carbon nanocomposite is defined as polyphenylene sulfide resin. Next, the mixture is put into a precision same-direction biaxial kneader (Microrheology Compounder HAAKE-MiniLab, manufactured by Thermo Fisher Scientific Co., Ltd.), under a nitrogen atmosphere at a temperature of 290 ° C. and a screw rotation speed of 300 rpm. The torque value (N · m) after melt kneading for 10 minutes is measured while circulating the molten resin in the kneader. The torque value is divided by the torque value when 100% by volume of the polyphenylene sulfide resin is evaluated under the above conditions. The torque ratio to the polyphenylene sulfide resin single system thus obtained is defined as the fluidity value of the carbon nanocomposite. In addition, the closer the torque ratio is to 1, the smaller the increase in melt viscosity due to the inclusion of the carbon nanostructure, and the better the fluidity.

  Further, in the carbon nanocomposite of the present invention, by changing the type of the structural unit (I) in the graft-type vinyl polymer, it is possible to easily impart functionalities such as imparting electrical properties, imparting frictional properties, and imparting reactivity. Can do. For example, when a polysiloxane macromonomer is included, electric resistance (surface resistivity) can be improved. In the present invention, since the graft type vinyl polymer is adsorbed on the carbon nanostructure, the polymer chain (polymer graft portion) of the graft type vinyl polymer causes the carbon nanocomposite. The affinity to the solvent and resin is improved, and the presence of the polymer chain increases the steric repulsion between the carbon nanostructures, thereby improving dispersibility and fluidity.

  Such a carbon nanocomposite of the present invention can be developed for a wide variety of uses that make use of the original characteristics of the carbon nanostructure. For example, when added to a resin, ceramics, metal, etc., the mechanical properties are Wide range of applications such as applications that require electromagnetic shielding, applications that require heat resistance, applications that require dimensionality (decrease in thermal expansion coefficient), applications that require thermal conductivity, and applications that require electrical conductivity In particular, it can be suitably used for applications such as a resin molded body, a resin sheet, and a resin film that require improvement in thermal conductivity by improving dispersibility.

[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 graft-type vinyl polymer to the carbon nanostructure. A method is mentioned.
(I) A method of mixing the carbon nanostructure and the graft-type vinyl polymer in a solvent.
(Ii) A method of mixing the carbon nanostructure and the graft-type vinyl polymer without using a solvent.
(Iii) A method of mixing the carbon nanostructure and the melted graft-type vinyl polymer.
(Iv) A method in which the carbon nanostructure and the graft-type vinyl polymer are mixed without using a solvent, and then the graft-type vinyl polymer is melted.
(V) The carbon nanostructure and the silyl group-containing polymer or the hydrophilic group-containing polymer are mixed in a solvent as necessary to adsorb the polymer to the carbon nanostructure. Thereafter, alkoxysilane is added thereto, and the polymer on the carbon nanostructure and the alkoxysilane are subjected to dehydration polycondensation to form a graft-type vinyl polymer on the carbon nanostructure.

  Such a method for producing the carbon nanocomposite may be carried out alone or in combination of two or more. Further, in such a production method, at the time of the mixing or after the polymerization, at least a treatment such as ultrasonic treatment, vibration, stirring, application of an external field (for example, magnetic field application, electric field application, etc.), melt kneading, or the like. It is preferable to apply one, and it is more 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 case of performing the melt-kneading process, the carbon nanostructure, the graft-type vinyl polymer, and if necessary, the resin and / or additive in pellets, powders or strips, respectively. Then, after uniformly mixing by a stirrer, a drive lender or hand mixing, it can be melt-kneaded using an extruder, a rubber roll machine, a Banbury mixer or the like having a uniaxial or multiaxial vent.

  Further, among the methods for producing such a carbon nanocomposite, from the viewpoint of improving the adsorption amount of the graft-type vinyl polymer to the carbon nanostructure, the production method of (i), ie, the above The carbon nanocomposite of the present invention to obtain a carbon nanocomposite by mixing the carbon nanostructure and the grafted vinyl polymer in a solvent to adsorb the grafted vinyl polymer to the carbon nanostructure. It is particularly preferable to adopt a method for producing a body, and it is most preferable to perform ultrasonic treatment during mixing using such a production method.

  Further, in the method for producing such a carbon nanostructure, there is no particular limitation on the method of mixing the carbon nanostructure and the graft-type vinyl polymer. And may be mixed. The order is not particularly limited, and the graft vinyl polymer may be added to the carbon nanostructure, or the carbon nanostructure may be added to the graft vinyl polymer. Alternatively, the carbon nanostructure and the polymer according to the present invention may be added simultaneously or may be added alternately. In the method for producing a carbon nanocomposite of the present invention, another resin or additive may be added when the carbon nanostructure and the graft-type 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.

  Further, the mixing ratio of the carbon nanostructure and the graft vinyl polymer in the mixing is not particularly limited, but the amount of the graft vinyl polymer added is 100 parts by mass of the carbon nanostructure. On the other hand, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1.0 parts by mass or more, and 2.0 parts by mass or more. Particularly preferred is 3.0 parts by mass or more. When the added amount of the graft type vinyl polymer is less than the lower limit, the dispersibility and heat resistance of the carbon nanocomposite tend to decrease. In addition, the upper limit of the amount of the graft-type 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. 100 parts by mass or less is more preferred, 95 parts by mass or less is particularly preferred, from the viewpoint of improving the thermal conductivity in applications where flowability (molding processability) of the resin composition containing the body and thermal conductivity are required. Most preferred is less than or equal to parts by weight.

  Moreover, there is no restriction | limiting in particular as a solvent used in the manufacturing method as described in 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 , Tetramethylene glycol, tetraethylene glycol, hexamethylene glycol, polyethylene Glycol, 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. When the graft vinyl polymer according to the present invention has a polymer chain containing a siloxane structure, the graft vinyl polymer can be obtained by using a nonpolar solvent such as cyclohexane or hexane among these solvents. The polymer tends to dissolve efficiently, whereby the carbon nanocomposite of the present invention tends to disperse well.

  In addition, in the production method (i) or (v) in which the carbon nanocomposite is produced in a solvent, the lower limit of the addition amount of the carbon nanostructure is not particularly limited, but is 0.1% with respect to 100 parts by mass of the solvent. 0001 parts by mass is preferable, 0.001 parts by mass is more preferable, 0.005 parts by mass is further preferable, and 0.1 parts by mass is particularly 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 nanostructure is lowered and aggregation easily occurs, the amount of adsorption of the graft-type 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 recovering a portion (for example, a supernatant) in which there is no aggregation or precipitation in the dispersion.

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

  Further, when the graft-type vinyl polymer is adsorbed to the carbon nanostructure by the production method of (i) or (v), the mixed dispersion is filtered as necessary to remove 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 polymer concerning this invention.

[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 such a carbon nanocomposite is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass or more with respect to 100% by mass of the resin composition. Is more preferable, 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 0.1 to 200 g / (10 minutes, load 2.16 kg) in terms of MFR at the molding temperature.

  The relationship between the properties of the obtained resin composition and the content of the carbon nanocomposite varies depending on the type of carbon nanocomposite, and cannot be generally stated. When the composite is added in an amount of 0.1 to 5% by weight (preferably 0.1 to 3% by weight) with respect to 100 parts by weight of the resin, the thermal conductivity of the resulting resin composition (resin matrix) is preferably 1. .1 times or more, more preferably 1.2 times or more, still more preferably 1.3 times or more, particularly preferably 1.4 times or more, and most preferably 1.5 times or more. That is, by containing an appropriate amount of the carbon nanocomposite of the present invention, the thermal conductivity of the resin composition (resin matrix) itself of the present invention tends to be efficiently improved. And in the case where the thermal conductivity of the resin composition itself is improved by 1.5 times by the addition of the carbon nanocomposite, the case where a thermal conductive filler such as alumina or boron nitride is further added to the resin composition In addition, the thermal conductivity value is about 1.5 times that of the resin with no carbon nanocomposite added, compared to the thermal conductivity when the thermal conductive filler is added. An effect can be expressed.

  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 -Aromatic vinyl resins such as styrene resin, styrene-butadiene-styrene block copolymer and styrene-ethylene-butylene-styrene block copolymer, polymethyl methacrylate, polyacrylic acid , Polymethacrylic acid, copolymers thereof, acrylic resins such as acrylic rubber, vinyl cyanide resins such as polyacrylonitrile, acrylonitrile-methyl acrylate resin, and acrylonitrile-butadiene resin, imide group-containing vinyl resins, polyethylene , Polypropylene, polyneoprene, polyisoprene, polybutene, polyisobutene, hydrogenated polyisobutene, polybutadiene, hydrogenated polybutadiene, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene copolymer Polyolefin resin, 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, polyarylate, liquid crystal polyester, polyphenylene ether, polyarylene sulfide, Polysulfone, polyethersulfone, polyoxymethylene, polytetrafluoroethylene, fluorinated ethylene propylene, polychlorotrifluoroethylene, fluororesin represented by polyvinylidene fluoride and polyvinyl fluoride, polylactic acid, polyvinyl chloride, heat Plastic polyimide, thermoplastic polyamideimide, polyetherimide, polyetheretherketone, polyetherketone Examples thereof include thermoplastic resins such as ketones and polyether amides. These resins may be used alone or in combination of two or more. In addition, among the above resins, from the viewpoint of further improving the thermal conductivity and the insulating property when aiming to achieve both the thermal conductivity and the insulating property, a polyolefin-based resin and / or an epoxy-modified polyolefin resin are used. It is particularly preferable to use one or more of other resins such as polyphenylene sulfide in combination, or to use one or more of polyamide resin and one or more other resins in combination.

  Furthermore, 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, zinc oxide, magnesium oxide, and soft magnetic ferrite. These heat conductive fillers may be used alone or in combination of two or more. The thermal conductivity of the thermally conductive filler is not particularly limited, but is preferably 0.5 W / mK or more, more preferably 1.0 W / mK or more, still more preferably 10 W / mK or more, and particularly preferably 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.

  Moreover, 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.

  The resin composition of the present invention can also be produced by adsorbing a graft-type vinyl polymer to a carbon nanostructure in a resin. 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. In addition, when the carbon nanocomposite is aggregated, it can be rapidly dispersed in the resin even if it is used as it is, but it is preferable that the carbon nanocomposite is crushed in advance by pulverization or freeze pulverization.

  In the present invention, it is preferable that at least a part of the resin and / or various additives are preliminarily mixed with the carbon nanocomposite in advance in order to improve the dispersibility of the carbon nanocomposite. 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. As the method, at least a part of the resin and / or various additives are added to the dispersion containing the carbon nanocomposite of the present invention and mixed, A method in which at least a part and / or various additives are dissolved and / or dispersed (without dissolution) in a solvent, and the carbon nanocomposite of the present invention is added thereto and mixed 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, molding using a magnetic field, electric field) A resin composite material can be obtained by performing a conventionally known molding process such as molding using

  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. The present invention is not limited to the following examples. First, methods for measuring various physical properties of the graft-type vinyl polymer and the carbon nanocomposite will be described.

[Measurement method for characteristic values]
(1) Method for measuring molecular weight of structural unit (I) in graft-type vinyl polymer The molecular weight of structural unit (I) in graft-type vinyl polymer obtained in each of the preparation examples is as follows. The method was employed for measurement. In each preparation example, a graft-type vinyl polymer was produced using a macromonomer.

  First, 2 mg of macromonomer used in each preparation example was dissolved in 2 ml of chloroform, and gel permeation chromatograph (Shodex GPC-101, pump: DU-H7000, manufactured by Showa Denko KK, column: K-805L, Showa Denko) The number average molecular weight of the macromonomer was measured using a product manufactured by (Co., Ltd.). In addition, the column temperature in the case of this measurement was 40 degreeC, and the ultraviolet detector (RI-71S, Showa Denko Co., Ltd. product) was used for the detector. The number average molecular weight is determined by using polyethylene glycol standard as the standard reagent when the polymer chain of the macromonomer polymer chain part is polyethylene glycol, and the polymer chain of the macromonomer polymer chain part other than polyethylene glycol. In this case, it was calculated by using polystyrene standard as a standard reagent. And the number average molecular weight of each macromonomer measured in this way was made into the molecular weight of structural unit (I) as it was.

(2) Measuring method of number average molecular weight of graft type vinyl polymer The molecular weight of the graft type vinyl polymer obtained in each of the preparation examples was measured as follows. That is, first, 2 mg of graft-type vinyl polymer was dissolved in 2 ml of chloroform, and gel permeation chromatograph (Shodex GPC-101, pump: DU-H7000, manufactured by Showa Denko KK, column: K-805L, Showa Denko) The number average molecular weight of the graft-type vinyl polymer was measured using a product manufactured by (Co., Ltd., three in series), and the measured value was taken as the molecular weight of the graft-type vinyl polymer. The column temperature was 40 ° C., and an ultraviolet detector (RI-71S, Showa Denko KK) was used as the detector. Further, such a number average molecular weight was obtained by conversion using a polystyrene standard as a standard reagent.

(3) Composition analysis method of graft type vinyl polymer The composition of the graft type vinyl polymer was measured as follows. That is, first, the graft-type vinyl polymer obtained in each preparation example was dissolved in deuterated chloroform, and ¹ H-NMR measurement was carried out under conditions of 30 ° C. and 400 MHz. Then, from the measurement results, the integral value of the protons of each structural unit is determined according to the chemical shift shown in Table 1 below, and the molar ratio of each structural unit in each graft-type vinyl polymer is determined from these ratios. Converted to mass ratio.

(4) Method of measuring the adsorption amount of the graft-type vinyl polymer First, the carbon nanostructure and the graft-type vinyl polymer were vacuum-dried to remove volatile components such as residual solvent, and then thermogravimetric analysis was 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 graft type 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.

  Next, for each carbon nanocomposite obtained in each example, a thermogravimetric analyzer (“Thermo plus TG8120” manufactured by Rigaku Denki Co., Ltd.) was used at room temperature at a heating rate of 20 ° C./min in a nitrogen atmosphere. To 500 ° C. (when the thermal decomposition end temperature of the graft-type vinyl polymer contained in the carbon nanocomposite is 500 ° C. or higher, the thermogravimetric analysis) was performed. Of the mass reduction of the carbon nanocomposite, the amount derived from the grafted vinyl polymer is defined as the amount of the grafted vinyl polymer adsorbed to the carbon nanocomposite, and the amount with respect to 100 parts by mass of the carbon nanostructure [parts by mass ].

(5) Dispersibility The dispersibility of the carbon nanocomposite obtained in each example was evaluated as follows. That is, using the graft-type vinyl polymer and carbon nanostructure (a-1) used in each example, the same method as the method for measuring the absorbance of the dispersion liquid described above was adopted, and UV-visible light was used. The spectrum was measured and the dispersibility was evaluated from the absorbance at 650 nm. In addition, it is shown that the larger the absorbance value, the more carbon nanostructures are dispersed in the solvent even after centrifugation, and the more excellent the dispersibility.

(6) Redispersibility The redispersibility of the carbon nanocomposites obtained in each example was evaluated as follows. That is, the carbon nanocomposites (e-1) to (e-5) obtained in Examples 6 to 10 and the carbon nanocomposites (f-1) to (f-3) obtained in Comparative Examples 5 to 7 ), The UV-visible light spectrum was measured using the above-described method for measuring absorbance after redispersion, and the dispersibility was evaluated from the absorbance at 650 nm. In addition, it is shown that the larger the absorbance value, the more carbon nanostructures are dispersed in the solvent even after centrifugation, and the more excellent the dispersibility.

(7) Fluidity The fluidity of the carbon nanocomposites obtained in each example was evaluated as follows. That is, first, the carbon nanocomposites (e-1) to (e-6) obtained in Examples 7 to 12 and the carbon nanocomposites (f-1) to (f) obtained in Comparative Examples 5 to 7 -3) and one of the carbon nanostructures (a-1) and a polyphenylene sulfide resin (manufactured by Aldrich, polyphenylene sulfide, melt viscosity 275 poise (310 ° C.)) of 7 cc Each was produced. Here, the amount of the carbon nanocomposite is determined based on the amount of the carbon nanostructure contained in 100% by volume of the mixture after taking into consideration the amount of the graft vinyl polymer adsorbed to the carbon nanostructure. The volume was determined so as to be 1% by volume, and the remainder excluding the carbon nanocomposite was defined as polyphenylene sulfide resin. Next, each obtained mixture was put into a precision same-direction biaxial kneader (Microrheology Compounder HAAKE-MiniLab, manufactured by Thermo Fisher Scientific Co., Ltd.), and the temperature was 290 ° C. and screw rotation in a nitrogen atmosphere. The torque value (N · m) after performing melt-kneading for 10 minutes while circulating the molten resin in the kneader at several 300 rpm was measured. Then, the torque value obtained was divided by the torque value when 100% by volume of the polyphenylene sulfide resin was evaluated under the above conditions to obtain the torque ratio with respect to the polyphenylene sulfide resin alone system (torque ratio is close to 1). Thus, it can be said that the increase in melt viscosity due to the inclusion of the carbon nanostructure is small and the fluidity is excellent).

(8) Thermal conductivity The thermal conductivity of the carbon nanocomposite obtained in each example was evaluated as follows. That is, first, the same method as that used when evaluating the above-described fluidity is employed to produce each mixture, and each mixture is further subjected to the same conditions as those employed when evaluating the above-described fluidity. Under the conditions, each was melt kneaded for 10 minutes. The gut-like samples thus obtained were each vacuum-dried at 130 ° C. for 6 hours and then press-molded at a molding temperature of 300 ° C. to obtain molded products having a thickness of 2 mm. And each 25 mm x 25 mm x 2 mm sample was cut out from each molded article, and the thermal conductivity of the carbon nanocomposite obtained in each example was measured. In addition, the measurement temperature was 40 degreeC (up-and-down temperature difference 24 degreeC) using the regular method thermal conductivity measuring apparatus GH-1 by ULVAC-RIKO for the measurement of such heat conductivity. Further, in such measurement, the thermal conductivity in the thickness direction was measured.

[Materials used in Preparation Examples and Examples]
As the carbon nanostructure, vinyl monomer, polymer (d-3) and compound (d-4) used in Preparation Examples and Examples described later, those described below were used. In addition, the number average molecular weight of the monomer shown below shows the value obtained by measuring by the method as described in said (1). In addition, the G / D value of the carbon nanostructure is measured at an excitation laser wavelength of 532 nm using a laser Raman spectroscopy system (“NRS-3300” manufactured by JASCO Corporation), and is observed in the vicinity of about 1585 cm ^−1. And the peak intensity of the Raman spectrum of the D band observed in the vicinity of about 1350 cm ⁻¹ .
Carbon nanostructure (a-1):
Multi-walled carbon nanotube (manufactured by Nanocarbon Technologies, MWNT-7), diameter distribution 40 to 90 nm, aspect ratio 100 or more, G / D value: 8.0, true specific gravity: 2.1
Carbon nanostructure (a-2):
Multi-walled carbon nanotube (CNT, manufactured by CNT, diameter distribution: 10 to 40 nm, aspect ratio: 100 or more, G / D value: 0.9, true specific gravity: 2.1
Macromonomer (b-1):
α-Butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane (manufactured by Chisso Corporation, Silaplane FM-0711, number average molecular weight 1000)
Macromonomer (b-2):
AS-6 manufactured by Toagosei Co., Ltd. (the radically polymerizable group is a methacryloxy group and the polymer chain of the polymer chain portion is polystyrene, number average molecular weight 6000)
Macromonomer (b-3):
Methoxypolyethyleneglycol monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester M230G (the radically polymerizable group is a methacryloxy group and the polymer chain of the polymer chain is polyethylene glycol, number average molecular weight 1100)
Macromonomer (b-4):
Methoxypolyethylene glycol monomethacrylate (manufactured by Aldrich, number average molecular weight 500)
Macromonomer (b-5):
Methoxy polyethylene glycol monomethacrylate (manufactured by Aldrich, number average molecular weight 300)
Polymer (d-3):
Poly (3-decylthiophene) (Aldrich, number average molecular weight 30000)
Compound (d-4):
Sodium dodecyl sulfate (Wako Pure Chemical Industries, Ltd.)

(Preparation Example 1)
Preparation of 1-pyrenylbutyl methacrylate:
5.0 g of 1-pyrenebutanol and 3.68 g of triethylamine were dissolved in 100 ml of tetrahydrofuran, and 1.90 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-pyrenylbutyl methacrylate.

(Preparation Example 2)
Preparation of graft type vinyl polymer (c-1):
In a reaction vessel equipped with a stirrer, 100 parts by weight of a mixture comprising 45 mol% of macromonomer (b-1), 25 mol% of 1-pyrenylbutyl methacrylate and 30 mol% of methyl methacrylate, and 2,2'-azo A solution was obtained by dissolving 1.0 part by weight of bisisobutyronitrile in 250 parts by weight of anhydrous toluene. Next, the temperature of the solution was increased to 75 ° C. while stirring at 200 rpm under a nitrogen stream, and the monomer was polymerized by maintaining the solution at 75 ° C. for 4 hours. Next, after cooling the temperature of the solution after polymerizing the monomer to 30 ° C., the solution is poured into 5 equivalents of methanol, purified by reprecipitation, and the solvent is completely distilled off by drying to graft. Type vinyl polymer (c-1) was obtained.

When the composition of such a graft-type vinyl polymer (c-1) was determined by ¹ H-NMR, the graft-type vinyl polymer (c-1) was a structural unit derived from the macromonomer (b-1). (Macromonomer (b-1) unit: equivalent to structural unit (I)) 50 mol%, 1-pyrenylbutyl methacrylate unit 24 mol%, and methyl methacrylate unit 26 mol% Was confirmed. Therefore, the graft-type vinyl polymer (c-1) is represented by the following formula (6):

(In the formula, m ¹ represents the number of repeating units in parentheses.)
(A: b: c = 24: 50: 26 [mol%]). Moreover, the number average molecular weight measured using the gel permeation chromatograph of the graft type vinyl polymer (c-1) was 26400, and the molecular weight distribution was 1.94. In addition, since the polymer (c-1) obtained in this way contained a polysiloxane side chain having a very low polarity in the structure, it was dissolved in alkane and cycloalkane in addition to chloroform and tetrahydrofuran.

(Preparation Example 3)
Preparation of graft type vinyl polymer (c-2):
In a reaction vessel equipped with a stirrer, 100 parts by weight of a mixture comprising 10 mol% of macromonomer (b-1), 70 mol% of N-phenylmaleimide and 20 mol% of methyl methacrylate, and 2,2′-azobis A solution was obtained by dissolving 0.4 parts by weight of isobutyronitrile in 500 parts by weight of anhydrous toluene. Next, the temperature of the solution was increased to 75 ° C. while stirring at 200 rpm under a nitrogen stream, and the monomer was polymerized by maintaining the solution at 75 ° C. for 4 hours. Next, after cooling the temperature of the solution after polymerizing the monomer to 30 ° C., the solution is diluted with chloroform, poured into an excessive amount of methanol, purified by reprecipitation, and the solvent is completely removed by drying. Distilled off to obtain a graft-type vinyl polymer (c-2).

When the composition of such a graft-type vinyl polymer (c-2) was determined by ¹ H-NMR, the graft-type vinyl polymer (c-2) was a macromonomer (b-1) unit (structural unit ( Equivalent to I)), 8 mol%, 73 mol% of N-phenylmaleimide units, and 19 mol% of methyl methacrylate units. Therefore, the graft type vinyl polymer (c-2) is represented by the following formula (7):

(In the formula, m ¹ represents the number of repeating units in parentheses.)
(D: b: c = 73: 8: 19 [mol%]). Moreover, the number average molecular weight measured using the gel permeation chromatograph of the graft type vinyl polymer (c-2) was 11100, and the molecular weight distribution was 3.30.

(Preparation Example 4)
Preparation of graft type vinyl polymer (c-3):
In a reaction vessel equipped with a stirrer, 100 parts by weight of a mixture comprising 2 mol% of macromonomer (b-2), 80 mol% of N-phenylmaleimide and 18 mol% of methyl methacrylate, and 2,2′-azobisiso A solution was obtained by dissolving 0.3 part by weight of butyronitrile in 500 parts by weight of anhydrous toluene. Next, the temperature of the solution was increased to 75 ° C. while stirring at 200 rpm under a nitrogen stream, and the monomer was polymerized by maintaining the solution at 75 ° C. for 4 hours. Next, after cooling the temperature of the solution after polymerizing the monomer to 30 ° C., the solution is poured into 5 equivalents of methanol, purified by reprecipitation, and the solvent is completely distilled off by drying. Type vinyl polymer (c-3) was obtained.

When the composition of such a graft-type vinyl polymer (c-3) was determined by ¹ H-NMR, the graft-type vinyl polymer (c-3) was a macromonomer (b-2) unit (structural unit ( It was confirmed that the compound contained 2 mol% of N), 83 mol% of N-phenylmaleimide units, and 15 mol% of methyl methacrylate units. Therefore, the graft-type vinyl polymer (c-3) has the following formula (8):

(In the formula, m ² represents the number of repeating units in parentheses.)
(D: b: c = 83: 2: 15 [mol%]). Moreover, the number average molecular weight measured using the gel permeation chromatograph of the graft type vinyl polymer (c-3) was 30000, and the molecular weight distribution was 5.01.

(Preparation Example 5)
Preparation of graft type vinyl polymer (c-4):
In a reaction vessel equipped with a stirrer, 100 parts by weight of a mixture of 40 mol% of macromonomer (b-3), 25 mol% of 1-pyrenylbutyl methacrylate and 35 mol% of methyl methacrylate, and 2,2′-azobis A solution was obtained by dissolving 1.0 part by weight of isobutyronitrile in 250 parts by weight of anhydrous toluene. Next, the temperature of the solution was increased to 75 ° C. while stirring at 200 rpm under a nitrogen stream, and the monomer was polymerized by maintaining the solution at 75 ° C. for 4 hours. Next, after cooling the temperature of the solution after polymerizing the monomer to 30 ° C., the solution is poured into 5 times equivalent of hexane, purified by reprecipitation, the solvent is completely distilled off by drying, Type vinyl polymer (c-4) was obtained.

When the composition of such a graft-type vinyl polymer (c-4) was determined by ¹ H-NMR, the graft-type vinyl polymer (c-4) was a macromonomer (b-4) unit (structural unit). (Corresponding to (I)) was confirmed to contain 55 mol%, 1-pyrenylbutyl methacrylate unit of 16 mol%, and methyl methacrylate unit of 29 mol%. Accordingly, the graft-type vinyl polymer (c-4) has the following formula (9):

(In the formula, m ³ represents the number of repeating units in parentheses.)
(A: e: c = 16: 55: 29 [mol%]). Moreover, the number average molecular weight measured using the gel permeation chromatograph of the graft type vinyl polymer (c-4) was 33200, and the molecular weight distribution was 3.43. The graft type vinyl polymer (c-4) thus obtained was soluble not only in chloroform but also in highly polar alcohol, and further in water.

(Preparation Example 6)
Preparation of graft type vinyl polymer (c-5):
In a reaction vessel equipped with a stirrer, 100 parts by weight of a mixture composed of 75 mol% of macromonomer (b-4) and 25 mol% of 1-pyrenylbutyl methacrylate, and 2,2′-azobisisobutyronitrile 1.0 Part by weight was dissolved in 250 parts by weight of anhydrous toluene to obtain a solution. Next, the temperature of the solution was increased to 75 ° C. while stirring at 200 rpm under a nitrogen stream, and the monomer was polymerized by maintaining the solution at 75 ° C. for 4 hours. Next, after cooling the temperature of the solution after polymerizing the monomer to 30 ° C., the solution is poured into 5 times equivalent of hexane, purified by reprecipitation, the solvent is completely distilled off by drying, Type vinyl polymer (c-5) was obtained.

The composition of such graft-type vinyl polymer (c-5) was determined by ¹ H-NMR. As a result, the graft-type vinyl polymer (c-5) was composed of macromonomer (b-4) units (structural units). (Corresponding to (I)) was confirmed to contain 76 mol% and 1-pyrenylbutyl methacrylate unit of 24 mol%. Moreover, the number average molecular weight measured using the gel permeation chromatograph of graft type vinyl polymer (c-5) was 21000, and molecular weight distribution was 1.89. The graft-type vinyl polymer (c-5) thus obtained was soluble not only in chloroform but also in highly polar alcohol, and further in water.

(Preparation Example 7)
Preparation of graft type vinyl polymer (c-6):
In a reaction vessel equipped with a stirrer, 100 parts by weight of a mixture consisting of 75 mol% of macromonomer (b-5) and 25 mol% of 1-pyrenylbutyl methacrylate, and 2,2′-azobisisobutyronitrile 1.0 Part by weight was dissolved in 250 parts by weight of anhydrous toluene to obtain a solution. Next, the temperature of the solution was increased to 75 ° C. while stirring at 200 rpm under a nitrogen stream, and the monomer was polymerized by maintaining the solution at 75 ° C. for 4 hours. Next, after cooling the temperature of the solution after polymerizing the monomer to 30 ° C., the solution is poured into 5 times equivalent of hexane, purified by reprecipitation, the solvent is completely distilled off by drying, Type vinyl polymer (c-6) was obtained.

The composition of such graft type vinyl polymer (c-6) was determined by ¹ H-NMR. As a result, the graft type vinyl polymer (c-6) contained macromonomer (b-5) units (structural units). (Corresponding to (I)) was confirmed to contain 76 mol% and 1-pyrenylbutyl methacrylate unit of 24 mol%. Moreover, the number average molecular weight measured using the gel permeation chromatograph of the graft type vinyl polymer (c-6) was 23000, and the molecular weight distribution was 1.85. The graft-type vinyl polymer (c-6) thus obtained was soluble not only in chloroform but also in highly polar alcohol, and further in water.

(Preparation Example 8)
Preparation of graft type vinyl polymer (c-7):
In a reaction vessel equipped with a stirrer, 100 parts by weight of a mixture composed of 40% by mole of macromonomer (b-3) and 60% by mole of N-phenylmaleimide, 0.3% by weight of 2,2′-azobisisobutyronitrile Parts and 0.05 parts by weight of tert-dodecyl mercaptan were dissolved in 300 parts by weight of methyl ethyl ketone to obtain a solution. Next, the temperature of the solution was increased to 75 ° C. while stirring at 200 rpm under a nitrogen stream, and the monomer was polymerized by maintaining the solution at 75 ° C. for 4 hours. Next, after cooling the temperature of the solution after polymerizing the monomer to 30 ° C., the solution is poured into 5 times equivalent of hexane, purified by reprecipitation, the solvent is completely distilled off by drying, Type vinyl polymer (c-7) was obtained.

The composition of such graft-type vinyl polymer (c-7) was determined by ¹ H-NMR. As a result, the graft-type vinyl polymer (c-7) contained macromonomer (b-3) units (structural units). (Corresponding to (I)) was confirmed to contain 40 mol% and N-phenylmaleimide units 60 mol%. Moreover, the number average molecular weight measured using the gel permeation chromatograph of graft type vinyl polymer (c-7) was 25000, and molecular weight distribution was 2.30. The graft-type vinyl polymer (c-7) thus obtained was soluble not only in chloroform but also in highly polar alcohol, and further in water.

(Preparation Example 9)
Preparation of methyl methacrylate / 1-pyrenylbutyl methacrylate copolymer (polymer (d-1)):
In a reaction vessel equipped with a stirrer, 75 mol% of methyl methacrylate, 25 mol% of 1-pyrenylbutyl methacrylate, 0.4 parts by weight of 2,2′-azobisisobutyronitrile and 550 parts by weight of toluene were charged. . Next, the system was replaced with nitrogen gas while stirring the solution obtained in the reaction can. Subsequently, the temperature of the said solution was heated up to 75 degreeC, and the monomer in a solution was polymerized by keeping at 75 degreeC for 4 hours. Next, after cooling the temperature of the solution after polymerizing the monomer to 30 ° C., the solution is poured into an excess amount of methanol, purified by reprecipitation, and the solvent is completely distilled off by vacuum drying. A polymer (d-1) was obtained.

The composition of the polymer (d-1) was determined by ¹ H-NMR. As a result, the polymer (d-1) contained 70 mol% of methyl methacrylate units and 30 units of 1-pyrenylbutyl methacrylate units. It was confirmed that the content was mol%. The number average molecular weight of the polymer (d-1) was 22000, and the molecular weight distribution was 2.55.

(Preparation Example 10)
Preparation of 1-pyrenylbutyl methacrylate / decyl methacrylate copolymer (polymer (d-2)):
In a reaction vessel equipped with a stirrer, 75 mol% of decyl methacrylate, 25 mol% of 1-pyrenylbutyl methacrylate, 0.4 parts by weight of 2,2′-azobisisobutyronitrile and 550 parts by weight of toluene were then added. While stirring the solution obtained in the reaction can, the inside of the system was replaced with nitrogen gas. Subsequently, the temperature of the said solution was heated up to 75 degreeC, and the monomer in a solution was polymerized by keeping at 75 degreeC for 4 hours. Next, after cooling the temperature of the solution after polymerizing the monomer to 30 ° C., the solution is poured into an excess amount of methanol, purified by reprecipitation, and the solvent is completely distilled off by vacuum drying. A polymer (d-2) was obtained.

The composition of such a polymer (d-2) was determined by ¹ H-NMR. As a result, the polymer (d-2) had a decyl methacrylate unit of 68 mol% and a 1-pyrenylbutyl methacrylate unit of 32 mol. It was confirmed that the content was mol%. The number average molecular weight of the polymer (d-2) was 20000, and the molecular weight distribution was 2.65.

Example 1
2 mg of the graft-type vinyl polymer (c-1) obtained in Preparation Example 2 and 2 mg of the carbon nanostructure (A-1) were weighed, put into 20 ml of chloroform, and sonicated for 1 hour. (BRANSON made tabletop ultrasonic cleaner BRANSONIC B-220, oscillation frequency 45 kHz) to adsorb the graft type vinyl polymer (c-1) to the carbon nanostructure (a-1) A carbon nanocomposite was produced therein, thereby obtaining a dispersion in which the carbon nanocomposite was dispersed in a solvent. The dispersibility of the dispersion thus obtained was evaluated by the method described in (5) above. The obtained results are shown in Table 2.

(Examples 2 to 6)
Carbon was prepared in the same manner as in Example 1 except that instead of the graft type vinyl polymer (c-1) obtained in Preparation Example 2, the type of graft type vinyl polymer shown in Table 1 below was used. A nanocomposite and a dispersion liquid in which the carbon nanocomposite was dispersed were obtained. The dispersibility of the dispersion thus obtained was evaluated by the method described in (5) above. The obtained results are shown in Table 2.

(Comparative Examples 1-3)
Carbon for comparison was obtained in the same manner as in Example 1 except that the polymer of the type shown in Table 2 below was used instead of the graft-type vinyl polymer (c-1) obtained in Preparation Example 2. A comparative dispersion liquid in which the nanocomposite and the carbon nanocomposite were dispersed was obtained. The dispersibility of the dispersion thus obtained was evaluated by the method described in (5) above. The obtained results are shown in Table 2.

(Comparative Example 4)
Dispersion for comparison in the same manner as in Example 1 except that only the carbon nanostructure (a-1) was used without using the graft-type vinyl polymer (c-1) obtained in Preparation Example 2. A liquid was obtained. The dispersibility of the dispersion thus obtained was evaluated by the method described in (5) above. The obtained results are shown in Table 2.

  As is clear from the results shown in Table 2, the absorbance of the dispersions of the present invention (Examples 1 to 6) was sufficiently higher than that of the dispersion for comparison. From these results, it was confirmed that the carbon nanocomposite of the present invention using a graft type vinyl polymer exhibits sufficiently high dispersibility in a solvent.

(Example 7)
42 mg of the graft-type vinyl polymer obtained in Preparation Example 2 and 210 mg of the carbon nanostructure (a-1) were weighed, put into 210 ml of chloroform, and subjected to ultrasonic treatment for 1 hour (BRANSON made tabletop ultra A sonic cleaner BRANSONIC B-220, oscillation frequency 45 kHz) was performed to obtain a dispersion. Next, the dispersion was subjected to suction filtration while washing with 630 mL of chloroform using a Kiriyama funnel (filter: Millipore membrane filter 1.0 μm). Subsequently, the carbon nanocomposite (e-1) of this invention was obtained by distilling a solvent off from the obtained solid content by vacuum drying. Table 3 shows the characteristics of each carbon nanocomposite measured using the measurement method described above.

(Examples 8 to 12)
Instead of the graft type vinyl polymer obtained in Preparation Example 2, Preparation Example 3 (Example 8), Preparation Example 4 (Example 9), Preparation Example 5 (Example 10), Preparation Example 6 (Example) 11) or carbon nanocomposites (e-2) to (e-2) to (e) of the present invention in the same manner as in Example 7 except that the graft type vinyl polymer obtained in Preparation Example 7 (Example 12) was used. e-6) was obtained respectively. Table 3 shows the characteristics of each carbon nanocomposite measured using the measurement method described above.

(Comparative Examples 5-7)
Instead of the graft-type vinyl polymer obtained in Preparation Example 2, the polymer or polymer (d-3) obtained in Preparation Example 9 (Comparative Example 5) and Preparation Example 10 (Comparative Example 6) was used. Carbon nanocomposites (f-1) to (f-3) for comparison were obtained in the same manner as in Example 7 except that they were used. Table 3 shows the characteristics of each carbon nanocomposite measured using the measurement method described above.

(Comparative Example 8)
The carbon nanostructure (a-1) was directly used as a carbon nanocomposite for comparison. Table 3 shows the characteristics of each carbon nanocomposite measured using the measurement method described above.

  As is clear from the results shown in Table 3, in the carbon nanocomposites (Examples 7 to 12) of the present invention, the adsorption amount of the graft type vinyl polymer to the carbon nanostructure was large. Such a result is presumed to be caused by the fact that the graft-type vinyl polymer contains a bulky polymer chain portion and is excellent in affinity with the solvent and the resin. Further, in the carbon nanocomposites of the present invention (Examples 7 to 12), a sufficient amount of the graft-type vinyl polymer is adsorbed, so that it has excellent redispersibility and fluidity when added to a resin. Was confirmed to be sufficiently excellent. Moreover, the carbon nanocomposites (e-1) to (e-3) of the present invention obtained in Examples 7 to 9 were more excellent in dispersibility, fluidity and thermal conductivity in organic solvents and resins. Showed the characteristics. Further, in the carbon nanocomposites (e-2) and (e-3) obtained in Examples 8 to 9, the gut obtained after the dispersibility and fluidity evaluation tests in the resin and melt-kneading. The external appearance was also particularly excellent. This is because the carbon nanocomposites (e-2) and (e-3) obtained in Examples 8 to 9 contain an imide unit in the structure of the adsorbed graft-type vinyl polymer, Since the heat resistance is high, the stability at high temperature is particularly excellent, and it is presumed that the graft-type vinyl polymer is not decomposed even when melt-kneading for 10 minutes at a high temperature of 290 ° C. In addition, in the carbon nanocomposites (e-1) to (e-3) obtained in Examples 7 to 9, the dispersibility in the resin is improved, and the graft-type vinyl system on the surface of the carbon nanostructure is used. The thermal conductivity is improved by improving the affinity between the carbon structure and the resin due to the large amount of polymer adsorption, and the rate of increase in torque value compared to polyphenylene sulfide resin alone (thermal conductivity: 0.24 W / mK). It was confirmed that the thermal conductivity was improved by 1.5 times or more while suppressing the content of Cd within 10%.

(Example 13)
2 mg of the graft type vinyl polymer (c-4) and 2 mg of the carbon nanostructure (a-1) were weighed, put into 20 mL of ion-exchanged water, and subjected to ultrasonic treatment for 1 hour (BRANSON made tabletop Type ultrasonic cleaner BRANSONIC B-220, oscillation frequency 45 kHz) to produce a carbon nanocomposite in ion-exchanged water, thereby obtaining a dispersion in which the carbon nanocomposite was dispersed in the ion-exchanged water.

  Next, the test (spectrum measurement test (I)) which measures a UV-visible light spectrum using the dispersion liquid obtained in this way was done. That is, after the centrifugal separation (relative centrifugal acceleration of 1000 G for 1 hour) was performed on the dispersion, a UV-visible light spectrum was measured for the obtained supernatant. Table 4 shows the absorbance values measured at 650 nm.

  Further, suction filtration was performed while washing the dispersion using 60 mL of ion exchange water. Next, the carbon nanocomposite obtained by removing the solvent from the obtained solid by vacuum drying was measured for the amount of adsorption of the graft-type vinyl polymer by the method described in (4) above. The adsorption amount of the type vinyl polymer (c-4) was confirmed to be 3.6% by mass.

(Example 14)
A dispersion was produced in the same manner as in Example 13 except that the graft type vinyl polymer (c-7) obtained in Preparation Example 8 was used instead of the graft type vinyl polymer (c-4). Then, the spectrum measurement test (I) and the amount of adsorption of the graft-type vinyl polymer were measured. Table 4 shows the absorbance values measured at 650 nm. Moreover, it was confirmed that the adsorption amount of the graft type vinyl polymer (c-7) is 3.6% by mass.

(Comparative Example 9)
A dispersion was produced in the same manner as in Example 13 except that the compound (d-4) was used instead of the graft-type vinyl polymer (c-4), and a spectrum measurement test (I) was performed. Table 4 shows the absorbance values measured at 650 nm.

(Comparative Example 10)
A dispersion was produced in the same manner as in Example 13 except that the macromonomer (b-3) was used instead of the graft type vinyl polymer (c-4), and the spectrum measurement test (I) was performed. Table 4 shows the absorbance values measured at 650 nm.

(Comparative Example 11)
A dispersion was produced in the same manner as in Example 13 except that the graft-type vinyl polymer (c-4) was not used, and the spectrum measurement test (I) was performed. Table 4 shows the absorbance values measured at 650 nm.

  As is clear from the results shown in Table 4, the dispersion containing the carbon nanocomposites of the present invention (Examples 13 to 14) using the graft type vinyl polymers (c-4) and (c-7). In the liquid, the carbon nanocomposite is in water compared with the dispersion liquid when the known compound (d-4), macromonomer (b-3), or the like is used as the dispersant (Comparative Examples 9 to 11). It was confirmed that the dispersion was sufficiently high. From these results, it was found that the carbon nanocomposites (Examples 13 to 14) of the present invention have sufficiently excellent dispersibility even in water.

(Example 15)
2 mg of the graft-type vinyl polymer (c-1) and 2 mg of the carbon nanostructure (a-2) were weighed, put into 20 mL of hexane, and subjected to ultrasonic treatment for 1 hour (BRANSON made tabletop ultra A sonic cleaner BRANSONIC B-220, oscillation frequency 45 kHz) was produced to produce a carbon nanocomposite in hexane, thereby obtaining a dispersion in which the carbon nanocomposite was dispersed in hexane.

  Next, the test (spectrum measurement test (II)) which measures a UV-visible light spectrum using the dispersion liquid obtained in this way was done. That is, after centrifuging the dispersion (with a relative centrifugal acceleration of 1000 G for 1 hour), a UV-visible light spectrum was measured for the obtained supernatant. Table 5 shows the absorbance values measured at 650 nm.

  Further, suction filtration was performed while washing the dispersion using 60 mL of hexane. Next, the carbon nanocomposite obtained by removing the solvent from the obtained solid by vacuum drying was measured for the amount of adsorption of the graft-type vinyl polymer by the method described in (4) above. The adsorption amount of the type vinyl polymer (c-1) was confirmed to be 5.8% by mass.

(Comparative Example 12)
A dispersion was produced in the same manner as in Example 15 except that the macromonomer (b-1) was used instead of the graft type vinyl polymer (c-1), and a spectrum measurement test (II) was performed. Table 5 shows the absorbance values measured at 650 nm.

(Comparative Example 13)
A dispersion was produced in the same manner as in Example 15 except that the graft-type vinyl polymer (c-1) was not used, and a spectrum measurement test (II) was performed. Table 5 shows the absorbance values measured at 650 nm.

  As is clear from the results shown in Table 5, in the dispersion containing the carbon nanocomposite of the present invention (Example 15) using the graft type vinyl polymer (c-1), the macromonomer (b -1) and the like (Comparative Examples 12 to 13), compared with the dispersion liquids, carbon nanostructures in hexane, which has been difficult to disperse in the conventional carbon nanostructures due to low polarity and low specific gravity, It was confirmed that the composite was sufficiently highly dispersed. From these results, it was found that the carbon nanocomposite of the present invention (Example 15) has sufficiently excellent dispersibility even in a solvent having low polarity and low specific gravity. In addition, none of the compounds (d-1) to (d-3) was dissolved in hexane, and there was no effect of improving the dispersibility of the carbon nanostructure.

  As described above, according to the present invention, a carbon nanocomposite excellent in dispersibility and fluidity in a solvent or a resin, a dispersion containing the same and a resin composition, and production of the carbon nanocomposite It becomes possible to provide a method.

  As described above, the carbon nanocomposite of the present invention is particularly excellent in dispersibility and fluidity in a solvent or a resin. For various applications such as applications that require electromagnetic shielding, applications that require heat resistance, applications that require dimensionality (decrease in thermal expansion coefficient), applications that require electrical conductivity, and applications that require thermal conductivity In particular, it can be suitably used for resin molded bodies, resin sheets, resin films, and the like that require these characteristics.

Claims (6)

Carbon nanostructures,
A main chain comprising a vinyl polymer and a side chain comprising at least one polymer chain of vinyl polymer, polysiloxane and polyoxyalkylene , wherein one of the polymer chains and the polymer chain are A structural unit having a molecular weight of 300 or more composed of a vinyl monomer unit in the main chain to be bonded, and the following general formula (3):

(R ¹ represents a divalent organic group having 1 to 20 carbon atoms, R ² represents a monovalent polycyclic aromatic-containing group, and R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom and a carbon atom. Represents any of the monovalent organic groups of formulas 1 to 20.)
A polycyclic aromatic group-containing vinyl monomer unit represented by the following general formula (4):

(R ⁶ and R ⁷ each independently represents one of a hydrogen atom and an alkyl group, and R ⁸ represents a hydrogen atom, an alkyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group or an amino group. Represents either one.)
A graft-type vinyl polymer containing at least one structural unit of maleimide monomer units represented by formula (1 ) and adsorbed to the carbon nanostructure;
A carbon nanocomposite characterized by comprising: The carbon nanocomposite according to claim 1, wherein the molecular weight of a structural unit composed of one of the polymer chains and a vinyl monomer unit in the main chain to which the polymer chain is bonded is 400 or more. .   The carbon nanocomposite according to claim 1 or 2, wherein the carbon nanostructure has a diameter of 1 µm or less.   A dispersion comprising the carbon nanocomposite according to any one of claims 1 to 3 and a solvent.   A resin composition comprising the carbon nanocomposite according to any one of claims 1 to 3 and a resin. Carbon nanostructures,
A main chain composed of a vinyl polymer and a side chain composed of at least one polymer chain of vinyl polymer, polysiloxane and polyoxyalkylene, and one of the polymer chains and the polymer chain are A structural unit having a molecular weight of 300 or more composed of a vinyl monomer unit in the main chain to be bonded, and the following general formula (3):

(R ¹ represents a divalent organic group having 1 to 20 carbon atoms, R ² represents a monovalent polycyclic aromatic-containing group, and R ³ , R ⁴ and R ⁵ each independently represents a hydrogen atom and a carbon atom. Represents any of the monovalent organic groups of formulas 1 to 20.)
A polycyclic aromatic group-containing vinyl monomer unit represented by the following general formula (4):

(R ⁶ and R ⁷ each independently represents one of a hydrogen atom and an alkyl group, and R ⁸ represents a hydrogen atom, an alkyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group or an amino group. Represents either one.)
A graft-type vinyl polymer containing at least one structural unit of maleimide monomer units represented by :
A method for producing a carbon nanocomposite comprising mixing a carbon nanostructure in a solvent to adsorb the grafted vinyl polymer to the carbon nanostructure to obtain a carbon nanocomposite.