WO2023042856A1 - Nanocarbon-blended aggregates and method for producing same - Google Patents

Nanocarbon-blended aggregates and method for producing same Download PDF

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WO2023042856A1
WO2023042856A1 PCT/JP2022/034428 JP2022034428W WO2023042856A1 WO 2023042856 A1 WO2023042856 A1 WO 2023042856A1 JP 2022034428 W JP2022034428 W JP 2022034428W WO 2023042856 A1 WO2023042856 A1 WO 2023042856A1
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nanocarbon
blended
aggregate
mass
aggregates
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French (fr)
Japanese (ja)
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宏史 山本
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三菱商事株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a nanocarbon compound aggregate and a method for producing the same.
  • CNT carbon nanotubes
  • CNF carbon nanofibers
  • CNC carbon nanocoils
  • GPN graphene
  • CNTs are carbon crystals with a diameter of several nm to about 500 nm, a length of about 10 ⁇ m to 1000 ⁇ m, a large aspect ratio, and a tubular structure.
  • types including single-wall CNTs having a single-layer structure, double-wall CNTs having two layers that fall into the category of multi-wall CNTs having a multi-layer structure, and the like.
  • CNTs are known to impart electrical conductivity, high elasticity, high strength, thermal conductivity, etc. to base materials by being blended with base materials such as various synthetic resins and rubbers.
  • Patent Document 1 CNTs are impregnated with an aqueous solution containing a water-soluble polymer at a predetermined concentration to form a solid aggregate, which is subjected to a shear crushing treatment and then dried to achieve a high bulk density and dispersibility in a simple and convenient manner.
  • the present applicant has reported that CNT-blended agglomerates with a low M can be efficiently obtained.
  • Patent Document 1 does not report anything about the dispersibility of CNT-blended aggregates.
  • the aggregation medium When preparing a nanocarbon-containing aggregate of nanocarbon such as CNT or graphene and an aggregation medium, the aggregation medium does not uniformly adhere to and permeate the nanocarbon, forming a non-uniform nanocarbon-containing aggregate, resulting in a poor particle size distribution. This can result in inconsistent quality of the CNT-blended agglomerate and reduced handling properties. Therefore, it can be said that efficiently obtaining nanocarbon-blended agglomerates with improved dispersibility is still an important issue in this technical field.
  • One object of the present invention is to efficiently obtain nanocarbon-blended aggregates with good dispersibility.
  • the inventors of the present invention impregnated CNTs with a solution containing a predetermined concentration of a binder agent to form aggregates, and then pulverized the aggregates to efficiently obtain nanocarbon-blended aggregates with good dispersibility. I found what I could do. The present invention is based on such findings.
  • a method for producing a nanocarbon-blended agglomerate comprising: (1) A step of impregnating 100 parts by mass of nanocarbon with 1 to 10 parts by mass of a binder agent and 43 to 233 parts by mass of a liquid medium to obtain a solid aggregate, and (2) dissolving the solid aggregate. a step of crushing to obtain a nanocarbon-blended aggregate; comprising A method is provided, wherein the hardness of the nanocarbon-blended aggregate measured according to JIS K 6219-3 is 10 g or less.
  • the present invention it is possible to efficiently obtain nanocarbon-blended aggregates with good dispersibility.
  • INDUSTRIAL APPLICABILITY The present invention can be advantageously used to efficiently obtain a nanocarbon-containing agglomerate that has good dispersibility, high bulk density, and low scattering properties. Further, according to the present invention, by improving the dispersibility of the nanocarbon-containing aggregate, it is possible to improve workability such as workability and handleability.
  • the blending treatment and the crushing treatment can be continuously performed in a closed system solid phase state to provide nanocarbon-blended agglomerates, which is advantageous in terms of reducing the environmental load. .
  • the nanocarbon-blended agglomerates can be mass-produced simply and quickly at low cost without requiring large-scale equipment, which is particularly advantageous in terms of industrial production.
  • a method for producing a nanocarbon-blended agglomerate comprising: (1) A step of impregnating 100 parts by mass of nanocarbon with 1 to 10 parts by mass of a binder agent and 43 to 233 parts by mass of a liquid medium to obtain a solid aggregate, and (2) dissolving the solid aggregate. a step of crushing to obtain a nanocarbon-blended aggregate; comprising A method is provided, wherein the hardness of the nanocarbon-blended aggregate measured in accordance with JIS K 6219-3 is 10 g or less.
  • each step of the method for producing a nanocarbon-containing aggregate according to the present invention will be described in detail.
  • Step (1) 100 parts by mass of nanocarbon is impregnated with 1 to 10 parts by mass of a binder agent and 43 to 233 parts by mass of a liquid medium to form a solid aggregate. obtain.
  • the binder agent and liquid medium present between two or more nanocarbon particles bind the particles by interfacial tension to form large nanocarbon-containing particles, while the surface of the nanocarbon-containing particles
  • the binder agent and liquid medium adhering to the nanocarbon-containing particles coat the nanocarbon-containing particles to form a layer. It is considered that solid aggregates are stably generated by repeating such aggregation phenomenon and coating phenomenon.
  • Nanocarbon as used in the present invention is a general term for a group of substances made of carbon having a nanometer (1/1,000,000,000 m) size structure.
  • examples of nanocarbon include CNT, CNF, CNC, GPN, fullerene, GPN and the like, preferably CNT or GPN, more preferably CNT.
  • graphene (GPN) refers not only to a one-atom-thick sheet of sp2-bonded carbon atoms, but also to a substance composed of multiple sheets but commercially named graphene. include.
  • the CNTs used in the present invention are not particularly limited, and may be in any form, such as single-wall CNTs having a single-layer structure, double-wall CNTs falling into the category of multi-wall CNTs having a multi-layer structure, and the like.
  • CNTs have different morphologies depending on the manufacturing method. It may be obtained.
  • the CNT as a raw material used in the method for producing the nanocarbon compound aggregate of the present invention preferably has a fiber diameter of 1 nm from the viewpoint of ensuring superior physical properties such as electrical and mechanical properties and dispersibility. ⁇ 200 nm, more preferably 1 nm to 150 nm, even more preferably 1 nm to 100 nm.
  • the fiber length of CNT is preferably 0.1 ⁇ m to 2000 ⁇ m, more preferably 0.1 ⁇ m to 1000 ⁇ m, from the viewpoint of ensuring conductivity, mechanical properties, dispersibility, and avoiding fiber breakage. More preferably, it is 0.1 ⁇ m to 500 ⁇ m.
  • the aspect ratio of CNT is usually about 10 to 10,000, and a structure in which a hexagonal network-like graphite sheet has a cylindrical shape is preferably used.
  • Either single-layer CNTs or multilayer CNTs may be used, and can be selected according to the final purpose.
  • the CNT production method is not limited, and includes a thermal decomposition method in which a carbon-containing gas is brought into contact with a catalyst, an arc discharge method in which an arc discharge is generated between carbon rods, and a laser evaporation method in which a carbon target is irradiated with a laser.
  • CVD method in which carbon source gas is reacted at high temperature in the presence of fine metal particles
  • HiPco method in which carbon monoxide is decomposed under high pressure.
  • CNTs doped with metal atoms may also be used. In addition, these CNTs may be used singly or in combination.
  • a surfactant such as an amphipathic polymer or low-molecular-weight compound is used.
  • a surfactant such as an amphipathic polymer or low-molecular-weight compound is used.
  • it is preferably a graft type polymer having a polyoxyalkylene chain, an amine-based polymer, a cellulose-based polymer, or the like.
  • graft-type polymers having polyoxyalkylene chains include polyfunctional comb-shaped functional polymers having polyoxyalkylene chains as graft chains.
  • the functional polymer is (a) a polyoxyalkylene alkyl represented by the following formula (I) an allyl alcohol/maleic anhydride copolymer and a poly It is a grafted product with oxyalkylene monoalkyl alcohol.
  • the number of moles of added ethylene oxide units in the component (b), preferably m in formula (I), is 5 to 50 moles.
  • R is a linear or branched alkyl group having 1 to 5 carbon atoms, for example, linear methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group; isopropyl a branched group such as a group, an isobutyl group and an isopentyl group; a cyclic group such as a cyclopropyl group and a cyclopentyl group;
  • allyl alcohol/maleic anhydride/styrene copolymer and polyoxyalkylene monoalkyl ether grafted product used in the present invention include the following formula (II), and the allyl alcohol/maleic anhydride copolymer and poly Grafted products with oxyalkylene monoalkyl ethers are exemplified by those represented by the following formula (III), and these can be used alone or in combination of two or more.
  • a diallylamine-based cationic polymer can be suitably used as the amine-based polymer.
  • the diallylamine-based cationic polymer include polymers of secondary amine salts such as diallylamine hydrochloride and sulfate, and polymers of quaternary ammonium salts such as polydiallyldialkylammonium chloride and polydiallyldialkylammonium bromide. Polymers of quaternary ammonium salts are preferred, and polymers such as poly(diallyldimethylammonium chloride) (PDADMAC) are particularly preferred.
  • PDADMAC poly(diallyldimethylammonium chloride)
  • the amine-based polymer is obtained by polymerization of at least one monomer having a quaternary ammonium group and at least one polyfunctional monomer having no quaternary ammonium group. It may be a copolymer that is The mass ratio of the monomer having a quaternary ammonium group to the polyfunctional monomer is preferably from 90/10 to 10/90, more preferably from 75/25 to 40/60, even more preferably from 60/40 to 50. /50.
  • the monomer having a quaternary ammonium group preferably has the following formula (IV):
  • R 1 is H or C 1 -C 4 -alkyl
  • R 2 is H or methyl
  • R 3 is C 1 -C 4 -alkylene
  • R 4 , R 5 and R 6 are each independently H or C 1 -C 30 -alkyl
  • X is —O— or —NH—
  • Y is Cl, Br, I, hydrogensulfate or methosulfate salts.
  • R 1 and R 2 are each H, or R 1 is H and R 2 is CH 3 or preferably H as well.
  • Particularly preferred monomers of formula (IV) are [2-(acryloyloxy)ethyl]trimethylammonium chloride, also called dimethylaminoethyl acrylate metochloride (DMA3*MeCl) or dimethylaminoethyl methacrylate metochloride (DMAEMA*MeCl). trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium chloride.
  • At least one polyfunctional monomer having no quaternary ammonium group includes acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinylimidazole, Examples include methyl ester or ethyl ester of itaconic acid or maleic acid, ethyl acrylate or methyl acrylate, and the like.
  • the polyfunctional monomer having no quaternary ammonium group preferably has the following formula (V): (wherein R 7 is H or C 1 -C 4 -alkyl, R 8 is H or methyl, R 9 and R 10 are independently of each other H or C 1 -C 30 -alkyl is selected from the monomers represented by
  • the monomer of formula (V) above is preferably acrylamide, methacrylamide or dialkylaminoacrylamide.
  • the polyfunctional monomer having no quaternary ammonium group has the following formula (VI): (wherein Ra is H or C 6 -C 50 -alkyl, Rb is H or C1-C4-alkyl, Rc is H or methyl, n is an integer of 0 to 100).
  • Ra is preferably C 8 -C 30 -alkyl, more preferably C 16 -C 22 -alkyl, Rb is preferably H, n is preferably 3-50.
  • the non-amine monomer of formula (III) is preferably an aliphatic alcohol ethoxylate or its methacrylate.
  • each of the monomers of formula (I), formula (II), and formula (III) may be used in the copolymer constituting the amine-based polymer.
  • the R groups of the monomers of formula (III) above may be present in the copolymer with monomers having different chain lengths, such as C16 and C18 .
  • the copolymers that make up the amine-based polymer are preferably dialkylaminoalkyl (meth)acrylates and monomers selected from alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates and combinations thereof. It is a copolymer composed of units.
  • the copolymer preferably comprises diC 1 -C 2 alkylamino C 1 -C 2 alkyl (meth)acrylates, C 1 -C 4 alkyl ( meth ) acrylates, and (meth)acrylic
  • a copolymer comprising as monomer units selected from acid monohydroxy C 2 -C 4 alkyl and combinations thereof, more preferably methyl (meth)acrylate/butyl (meth)acrylate/(meth)acrylic acid It is a dimethylaminoethyl copolymer, more preferably a methyl methacrylate/butyl methacrylate/dimethylaminoethyl methacrylate copolymer.
  • methyl methacrylate/butyl methacrylate/dimethylaminoethyl methacrylate copolymer a commercially available one may be used, for example, Eudragit (registered trademark) E100 (Degussa).
  • the cellulosic polymer includes carboxymethylcellulose, hydrophobically modified carboxymethylcellulose, cationically modified hydroxyethylcellulose, cationically modified hydroxypropylcellulose, cationically and hydrophobically modified hydroxyethylcellulose, cationically and hydrophobically modified hydroxypropylcellulose, and mixtures thereof, preferably carboxymethyl cellulose, cation-modified hydroxyethyl cellulose, cation- and hydrophobically-modified hydroxyethyl cellulose, or mixtures thereof, more preferably carboxymethyl cellulose.
  • cellulosic polymers include Finnfix GDA (sold by CP Kelco), e.g., the alkylketene dimer derivative of carboxymethyl cellulose sold under the trade name Finnfix SH1 (CP Kelco), or the trade name Finnfix V (sold by CP Kelco) and the like.
  • binder agents other than those mentioned above include cationic starch, cationic guar gum, modified polyvinyl alcohol, cationic polyacrylamide, polyamide epichlorohydrin (PAE), melamine resin derivatives, polyvinylamine or its derivatives, polyvinyl Cationic groups (1 to quaternary ammonium salts, etc.) are introduced into the main chain or side chains, citric acid, sodium hydrogen carbonate, and the like.
  • the molecular weight of the binder agent depends on the type of nanocarbon impregnated with the binder agent. Good, but preferably 1,000 to 50,000, more preferably 1,500 to 3,000. Further, from the viewpoint of adhesion (aggregation) between granules when granules are formed by shearing after forming a solid aggregate, the weight average molecular weight is preferably 8,000 to 50,000. Incidentally, the mass average molecular weight can be measured according to a standard method by a gel permeation chromatography (GPC) method (polystyrene standard).
  • GPC gel permeation chromatography
  • the liquid medium used in step (1) is, for example, organic solvent oil, plasticizer, water, etc., preferably process oil.
  • the temperature at which step (1) is performed is not particularly limited, but is, for example, 5 to 50°C, preferably 30 to 40°C.
  • the step (1) can be carried out in two steps. That is, in a preferred embodiment of the present invention, the step (1) is (1a) a step of preparing a binder liquid containing a binder agent and a liquid medium; and (1b) a step of impregnating nanocarbon with the binder liquid to obtain a solid aggregate.
  • a binder liquid is prepared by mixing a binder agent and a liquid medium.
  • the amount of the binder used can be appropriately set within the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of nanocarbon, preferably 0.15 to 5 parts by mass, more preferably 0. .2 to 2 parts by mass.
  • the amount of the liquid medium used can be appropriately set in the range of 43 to 233 parts by mass with respect to 100 parts by mass of nanocarbon, preferably 80 to 200 parts by mass, more preferably 100 to 150 parts by mass. Department.
  • the concentration of the binder agent in the binder liquid is, for example, 0.1 to 5% by mass, It is preferably 0.2 to 3% by mass, more preferably 0.2 to 2% by mass.
  • Adjusting the binder agent and the liquid medium to the predetermined amounts as described above keeps the size of the droplets within an appropriate range when the binder liquid is dropped in step (1b), and the binder liquid impregnation treatment can be performed efficiently. can be done.
  • the binder agent and the liquid medium can be mixed by stirring using a known stirring device. It is preferred to use a bath.
  • the stirring speed in the stirring device is, for example, 5 to 20 rpm, preferably 5 to 12 rpm, more preferably 7 to 10 rpm.
  • the stirring may be continued when the binder liquid is added to the nanocarbon in step (1b).
  • step (1b) nanocarbon is impregnated with a binder liquid to obtain a solid aggregate.
  • the amount of the binder liquid used can be appropriately set in the range of 44 to 243 parts by mass with respect to 100 parts by mass of nanocarbon, preferably 80 to 200 parts by mass, more preferably 100 to 150 parts by mass. be.
  • the impregnation treatment in step (1b) is preferably carried out by dropping a binder liquid onto the nanocarbon.
  • the impregnation treatment may be carried out in a known stirring device, but from the viewpoint of preparing a uniform mixture, it is preferable to use an inclined stirring tank.
  • nanocarbon is charged in an inclined stirring vessel, and the binder liquid is dripped onto the nanocarbon in the inclined stirring vessel while rotating the inclined shaft stirring vessel at a predetermined number of revolutions. .
  • the impregnation treatment in step (1b) is performed under a reduced pressure atmosphere, a pressurized atmosphere, or a combination thereof. It is preferable to repeat the depressurization and pressurization operations in this way in order to adjust the adsorption speed of the binder liquid. Further, adjusting the pressure conditions in the step (1b) is advantageous in terms of allowing the binder liquid to uniformly permeate the inside of the nanocarbon and improving the wettability of the surface of the nanocarbon.
  • the reduced pressure condition is, for example, 5 to 50 Pa, preferably 10 to 40 Pa, more preferably It is 10-20Pa.
  • the pressurized conditions are, for example, 0.1 to 5 MPa, preferably 0.2 to 5 MPa. and more preferably 0.5 to 3 MPa.
  • step (1b) by adding a binder liquid to the nanocarbon in a predetermined amount as described above, it can be suitably prepared as a soft solid aggregate with plasticity.
  • Step (2) Crushing treatment step for solid aggregates
  • the solid agglomerate obtained in the step (1) is pulverized to obtain a nanocarbon-containing agglomerate.
  • the crushing treatment of the present invention refers to a dispersing treatment for disentangling lumpy solid aggregates, and is used in a broad sense including deflocculation.
  • the crushing treatment is preferably carried out using a shearing device, more preferably using a shearing crushing device.
  • shearing refers to a process of applying a shearing force to a sample to make the sample finer.
  • a shearing device As a shearing device, a high-speed rotating blade and a fixed cutting head blade are used to break up solid agglomerates thrown in. Apparatuses that utilize impact to simultaneously shear solid agglomerates and high-speed agitation are included.
  • More specific shearing devices include comitrolles, colloid mills, electric mills, mass colloiders, food processors, pulper finishers, rotary cutter mills, microhoffs, nano cutters, pulverizers and the like, preferably nano cutters. be.
  • the operating conditions of the shearing device are not particularly limited, but are preferably set from the viewpoint of efficient production of nanocarbon-blended agglomerates.
  • the temperature in the shearing device during the crushing process is, for example, about 20°C to 90°C.
  • the rotation speed of the blades in the shearing device is about 350 to 600 rpm, preferably about 500 to 600 rpm.
  • the crushing treatment may be performed once, or may be performed repeatedly two or more times.
  • the solid aggregates obtained in step (1) are subjected to the crushing treatment in step (2) to directly provide nanocarbon-blended aggregates without going through a drying step. can be done. Therefore, according to one embodiment, the method of the present invention does not include a drying step. Since the production method of the present invention can be easily carried out without a drying step, it is advantageous in efficiently obtaining nanocarbon-containing aggregates in a short period of time.
  • Nanocarbon compound aggregate According to one embodiment of the present invention, there is provided a nanocarbon-containing agglomerate obtained by the above method. According to a preferred embodiment of the present invention, the nanocarbon-loaded agglomerate is provided as a non-dried product (storage, packaging, etc.).
  • the hardness of the nanocarbon-containing agglomerates of the present invention is adjusted to 10 g or less, which is advantageous in exhibiting excellent dispersibility and handleability.
  • "hardness” means hardness measured according to JIS K 6219-3.
  • the hardness of the nanocarbon-containing agglomerates may be within a range of 20 g or less, preferably 5 to 15 g, more preferably 5 to 10 g.
  • the bulk density of the nanocarbon-blended aggregates is preferably 0.5-2.3 g/cm 3 , more preferably 0.8-2.0 g/cm 3 . and more preferably 0.8 to 1.5 g/cm 3 .
  • the nanocarbon-blended agglomerate obtained by the production method of the present invention has a very high bulk density as described above, therefore, for example, in the kneading step of synthetic resin etc., it is possible to prevent the occurrence of bridges in the storage tank and supply It also has the advantage of enabling automatic weighing of time and reducing transportation and inventory costs.
  • the nanocarbon-containing aggregates are granular.
  • the average particle diameter of the nanocarbon-blended aggregates is preferably 0.15-2.0 mm, more preferably 0.25-1.8 mm, still more preferably 0.25-1.0 mm.
  • the average particle size is the average value obtained by calculating the particle size of each of 100 randomly extracted aggregates by microscopic observation of the nanocarbon-blended aggregates.
  • nanocarbon-containing agglomerate of the present invention can exhibit excellent dispersibility, it can be provided as an aggregate in which variation in particle size is suitably suppressed.
  • nanocarbon-loaded agglomerates are provided as compositions.
  • JIS K 6219-1 2005 (Carbon black for rubber-Characteristics of granulated particles-Part 1: How to determine fine powder)
  • the particle size (R) of the nanocarbon-blended aggregate measured by is, for example, 0.1 to 5%, preferably 0.2 to 3%, more preferably 0.2 to 1.5%. be.
  • the particle size (R) can be calculated based on the following formula.
  • R particle size (%)
  • E mass of nanocarbon on the sieve surface (g)
  • B Mass (g) of sample (containing all components)
  • a method for producing a nanocarbon-blended aggregate (1) A step of impregnating 100 parts by mass of nanocarbon with 0.1 to 10 parts by mass of a binder agent and 43 to 233 parts by mass of a liquid medium to obtain a solid aggregate, and (2) the solid aggregate.
  • a step of crushing to obtain a nanocarbon-blended aggregate comprising A method, wherein the hardness of the nanocarbon-blended aggregate measured in accordance with JIS K 6219-3 is 20 g or less.
  • the nanocarbon is at least one selected from carbon nanotubes and graphene.
  • the binder agent is at least one selected from the group consisting of a graft type polymer having a polyoxyalkylene chain, an amine-based polymer and a cellulose-based polymer, citric acid, and sodium bicarbonate [1] The method according to any one of to [3].
  • step (1) is (1a) a step of preparing a binder liquid containing the binder agent and the liquid medium; and (1b) a step of impregnating the nanocarbon with the binder liquid to obtain the solid aggregate, [1] to The method according to any one of [5].
  • step (1b) is performed under conditions selected from the group consisting of a reduced pressure atmosphere, a pressurized atmosphere and a combination thereof.
  • the reduced pressure atmosphere is 50 to 5 Pa.
  • pressurized atmosphere is 0.1 to 5 MPa.
  • JIS Japanese Industrial Standards
  • Table 1 shows the physical properties of the CNTs (trade names: K-Nanos-100P, 100T, 210T, 300T, 500T, manufactured by Kumho Petrochemical) used in the following experiments.
  • the obtained solid agglomerate was continuously sheared and crushed by a multi-stage rotary cutter mill to obtain the desired CNT-blended agglomerate.
  • the physical properties (bulk density, carbon content, average particle size, particle size, particle hardness) of the CNT-blended agglomerates were measured by the following methods.
  • the bulk density was obtained according to the method for measuring the bulk density of carbon black specified in JIS K 6219.
  • carbon content The carbon content was obtained by subtracting the ash content (%) measured according to JIS K 6218-2 from 100%.
  • the morphology of the CNT-blended aggregates was observed by scanning electron microscopy (SEM). Observation was performed by using a 300-fold SEM image, measuring the outer diameter of 100 CNT-blended aggregates at random, and taking the number average value as the average particle size (mm) of the CNT-blended aggregates.
  • particle size In addition, the particle size (R) of the CNT blended aggregate was calculated based on the following formula according to JIS K 6219-1:2005. R: particle size (%) E: mass of nanocarbon on the sieve surface (g) B: Mass (g) of sample (containing all components)
  • the hardness of the particles was measured according to JIS K 6219-3 (Carbon black-Determination of hardness of granulated particles).
  • a 2 mm wide section is cut from the edge of the sheet of the obtained CNT-blended aggregate, and the cut surface is scanned using an atomic force microscope (MFP-3D-SA-J, manufactured by Oxford Instruments). It was observed (100 times) in AC mode (tapping mode) at a size of 40 ⁇ m ⁇ 40 ⁇ m. An AFM photograph is shown in FIG.
  • Example 1 2 kg of powdered nanocarbon (CNT) was placed in an inclined stirring tank (PT40SMV, manufactured by Masellar), and the pressure was reduced. Next, in an inclined shaft type stirring tank (ST-J-ASC-36, manufactured by Shinto Corporation), a liquid medium (process oil, manufactured by Nippon Sun Oil Co., Ltd.) and a binder agent (Malialim AKM0531, manufactured by NOF Corporation). was stirred (100 rpm) to prepare a binder solution (binder concentration: 10% by mass, 4 g), and the binder solution was added dropwise to the CNTs in an inclined stirring vessel while being stirred in a reduced pressure atmosphere (10 Pa).
  • a binder solution binder concentration: 10% by mass, 4 g
  • Example 2 A CNT-blended agglomerate was produced in the same manner as in Example 1 except that the binder was changed to polyethylene wax (with a binder concentration of 10% by mass), and AFM observation was performed in the same manner as described above.
  • the hardness of the particles of the CNT-blended aggregates of Examples was 10 g or less, and the hardness particle size distribution was narrow.
  • the hardness of the particles is suppressed to a low level, and as a result, it is considered that the dispersion is suppressed and the dispersibility is improved.
  • Example 1 since it is not necessary to perform the drying process, it is possible to avoid an increase in the hardness of the particles due to densification in the granulation process, which is considered to contribute to the improvement of the dispersibility of the particles of the CNT-blended aggregates. .
  • Example 1 CNT-blended agglomerates with high bulk density and dispersibility are continuously and efficiently produced in a closed system, so CNT dispersal can be prevented, and safety risks can be suppressed. It is possible.
  • the present invention it is possible to efficiently produce a nanocarbon-containing agglomerate that has good dispersibility, high bulk density, and low scattering properties. Moreover, according to the present invention, the dispersibility of the nanocarbon-containing aggregate can be improved, and the workability such as workability and handleability can be significantly improved.
  • the blending treatment is performed in a closed system in a solid state, and the nanocarbon-blended agglomerate particles can be produced by continuous pulverization treatment, which is advantageous in terms of reducing the environmental load. .
  • nanocarbon-blended aggregates with good particle size distribution can be rapidly mass-produced at low cost without the need for large-scale equipment, which is particularly advantageous in terms of industrial production.

Abstract

[Problem] To produce nanocarbon-blended aggregates having satisfactory dispersion properties with high efficiency. [Solution] A method for producing nanocarbon-blended aggregates is employed, which comprises (1) a step for impregnating 100 parts by mass of nanocarbon with 1 to 10 parts by mass of a binder agent and 43 to 233 parts by mass of a liquid medium to produce solid aggregates and (2) a step for disintegrating the solid aggregates to produce nanocarbon-blended aggregates, in which the hardness of the nanocarbon-blended aggregates as measured in accordance with JIS K 6219-3 is 10 g or less.

Description

ナノカーボン配合凝集物およびその製造方法Nanocarbon compound aggregate and method for producing same
　本発明は、ナノカーボン配合凝集物およびその製造方法に関する。 The present invention relates to a nanocarbon compound aggregate and a method for producing the same.
　近年、カーボンナノチューブ（以下、「ＣＮＴ」ともいう。）、カーボンナノファイバー（以下、「ＣＮＦ」ともいう。）、カーボンナノコイル（以下、「ＣＮＣ」ともいう。）、グラフェン（以下、「ＧＰＮ」ともいう。）等のナノカーボン材料の様々な分野における応用が期待されている。中でも、ＣＮＴは夢の次世代材料として注目され、帯電防止剤や導電性付与材としての使用はもちろん、タイヤ、キャパシタ、Ｌｉ電池の導電助剤、繊維強化プラスチックス等への活用に向けた用途開発が進められている。 In recent years, carbon nanotubes (hereinafter also referred to as “CNT”), carbon nanofibers (hereinafter also referred to as “CNF”), carbon nanocoils (hereinafter also referred to as “CNC”), graphene (hereinafter referred to as “GPN”) It is also called.) and other nanocarbon materials are expected to be applied in various fields. Among them, CNT is attracting attention as a dream next-generation material, and it is used not only as an antistatic agent and conductivity imparting agent, but also for tires, capacitors, conductive additives for Li batteries, fiber-reinforced plastics, etc. Development is underway.
　ＣＮＴは直径が数ｎｍ～約５００ｎｍで、長さが１０μｍ～１０００μｍ程度であり、アスペクト比が大きく、チューブ状構造の炭素の結晶である。その種類は多岐にわたり、単層構造を有するシングルウオールＣＮＴ、多層構造を有するマルチウオールＣＮＴの範疇に入る２層のダブルウオールＣＮＴ等がある。また、両端が封鎖されているものから、片末端だけが封鎖されているもの、両末端とも開いているものがあり、また、丸め方の構造にもアームチェア型等いくつか種類がある。 CNTs are carbon crystals with a diameter of several nm to about 500 nm, a length of about 10 μm to 1000 μm, a large aspect ratio, and a tubular structure. There are a wide variety of types, including single-wall CNTs having a single-layer structure, double-wall CNTs having two layers that fall into the category of multi-wall CNTs having a multi-layer structure, and the like. In addition, there are some that are closed at both ends, some that are closed only at one end, and others that are open at both ends.
　一般に、ＣＮＴは、種々の合成樹脂やゴム等の基材に配合されることで、基材に電気伝導性や高弾性、高強度、熱伝導性等を付与することが知られている。 　In general, CNTs are known to impart electrical conductivity, high elasticity, high strength, thermal conductivity, etc. to base materials by being blended with base materials such as various synthetic resins and rubbers.
　しかしながら、ナノカーボンを使用するにあたっては、その低い嵩密度による粉塵飛散の問題や、ナノカーボン粒子の凝集による分散不良等の課題がある。そのため「夢の素材」と期待された割には実用化が進んでいない。 However, when using nanocarbon, there are problems such as dust scattering due to its low bulk density and poor dispersion due to aggregation of nanocarbon particles. For this reason, although it was expected to be a "dream material," it has not been put to practical use.
　近年、ナノカーボン配合凝集物の嵩密度を向上させ、粉塵飛散を防止するための様々な手法が報告されている。例えば、特許文献１では、水溶性ポリマーを所定濃度で含有する水溶液をＣＮＴに含浸させて固体凝集物とし、それを剪断破砕処理した後に乾燥することで、簡易かつ簡便に嵩密度が高く飛散性の低いＣＮＴ配合凝集物を効率的に取得しうることが、本出願人により報告されている。しかしながら、特許文献１には、ＣＮＴ配合凝集物による分散性については何ら報告されていない。 In recent years, various methods have been reported to improve the bulk density of nanocarbon-containing agglomerates and prevent dust scattering. For example, in Patent Document 1, CNTs are impregnated with an aqueous solution containing a water-soluble polymer at a predetermined concentration to form a solid aggregate, which is subjected to a shear crushing treatment and then dried to achieve a high bulk density and dispersibility in a simple and convenient manner. The present applicant has reported that CNT-blended agglomerates with a low M can be efficiently obtained. However, Patent Document 1 does not report anything about the dispersibility of CNT-blended aggregates.
　ＣＮＴもしくはグラフェン等のナノカーボンと凝集媒体とのナノカーボン配合凝集物を調製する場合、凝集媒体がナノカーボンに均一に付着浸透せず、不均一なナノカーボン配合凝集物が形成されて粒度分布が歪になり、その結果、ＣＮＴ配合凝集物の品質が一定せず、ハンドリング性が低下することがある。したがって、分散性の向上したナノカーボン配合凝集物を効率的に取得ことは、当該技術分野において依然として重要な課題といえる。 When preparing a nanocarbon-containing aggregate of nanocarbon such as CNT or graphene and an aggregation medium, the aggregation medium does not uniformly adhere to and permeate the nanocarbon, forming a non-uniform nanocarbon-containing aggregate, resulting in a poor particle size distribution. This can result in inconsistent quality of the CNT-blended agglomerate and reduced handling properties. Therefore, it can be said that efficiently obtaining nanocarbon-blended agglomerates with improved dispersibility is still an important issue in this technical field.
特許第６７１４１３４号公報Japanese Patent No. 6714134
　本発明は、分散性の良好なナノカーボン配合凝集物を効率的に取得することを一つの目的としている。 One object of the present invention is to efficiently obtain nanocarbon-blended aggregates with good dispersibility.
　本発明者らは、今般、バインダー剤を所定濃度で含有する溶液をＣＮＴに含浸させて凝集物とし、それを解砕処理することで分散性の良好なナノカーボン配合凝集物を効率的に取得しうることを見出した。本発明はかかる知見に基づくものである。 The inventors of the present invention impregnated CNTs with a solution containing a predetermined concentration of a binder agent to form aggregates, and then pulverized the aggregates to efficiently obtain nanocarbon-blended aggregates with good dispersibility. I found what I could do. The present invention is based on such findings.
　本発明の一実施形態によれば、ナノカーボン配合凝集物の製造方法であって、
（１）ナノカーボン１００質量部に対して、１～１０質量部のバインダー剤および４３～２３３質量部の液媒体を含浸させて固体凝集物を得る工程、および
（２）上記固体凝集物を解砕処理してナノカーボン配合凝集物を得る工程、
を含んでなり、
　ＪＩＳ　Ｋ　６２１９－３に準拠して測定される上記ナノカーボン配合凝集物の硬度が１０ｇ以下である、方法が提供される。 According to one embodiment of the present invention, a method for producing a nanocarbon-blended agglomerate, comprising:
(1) A step of impregnating 100 parts by mass of nanocarbon with 1 to 10 parts by mass of a binder agent and 43 to 233 parts by mass of a liquid medium to obtain a solid aggregate, and (2) dissolving the solid aggregate. a step of crushing to obtain a nanocarbon-blended aggregate;
comprising
A method is provided, wherein the hardness of the nanocarbon-blended aggregate measured according to JIS K 6219-3 is 10 g or less.
　また、本発明の別の実施形態によれば、上記方法により得られた、ナノカーボン配合凝集物が提供される。 In addition, according to another embodiment of the present invention, there is provided a nanocarbon-containing aggregate obtained by the above method.
　本発明によれば、分散性の良好なナノカーボン配合凝集物を効率的に取得することができる。本発明は、分散性が良好であり、嵩密度が高く飛散性の低いナノカーボン配合凝集物を効率的に取得する上で有利に利用することができる。また、本発明によれば、ナノカーボン配合凝集物の分散性を向上させることにより、加工性・ハンドリング性等の作業性を向上させることが可能である。また、本発明によれば、閉鎖系の固相状態で配合処理、解砕処理を連続的に実施してナノカーボン配合凝集物を提供しうることから、環境負荷を低減する上で有利である。また、本発明によれば、大掛かりな設備を必要とせず、ナノカーボン配合凝集物を低原価で簡便にかつ迅速に量産できることから、工業生産上特に有利である。 According to the present invention, it is possible to efficiently obtain nanocarbon-blended aggregates with good dispersibility. INDUSTRIAL APPLICABILITY The present invention can be advantageously used to efficiently obtain a nanocarbon-containing agglomerate that has good dispersibility, high bulk density, and low scattering properties. Further, according to the present invention, by improving the dispersibility of the nanocarbon-containing aggregate, it is possible to improve workability such as workability and handleability. In addition, according to the present invention, the blending treatment and the crushing treatment can be continuously performed in a closed system solid phase state to provide nanocarbon-blended agglomerates, which is advantageous in terms of reducing the environmental load. . Moreover, according to the present invention, the nanocarbon-blended agglomerates can be mass-produced simply and quickly at low cost without requiring large-scale equipment, which is particularly advantageous in terms of industrial production.
参考例１で得られたＣＮＴ配合凝集物のＡＦＭ写真（１００倍）。An AFM photograph (100 times) of the CNT-blended aggregate obtained in Reference Example 1. 実施例１で得られたＣＮＴ配合凝集物のＡＦＭ写真（１００倍）。An AFM photograph (100 times) of the CNT-blended aggregate obtained in Example 1. FIG. ＣＮＴ配合凝集物の凝集塊の大きさの分布Aggregate size distribution of CNT blended agglomerates
　本発明の一実施形態によれば、ナノカーボン配合凝集物の製造方法であって、
（１）ナノカーボン１００質量部に対して、１～１０質量部のバインダー剤および４３～２３３質量部の液媒体を含浸させて固体凝集物を得る工程、および
（２）上記固体凝集物を解砕処理してナノカーボン配合凝集物を得る工程、
を含んでなり、
　ＪＩＳ　Ｋ　６２１９－３に準拠して測定される上記ナノカーボン配合凝集の硬度が１０ｇ以下である、方法が提供される。
　以下、本発明によるナノカーボン配合凝集物の製造方法を工程毎に詳細に説明する。 According to one embodiment of the present invention, a method for producing a nanocarbon-blended agglomerate, comprising:
(1) A step of impregnating 100 parts by mass of nanocarbon with 1 to 10 parts by mass of a binder agent and 43 to 233 parts by mass of a liquid medium to obtain a solid aggregate, and (2) dissolving the solid aggregate. a step of crushing to obtain a nanocarbon-blended aggregate;
comprising
A method is provided, wherein the hardness of the nanocarbon-blended aggregate measured in accordance with JIS K 6219-3 is 10 g or less.
Hereinafter, each step of the method for producing a nanocarbon-containing aggregate according to the present invention will be described in detail.
［工程（１）］
　本発明の一実施形態によれば、工程（１）において、ナノカーボン１００質量部に対して、１～１０質量部のバインダー剤および４３～２３３質量部の液媒体を含浸させて固体凝集物を得る。理論に拘束されるものでないが、上記各成分を所定の配合量で接触させることにより、凝集現象と被覆現象が好適なバランスで生じ、固体凝集物が生成するものと考えられる。すなわち、凝集現象においては、２つ以上のナノカーボン粒子の間に存在するバインダー剤と液媒体が界面張力で粒子を結合して大きなナノカーボン含有粒子を形成し、一方で、ナノカーボン含有粒子表面に付着したバインダー剤と液媒体は、ナノカーボン含有粒子を被覆して層を形成する。このような凝集現象と被覆現象を繰り返して、固体凝集物は安定して生成するものと考えられる。 [Step (1)]
According to one embodiment of the present invention, in step (1), 100 parts by mass of nanocarbon is impregnated with 1 to 10 parts by mass of a binder agent and 43 to 233 parts by mass of a liquid medium to form a solid aggregate. obtain. Although it is not bound by theory, it is believed that by contacting each of the above components in a predetermined blending amount, the agglomeration phenomenon and the coating phenomenon occur in a suitable balance to form a solid agglomerate. That is, in the aggregation phenomenon, the binder agent and liquid medium present between two or more nanocarbon particles bind the particles by interfacial tension to form large nanocarbon-containing particles, while the surface of the nanocarbon-containing particles The binder agent and liquid medium adhering to the nanocarbon-containing particles coat the nanocarbon-containing particles to form a layer. It is considered that solid aggregates are stably generated by repeating such aggregation phenomenon and coating phenomenon.
　本発明でいう「ナノカーボン」とは、ナノメートル（１０億分の１ｍ）の大きさの構造をもつカーボンからなる物質群の総称である。ナノカーボンとしては、ＣＮＴ、ＣＮＦ、ＣＮＣ、ＧＰＮ、フラーレンまたはＧＰＮ等が挙げられるが、好ましくはＣＮＴまたはＧＰＮであり、より好ましくはＣＮＴである。なお、本発明でいう「グラフェン（ＧＰＮ）」とは、１原子の厚さのｓｐ２結合炭素原子のシートだけでなく、複数のシートからなるが商業的にグラフェンの名前が付けられている物質を含む。 "Nanocarbon" as used in the present invention is a general term for a group of substances made of carbon having a nanometer (1/1,000,000,000 m) size structure. Examples of nanocarbon include CNT, CNF, CNC, GPN, fullerene, GPN and the like, preferably CNT or GPN, more preferably CNT. In the present invention, “graphene (GPN)” refers not only to a one-atom-thick sheet of sp2-bonded carbon atoms, but also to a substance composed of multiple sheets but commercially named graphene. include.
　本発明において使用するＣＮＴに特に制限はなく、単層構造を有するシングルウオールＣＮＴ、多層構造を有するマルチウオールＣＮＴの範疇に入る２層のダブルウオールＣＮＴ等いずれの形態であってもよい。また、ＣＮＴは製造方法により得られる形態が異なることが知られているが、本発明においては、アーク放電型、触媒気相製造法、レーザーアブレーション法、その他の方法を含め、いずれの製造方法により得られたものであってもよい。 The CNTs used in the present invention are not particularly limited, and may be in any form, such as single-wall CNTs having a single-layer structure, double-wall CNTs falling into the category of multi-wall CNTs having a multi-layer structure, and the like. In addition, it is known that CNTs have different morphologies depending on the manufacturing method. It may be obtained.
　本発明のナノカーボン配合凝集物の製造方法に使用される原料としてのＣＮＴは、電気的・機
械的な特性や分散性等の物性の優位性を確保する観点から、繊維径は、好ましくは１ｎｍ～２００ｎｍであり、より好ましくは１ｎｍ～１５０ｎｍであり、さらに好ましくは１ｎｍ～１００ｎｍである。 The CNT as a raw material used in the method for producing the nanocarbon compound aggregate of the present invention preferably has a fiber diameter of 1 nm from the viewpoint of ensuring superior physical properties such as electrical and mechanical properties and dispersibility. ~200 nm, more preferably 1 nm to 150 nm, even more preferably 1 nm to 100 nm.
　また、ＣＮＴの繊維長は、導電性や機械的特性、分散性の確保や繊維の切断の回避の観点から、好ましくは０．１μｍ～２０００μｍであり、より好ましくは０．１μｍ～１０００μｍであり、さらに好ましくは０．１μｍ～５００μｍである。 In addition, the fiber length of CNT is preferably 0.1 μm to 2000 μm, more preferably 0.1 μm to 1000 μm, from the viewpoint of ensuring conductivity, mechanical properties, dispersibility, and avoiding fiber breakage. More preferably, it is 0.1 μm to 500 μm.
　ＣＮＴのアスペクト比としては、通常１０～１００００程度であり、六角網目状のグラファイトシートが円筒状をなした構造物が好適に用いられる。単層のＣＮＴ、多層のＣＮＴいずれでもよく、最終の目的に応じて選択することができる。また、ＣＮＴの製造方法に関しても制限されるものではなく、炭素含有ガスを触媒と接触させる熱分解法、炭素棒間にてアーク放電を発生させるアーク放電法、カーボンターゲットにレーザーを照射するレーザー蒸発法、金属微粒子の存在下で炭素源のガスを高温で反応させるＣＶＤ法、一酸化炭素を高圧下で分解するＨｉＰｃｏ法等のいずれでもよい。また、金属原子をドープしたＣＮＴでもよい。また、これらのＣＮＴは、単独または複数種を組み合わせて用いてもよい。 The aspect ratio of CNT is usually about 10 to 10,000, and a structure in which a hexagonal network-like graphite sheet has a cylindrical shape is preferably used. Either single-layer CNTs or multilayer CNTs may be used, and can be selected according to the final purpose. In addition, the CNT production method is not limited, and includes a thermal decomposition method in which a carbon-containing gas is brought into contact with a catalyst, an arc discharge method in which an arc discharge is generated between carbon rods, and a laser evaporation method in which a carbon target is irradiated with a laser. CVD method in which carbon source gas is reacted at high temperature in the presence of fine metal particles, HiPco method in which carbon monoxide is decomposed under high pressure. CNTs doped with metal atoms may also be used. In addition, these CNTs may be used singly or in combination.
　また、本発明の一実施形態によれば、バインダー剤としては、ナノカーボン表面の濡れ性を改善する観点から、例えば、両親媒性の高分子または低分子化合物等の界面活性剤が使用されるが、好ましくはポリオキシアルキレン鎖を有するグラフト型ポリマー、アミン系ポリマーまたはセルロース系ポリマー等である。 Further, according to one embodiment of the present invention, as the binder agent, from the viewpoint of improving the wettability of the nanocarbon surface, for example, a surfactant such as an amphipathic polymer or low-molecular-weight compound is used. However, it is preferably a graft type polymer having a polyoxyalkylene chain, an amine-based polymer, a cellulose-based polymer, or the like.
　ポリオキシアルキレン鎖を有するグラフト型ポリマーとしては、例えば、ポリオキシアルキレン鎖をグラフト鎖として有する多官能櫛型の機能性ポリマーが挙げられる。 Examples of graft-type polymers having polyoxyalkylene chains include polyfunctional comb-shaped functional polymers having polyoxyalkylene chains as graft chains.
　ポリオキシアルキレン鎖をグラフト鎖として有する多官能櫛型の機能性ポリマーとしては、例えば、（ａ）下式（Ｉ）で表されるポリオキシアルキレンアルキルエーテル単位、（ｂ）無水マレイン酸単位、（ｃ）スチレン単位で構成され、これらの組成比がモル％で（ａ）：（ｂ）：（ｃ）＝２５～７５：２５～７５：０～５０であるアリルアルコール・無水マレイン酸・スチレン共重合物とポリオキシアルキレンモノアルキルアルコールとのグラフト化物が挙げられる。
Figure JPOXMLDOC01-appb-C000001
 Examples of the polyfunctional comb-shaped functional polymer having a polyoxyalkylene chain as a graft chain include (a) a polyoxyalkylene alkyl ether unit represented by the following formula (I), (b) a maleic anhydride unit, ( c) an allyl alcohol/maleic anhydride/styrene mixture composed of styrene units and having a composition ratio of (a):(b):(c) = 25 to 75:25 to 75:0 to 50 in mol%; A grafted product of a polymer and a polyoxyalkylene monoalkyl alcohol can be mentioned.
Figure JPOXMLDOC01-appb-C000001
　上記（ｃ）のスチレン単位が０モル％の場合は、スチレン単位が含まれない場合であり、この場合は、機能性ポリマーは、（ａ）下記式（Ｉ）で表されるポリオキシアルキレンアルキルエーテル単位、（ｂ）無水マレイン酸単位で構成され、これらの組成比がモル％で（ａ）：（ｂ）＝２５～７５：２５～７５であるアリルアルコール・無水マレイン酸共重合物とポリオキシアルキレンモノアルキルアルコールとのグラフト化物である。 When the styrene unit in (c) is 0 mol%, it means that the styrene unit is not contained, and in this case, the functional polymer is (a) a polyoxyalkylene alkyl represented by the following formula (I) an allyl alcohol/maleic anhydride copolymer and a poly It is a grafted product with oxyalkylene monoalkyl alcohol.
　上記（ｃ）のスチレン単位を含む場合において、上記（ａ）～（ｃ）の好ましい組成比は、モル％で（ａ）：（ｂ）：（ｃ）＝２５～４０：２５～４０：２０～５０となるものが好ましい。 In the case where the above (c) styrene unit is included, the preferred composition ratio of the above (a) to (c) is (a):(b):(c) = 25 to 40:25 to 40:20 in mol%. ~50 is preferred.
　上記成分（ｂ）のエチレンオキサイド単位の付加モル数、好ましくは、式（Ｉ）中のｍは、５～５０モルである。 The number of moles of added ethylene oxide units in the component (b), preferably m in formula (I), is 5 to 50 moles.
　また、Ｒは炭素数１～５の直鎖または分岐を有するアルキル基であり、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基の直鎖のもの；イソプロピル基、イソブチル基、イソペンチル基の分岐鎖のもの；シクロプロピル基、シクロペンチル基の環状のもの等が挙げられる。 In addition, R is a linear or branched alkyl group having 1 to 5 carbon atoms, for example, linear methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group; isopropyl a branched group such as a group, an isobutyl group and an isopentyl group; a cyclic group such as a cyclopropyl group and a cyclopentyl group;
　本発明に用いるアリルアルコール・無水マレイン酸・スチレン共重合物とポリオキシアルキレンモノアルキルエーテルとのグラフト化物としては、例えば、下記式（ＩＩ）、また、アリルアルコール・無水マレイン酸共重合物とポリオキシアルキレンモノアルキルエーテルとのグラフト化物としては、下記式（ＩＩＩ）に示すものが例示され、これらは単独でまたは２種以上を混合して使用することができる。 Examples of the allyl alcohol/maleic anhydride/styrene copolymer and polyoxyalkylene monoalkyl ether grafted product used in the present invention include the following formula (II), and the allyl alcohol/maleic anhydride copolymer and poly Grafted products with oxyalkylene monoalkyl ethers are exemplified by those represented by the following formula (III), and these can be used alone or in combination of two or more.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　より具体的な例としては、上記式（ＩＩ）中、ｍ＝１１、ｎ＝２０となるグラフト化物、市販品ではマリアリムＡＫＭ－０５３１（日油社製）；上記式（ＩＩ）中、ｍ＝１３、ｎ＝１８、質量平均分子量：４００００となるグラフト化物、市販品ではマリアリムＡＡＢ－０８５１（日油社製）；上記式（ＩＩ）中、ｍ＝２８、ｎ＝２０となるグラフト化物、市販品ではマリアリムＡＦＢ－１５２１（日油社製）等が挙げられる。なお、上記式（ＩＩ）中のｎは、正の数である〔下記式（ＩＩＩ）中も同様〕。 More specific examples include a grafted product in which m = 11 and n = 20 in the above formula (II), a commercially available product of Marialim AKM-0531 (manufactured by NOF Corporation); 13, n = 18, mass average molecular weight: 40000 grafted product, commercially available product Marialim AAB-0851 (manufactured by NOF Corporation); in the above formula (II), m = 28, n = 20 grafted product, commercially available Products include Marialim AFB-1521 (manufactured by NOF Corporation). Note that n in the above formula (II) is a positive number [the same applies to the following formula (III)].
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　より具体的な例としては、上記式（ＩＩＩ）中、ｍ＝１１、ｎ＝１４となるグラフト化物〔メトキシポリエチレングリコール（エチレンオキサイド１１モル付加）アリルエーテルと無水マレイン酸の共重合体〕、市販品ではマリアリムＳＣ－０５０５Ｋ（日油社製）等が挙げられる。 As a more specific example, in the above formula (III), m = 11, n = 14 grafted product [copolymer of methoxypolyethylene glycol (11 mol of ethylene oxide added) allyl ether and maleic anhydride], commercially available Products include Marialim SC-0505K (manufactured by NOF Corporation).
　本発明の一実施形態によれば、アミン系ポリマーとしてはジアリルアミン系カチオンポリマーを好適に使用することができる。ジアリルアミン系カチオンポリマーはジアリルアミンの塩酸塩、硫酸塩等の２級アミン塩のポリマー、ポリジアリルジアルキルアンモニウムクロライド、ポリジアリルジアルキルアンモニウムブロマイド等の４級アンモニウム塩のポリマー等が挙げられるが、これらのうち、４級アンモニウム塩のポリマーが好ましく、ポリ（ジアリルジメチルアンモニウムクロイド）（ＰＤＡＤＭＡＣ）等のポリマーが特に好ましい。 According to one embodiment of the present invention, a diallylamine-based cationic polymer can be suitably used as the amine-based polymer. Examples of the diallylamine-based cationic polymer include polymers of secondary amine salts such as diallylamine hydrochloride and sulfate, and polymers of quaternary ammonium salts such as polydiallyldialkylammonium chloride and polydiallyldialkylammonium bromide. Polymers of quaternary ammonium salts are preferred, and polymers such as poly(diallyldimethylammonium chloride) (PDADMAC) are particularly preferred.
　また、本発明の別の実施形態によれば、アミン系ポリマーは、少なくとも１種の４級アンモニウム基を有するモノマーおよび少なくとも１種の４級アンモニウム基を有さない多官能性モノマーの重合により得られるコポリマーであってもよい。４級アンモニウム基を有するモノマーと多官能性モノマーに対する質量比は、好ましくは９０／１０～１０／９０であり、より好ましくは７５／２５～４０／６０であり、さらに好ましくは６０／４０～５０／５０である。 Also, according to another embodiment of the present invention, the amine-based polymer is obtained by polymerization of at least one monomer having a quaternary ammonium group and at least one polyfunctional monomer having no quaternary ammonium group. It may be a copolymer that is The mass ratio of the monomer having a quaternary ammonium group to the polyfunctional monomer is preferably from 90/10 to 10/90, more preferably from 75/25 to 40/60, even more preferably from 60/40 to 50. /50.
　アミン系ポリマーである上記コポリマーの構成要素のうち、４級アンモニウム基を有するモノマーは、好ましくは、下記式（ＩＶ）：
Figure JPOXMLDOC01-appb-C000004
 　（式（ＩＶ）において、Ｒ１は、ＨまたはＣ１～Ｃ４－アルキルであり、Ｒ２は、Ｈまたはメチルであり、Ｒ３は、Ｃ１～Ｃ４－アルキレンであり、Ｒ４、Ｒ５およびＲ６は、それぞれ独立にＨまたはＣ１～Ｃ３０－アルキルであり、Ｘは、－Ｏ－または－ＮＨ－であり、Ｙは、Ｃｌ、Ｂｒ、Ｉ、硫酸水素塩またはメト硫酸塩である。）のモノマーから選択されてもよい。好ましい式（Ｉ）のモノマーとしては、Ｒ１およびＲ２がそれぞれＨであるか、または、Ｒ１がＨでありＲ２がＣＨ３または好ましくは同様にＨである。 Among the constituents of the copolymer, which is an amine-based polymer, the monomer having a quaternary ammonium group preferably has the following formula (IV):
Figure JPOXMLDOC01-appb-C000004
 (In formula (IV), R 1 is H or C 1 -C 4 -alkyl, R 2 is H or methyl, R 3 is C 1 -C 4 -alkylene, R 4 , R 5 and R 6 are each independently H or C 1 -C 30 -alkyl, X is —O— or —NH—, Y is Cl, Br, I, hydrogensulfate or methosulfate salts.) monomers. For preferred monomers of formula (I), R 1 and R 2 are each H, or R 1 is H and R 2 is CH 3 or preferably H as well.
　特に好ましい式（ＩＶ）のモノマーは、ジメチルアミノエチルアクリレートメトクロリド（ＤＭＡ３＊ＭｅＣｌ）とも称される［２－（アクリロイルオキシ）エチル］トリメチルアンモニウムクロリドまたはジメチルアミノエチルメタクリレートメトクロリド（ＤＭＡＥＭＡ＊ＭｅＣｌ）とも称されるトリメチル－［２－（２－メチルプロパ－２－エノイルオキシ）エチル］アザニウムクロリドである。 Particularly preferred monomers of formula (IV) are [2-(acryloyloxy)ethyl]trimethylammonium chloride, also called dimethylaminoethyl acrylate metochloride (DMA3*MeCl) or dimethylaminoethyl methacrylate metochloride (DMAEMA*MeCl). trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium chloride.
　また、アミン系ポリマーである上記コポリマーの構成要素のうち、少なくとも１種の４級アンモニウム基を有さない多官能性モノマーとしては、アクリル酸、メタクリル酸、Ｎ－ビニルピロリドン、Ｎ－ビニルイミダゾール、イタコン酸またはマレイン酸のメチルエステルまたはエチルエステル、アクリル酸エチルまたはアクリル酸メチル等が挙げられる。 Further, among the constituents of the above-described copolymer which is an amine-based polymer, at least one polyfunctional monomer having no quaternary ammonium group includes acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinylimidazole, Examples include methyl ester or ethyl ester of itaconic acid or maleic acid, ethyl acrylate or methyl acrylate, and the like.
　また、一実施形態によれば、アミン系ポリマーである上記コポリマーの構成要素のうち、上記４級アンモニウム基を有さない多官能性モノマーは、好ましくは、下記式（Ｖ）：
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ７は、ＨまたはＣ１～Ｃ４－アルキルであり、Ｒ８は、Ｈまたはメチルであり、Ｒ９およびＲ１０は、互いに独立に、ＨまたはＣ１～Ｃ３０－アルキルである）で表されるモノマーから選択される。 Further, according to one embodiment, among the constituents of the copolymer, which is an amine-based polymer, the polyfunctional monomer having no quaternary ammonium group preferably has the following formula (V):
Figure JPOXMLDOC01-appb-C000005
 (wherein R 7 is H or C 1 -C 4 -alkyl, R 8 is H or methyl, R 9 and R 10 are independently of each other H or C 1 -C 30 -alkyl is selected from the monomers represented by
　上記式（Ｖ）のモノマーは、好ましくは、アクリルアミド、メタクリルアミドまたはジアルキルアミノアクリルアミドである。 The monomer of formula (V) above is preferably acrylamide, methacrylamide or dialkylaminoacrylamide.
　また、上記した多官能性モノマーにおいて、４級アンモニウム基を有さない多官能性モノマーとしては、下記式（ＶＩ）：
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒａは、ＨまたはＣ６～Ｃ５０－アルキルであり、Ｒｂは、ＨまたはＣ１～Ｃ４－アルキルであり、Ｒｃは、Ｈまたはメチルであり、
　ｎは、０～１００の整数である）で表される非アミン系モノマーでもよい。 In addition, among the polyfunctional monomers described above, the polyfunctional monomer having no quaternary ammonium group has the following formula (VI):
Figure JPOXMLDOC01-appb-C000006
 (wherein Ra is H or C 6 -C 50 -alkyl, Rb is H or C1-C4-alkyl, Rc is H or methyl,
n is an integer of 0 to 100).
　上記式（ＶＩ）の非アミン系モノマーにおいて、Ｒａは、好ましくはＣ８～Ｃ３０－アルキルであり、より好ましくはＣ１６～Ｃ２２－アルキルであり、Ｒｂは、好ましくはＨであり、ｎは、好ましくは３～５０である。 In the non-amine monomers of formula (VI) above, Ra is preferably C 8 -C 30 -alkyl, more preferably C 16 -C 22 -alkyl, Rb is preferably H, n is preferably 3-50.
　式（ＩＩＩ）の非アミン系モノマーは、好ましくは、脂肪族アルコールエトキシレートまたはそのメタクリレートである。 The non-amine monomer of formula (III) is preferably an aliphatic alcohol ethoxylate or its methacrylate.
　上記式（Ｉ）、上記式（ＩＩ）、および上記式（ＩＩＩ）のモノマーは各々、アミン系ポリマーを構成するコポリマー中において複数種を用いてもよい。したがって、例えば、上記式（ＩＩＩ）のモノマーのＲ基は、Ｃ１６およびＣ１８等、異なる鎖長を有するモノマーがコポリマー中に存在してもよい。 Multiple types of each of the monomers of formula (I), formula (II), and formula (III) may be used in the copolymer constituting the amine-based polymer. Thus, for example, the R groups of the monomers of formula (III) above may be present in the copolymer with monomers having different chain lengths, such as C16 and C18 .
　一実施形態によればアミン系ポリマーを構成するコポリマーは、好ましくは（メタ）アクリル酸ジアルキルアミノアルキルと、（メタ）アクリル酸アルキル、（メタ）アクリル酸ヒドロキシアルキルおよびこれらの組み合わせから選択されるモノマー単位とから構成されるコポリマーである。より具体的には、上記コポリマーは、好ましくは（メタ）アクリル酸ジＣ１～Ｃ２アルキルアミノＣ１～Ｃ２アルキルと、（メタ）アクリル酸Ｃ１～Ｃ４アルキル、および（メタ）アクリル酸モノヒドロキシＣ２～Ｃ４アルキルおよびこれらの組み合わせから選択されるモノマー単位して含んでなるコポリマーであり、より好ましくは（メタ）アクリル酸メチル・（メタ）アクリル酸ブチル・（メタ）アクリル酸ジメチルアミノエチルコポリマーであり、さらに好ましくはメタアクリル酸メチル・メタアクリル酸ブチル・メタアクリル酸ジメチルアミノエチルコポリマーである。このようなメタアクリル酸メチル・メタアクリル酸ブチル・メタアクリル酸ジメチルアミノエチルコポリマーとしては、市販のものを使用してもよく、例えば、オイドラギット（登録商標）Ｅ１００（デグサ社）が挙げられる。 According to one embodiment, the copolymers that make up the amine-based polymer are preferably dialkylaminoalkyl (meth)acrylates and monomers selected from alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates and combinations thereof. It is a copolymer composed of units. More specifically, the copolymer preferably comprises diC 1 -C 2 alkylamino C 1 -C 2 alkyl (meth)acrylates, C 1 -C 4 alkyl ( meth ) acrylates, and (meth)acrylic A copolymer comprising as monomer units selected from acid monohydroxy C 2 -C 4 alkyl and combinations thereof, more preferably methyl (meth)acrylate/butyl (meth)acrylate/(meth)acrylic acid It is a dimethylaminoethyl copolymer, more preferably a methyl methacrylate/butyl methacrylate/dimethylaminoethyl methacrylate copolymer. As such a methyl methacrylate/butyl methacrylate/dimethylaminoethyl methacrylate copolymer, a commercially available one may be used, for example, Eudragit (registered trademark) E100 (Degussa).
　本発明の一実施形態によれば、セルロース系ポリマーとしては、カルボキシメチルセルロース、疎水変性カルボキシメチルセルロース、カチオン変性ヒドロキシエチルセルロース、カチオン変性ヒドロキシプロピルセルロース、カチオンおよび疎水変性ヒドロキシエチルセルロース、カチオンおよび疎水変性ヒドロキシプロピルセルロース、またはこれらの混合物等が挙げられるが、好ましくはカルボキシメチルセルロース、カチオン変性ヒドロキシエチルセルロース、カチオンおよび疎水変性ヒドロキシエチルセルロース、またはこれらの混合物であり、より好ましくはカルボキシメチルセルロースである。 According to one embodiment of the present invention, the cellulosic polymer includes carboxymethylcellulose, hydrophobically modified carboxymethylcellulose, cationically modified hydroxyethylcellulose, cationically modified hydroxypropylcellulose, cationically and hydrophobically modified hydroxyethylcellulose, cationically and hydrophobically modified hydroxypropylcellulose, and mixtures thereof, preferably carboxymethyl cellulose, cation-modified hydroxyethyl cellulose, cation- and hydrophobically-modified hydroxyethyl cellulose, or mixtures thereof, more preferably carboxymethyl cellulose.
　セルロース系ポリマーの具体的な例としては、Ｆｉｎｎｆｉｘ　ＧＤＡ（ＣＰ　Ｋｅｌｃｏによって販売）、例えば、商品名Ｆｉｎｎｆｉｘ　ＳＨ１（ＣＰ　Ｋｅｌｃｏ）として販売されているカルボキシメチルセルロースのアルキルケテン二量体誘導体、または商品名Ｆｉｎｎｆｉｘ　Ｖ（ＣＰ　Ｋｅｌｃｏによって販売）として販売されているブロック系カルボキシメチルセルロース等が挙げられる。 Specific examples of cellulosic polymers include Finnfix GDA (sold by CP Kelco), e.g., the alkylketene dimer derivative of carboxymethyl cellulose sold under the trade name Finnfix SH1 (CP Kelco), or the trade name Finnfix V (sold by CP Kelco) and the like.
　上記した以外のバインダー剤との具体例としては、カチオン化でんぷん、カチオン化グァーガム、変性ポリビニルアルコール、カチオン化ポリアクリルアミド、ポリアミドエピクロロヒドリン（ＰＡＥ）、メラミン樹脂誘導体、ポリビニルアミンまたはその誘導体、ポリビニルピリジンまたはその誘導体、ポリメタクリル酸エステル誘導体、ポリアクリル酸エステル誘導体、ポリアクリル酸ナトリウム誘導体、ポリエチレンイミンまたはその誘導体、ポリダドマック、ポリアルキレンポリアミンまたはその誘導体、ポリアリルアミンまたはその誘導体等のカチオン基（１～４級アンモニウム塩等）を主鎖または側鎖に導入されたポリマー、クエン酸、炭酸水素ナトリウム等が挙げられる。 Specific examples of binder agents other than those mentioned above include cationic starch, cationic guar gum, modified polyvinyl alcohol, cationic polyacrylamide, polyamide epichlorohydrin (PAE), melamine resin derivatives, polyvinylamine or its derivatives, polyvinyl Cationic groups (1 to quaternary ammonium salts, etc.) are introduced into the main chain or side chains, citric acid, sodium hydrogen carbonate, and the like.
　バインダー剤の分子量は、バインダー剤を含浸させるナノカーボンの種類にもよるが、ナノカーボンを液媒体中で分散安定化させる観点から、質量平均分子量が１，０００～１００，０００程度であってもよいが、好ましくは１，０００～５０，０００であり、より好ましくは１，５００～３，０００である。また、固体凝集物とした後に剪断して粒状物とした際の粒状物どうしの付着性（凝集性）の観点からは、質量平均分子量が８，０００～５０，０００であることが好ましい。なお、質量平均分子量は、ゲル・パーミエーション・クロマトグラフィー法（ＧＰＣ）法（ポリスチレン標準）により、定法に従って測定することができる。 The molecular weight of the binder agent depends on the type of nanocarbon impregnated with the binder agent. Good, but preferably 1,000 to 50,000, more preferably 1,500 to 3,000. Further, from the viewpoint of adhesion (aggregation) between granules when granules are formed by shearing after forming a solid aggregate, the weight average molecular weight is preferably 8,000 to 50,000. Incidentally, the mass average molecular weight can be measured according to a standard method by a gel permeation chromatography (GPC) method (polystyrene standard).
　また、本発明の一実施形態によれば、工程（１）において使用する液媒体は、例えば、有機溶剤オイル、可塑剤、水等であり、好ましくはプロセスオイルである。 Further, according to one embodiment of the present invention, the liquid medium used in step (1) is, for example, organic solvent oil, plasticizer, water, etc., preferably process oil.
　本発明の一実施形態において、上記工程（１）を実施する温度は特に限定されないが、例えば、５～５０℃であり、好ましくは３０～４０℃である。 In one embodiment of the present invention, the temperature at which step (1) is performed is not particularly limited, but is, for example, 5 to 50°C, preferably 30 to 40°C.
　また、本発明の一実施形態において、上記工程（１）は、２工程に分けて実施することができる。
　すなわち、本発明の好ましい実施形態において、上記工程（１）は、
　（１ａ）バインダー剤と液媒体とを含有するバインダー液を準備する工程、および
　（１ｂ）バインダー液をナノカーボンに含浸させて固体凝集物を得る工程
を含んでなる。 Moreover, in one embodiment of the present invention, the step (1) can be carried out in two steps.
That is, in a preferred embodiment of the present invention, the step (1) is
(1a) a step of preparing a binder liquid containing a binder agent and a liquid medium; and (1b) a step of impregnating nanocarbon with the binder liquid to obtain a solid aggregate.
　本発明の一実施形態においては、工程（１ａ）において、バインダー剤と液媒体と混合することによりバインダー液を調製する。 In one embodiment of the present invention, in step (1a), a binder liquid is prepared by mixing a binder agent and a liquid medium.
　バインダー剤の使用量は、ナノカーボン１００質量部に対して０．１～１０質量部の範囲内で適宜設定することができるが、好ましくは０．１５～５質量部であり、より好ましくは０．２～２質量部である。 The amount of the binder used can be appropriately set within the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of nanocarbon, preferably 0.15 to 5 parts by mass, more preferably 0. .2 to 2 parts by mass.
　また、液媒体の使用量は、ナノカーボン１００質量部に対して４３～２３３質量部の範囲で適宜設定することができるが、好ましくは８０～２００質量部であり、より好ましくは１００～１５０質量部である。 In addition, the amount of the liquid medium used can be appropriately set in the range of 43 to 233 parts by mass with respect to 100 parts by mass of nanocarbon, preferably 80 to 200 parts by mass, more preferably 100 to 150 parts by mass. Department.
　また、上記のように、工程（１）を工程（１ａ）および（１ｂ）のようにして実施する場合は、バインダー液におけるバインダー剤の濃度は、例えば、０．１～５質量％であり、好ましくは０．２～３質量％であり、より好ましくは０．２～２質量％である。 Further, as described above, when step (1) is carried out as steps (1a) and (1b), the concentration of the binder agent in the binder liquid is, for example, 0.1 to 5% by mass, It is preferably 0.2 to 3% by mass, more preferably 0.2 to 2% by mass.
　バインダー剤および液媒体を上述のような所定量に調整することは、工程（１ｂ）においてバインダー液を滴下する際に、液滴の大きさを適切な範囲留め、バインダー液の含浸処理を効率的に行うことができる。 Adjusting the binder agent and the liquid medium to the predetermined amounts as described above keeps the size of the droplets within an appropriate range when the binder liquid is dropped in step (1b), and the binder liquid impregnation treatment can be performed efficiently. can be done.
　本発明の一実施形態においては、バインダー剤と液媒体との混合は、公知の撹拌装置を使用して撹拌により実施することができるが、均一な混合物の調製の観点からは、斜坑型撹拌翼槽を使用することが好ましい。 In one embodiment of the present invention, the binder agent and the liquid medium can be mixed by stirring using a known stirring device. It is preferred to use a bath.
　上記撹拌装置における撹拌速度は、例えば、５～２０ｒｐｍであり、好ましくは５～１２ｒｐｍであり、より好ましくは７～１０ｒｐｍである。上記撹拌は、工程（１ｂ）において、バインダー液をナノカーボンに添加する際に継続してもよい。 The stirring speed in the stirring device is, for example, 5 to 20 rpm, preferably 5 to 12 rpm, more preferably 7 to 10 rpm. The stirring may be continued when the binder liquid is added to the nanocarbon in step (1b).
　また、本発明の一実施形態によれば、工程（１ｂ）において、バインダー液をナノカーボンに含浸させて固体凝集物を得る。 Further, according to one embodiment of the present invention, in step (1b), nanocarbon is impregnated with a binder liquid to obtain a solid aggregate.
　バインダー液の使用量は、ナノカーボン１００質量部に対して４４～２４３質量部の範囲で適宜設定することができるが、好ましくは８０～２００質量部であり、より好ましくは１００～１５０質量部である。 The amount of the binder liquid used can be appropriately set in the range of 44 to 243 parts by mass with respect to 100 parts by mass of nanocarbon, preferably 80 to 200 parts by mass, more preferably 100 to 150 parts by mass. be.
　工程（１ｂ）における含浸処理は、ナノカーボンに対してバインダー液を滴下することにより実施することが好ましい。上記含浸処理は、公知の撹拌装置内で実施してよいが、均一な混合物の調製の観点からは、傾斜型撹拌槽を使用することが好ましい。本発明の好ましい実施形態によれば、傾斜型撹拌槽内にナノカーボンを仕込み、斜坑型撹拌槽を所定の回転数にて回転させながら、バインダー液を傾斜型撹拌槽中のナノカーボンに滴下する。 The impregnation treatment in step (1b) is preferably carried out by dropping a binder liquid onto the nanocarbon. The impregnation treatment may be carried out in a known stirring device, but from the viewpoint of preparing a uniform mixture, it is preferable to use an inclined stirring tank. According to a preferred embodiment of the present invention, nanocarbon is charged in an inclined stirring vessel, and the binder liquid is dripped onto the nanocarbon in the inclined stirring vessel while rotating the inclined shaft stirring vessel at a predetermined number of revolutions. .
　また、本発明の一実施形態によれば、工程（１ｂ）における含浸処理は、減圧雰囲気、加圧雰囲気またはそれらを組み合わせた条件下で実施される。このように減圧および加圧操作を繰り返して行うことは、バインダー液の吸着速度を調節する上で好ましい。また、工程（１ｂ）において、圧力条件を調整することは、ナノカーボン内部へバインダー液を均一に浸透させ、さらにはナノカーボン表面の濡れ性を向上させる上でも有利である。 Further, according to one embodiment of the present invention, the impregnation treatment in step (1b) is performed under a reduced pressure atmosphere, a pressurized atmosphere, or a combination thereof. It is preferable to repeat the depressurization and pressurization operations in this way in order to adjust the adsorption speed of the binder liquid. Further, adjusting the pressure conditions in the step (1b) is advantageous in terms of allowing the binder liquid to uniformly permeate the inside of the nanocarbon and improving the wettability of the surface of the nanocarbon.
　本発明の好ましい実施形態によれば、工程（１ｂ）における含浸処理は減圧雰囲気下で実施される場合、減圧条件は、例えば、５～５０Ｐａであり、好ましくは１０～４０Ｐａであり、より好ましくは１０～２０Ｐａである。 According to a preferred embodiment of the present invention, when the impregnation treatment in step (1b) is performed under a reduced pressure atmosphere, the reduced pressure condition is, for example, 5 to 50 Pa, preferably 10 to 40 Pa, more preferably It is 10-20Pa.
　本発明の好ましい実施形態によれば、工程（１ｂ）における含浸処理が加圧雰囲気下で実施される場合、加圧条件は、例えば、０．１～５ＭＰａであり、好ましくは０．２～５ＭＰａであり、より好ましくは０．５～３ＭＰａである。 According to a preferred embodiment of the present invention, when the impregnation treatment in step (1b) is performed under a pressurized atmosphere, the pressurized conditions are, for example, 0.1 to 5 MPa, preferably 0.2 to 5 MPa. and more preferably 0.5 to 3 MPa.
　工程（１ｂ）において、上述のような所定量でナノカーボンにバインダー液を添加することにより、可塑性を備えた軟性の固体凝集物として好適に調製することができる。 In the step (1b), by adding a binder liquid to the nanocarbon in a predetermined amount as described above, it can be suitably prepared as a soft solid aggregate with plasticity.
［工程（２）：固体凝集物の解砕処理工程］
　次いで、本発明の一実施形態によれば、上記工程（１）において得られた固体凝集物を解砕処理してナノカーボン配合凝集物を得る。 [Step (2): Crushing treatment step for solid aggregates]
Next, according to one embodiment of the present invention, the solid agglomerate obtained in the step (1) is pulverized to obtain a nanocarbon-containing agglomerate.
　本発明の解砕処理は、塊状の固体凝集物を解きほぐす分散処理をいい、解膠をも含めた広い意味に用いる。解砕処理は、剪断装置を用いて実施することが好ましく、剪断破砕装置を用いることがより好ましい。ここで、剪断とは、剪断力を試料に加えて試料を微細化する処理をいう。剪断装置としては、高速で回転する刃と固定されたカッティングヘッドの刃によって投入された固体凝集物が細分化されるものや、大きな相対速度を持つ２面のディスク間の間隙に起きる剪断力と衝撃を利用して固体凝集物の剪断と高速撹拌を同時に行うような装置が挙げられる。より具体的な剪断装置としては、コミトロール、コロイドミル、電動ミル、マスコロイダー、フードプロセッサー、パルパーフィニッシャー、ロータリーカッターミル、ミクロマイスター、ナノカッター、解砕機等が挙げられ、好ましくはナノカッターである。 The crushing treatment of the present invention refers to a dispersing treatment for disentangling lumpy solid aggregates, and is used in a broad sense including deflocculation. The crushing treatment is preferably carried out using a shearing device, more preferably using a shearing crushing device. Here, the term "shearing" refers to a process of applying a shearing force to a sample to make the sample finer. As a shearing device, a high-speed rotating blade and a fixed cutting head blade are used to break up solid agglomerates thrown in. Apparatuses that utilize impact to simultaneously shear solid agglomerates and high-speed agitation are included. More specific shearing devices include comitrolles, colloid mills, electric mills, mass colloiders, food processors, pulper finishers, rotary cutter mills, micromeisters, nano cutters, pulverizers and the like, preferably nano cutters. be.
　剪断装置の運転条件は、特に限定されないが、効率的なナノカーボン配合凝集物の生産の観点から設定することが好ましい。具体的には、解砕処理時の剪断装置中の温度は、例えば、２０℃～９０℃程度である。また、剪断装置を用いて解砕処理を実施する場合、剪断装置における刃の回転速度は、３５０～６００ｒｐｍ程度、好ましくは５００～６００ｒｐｍ程度である。 The operating conditions of the shearing device are not particularly limited, but are preferably set from the viewpoint of efficient production of nanocarbon-blended agglomerates. Specifically, the temperature in the shearing device during the crushing process is, for example, about 20°C to 90°C. When crushing is performed using a shearing device, the rotation speed of the blades in the shearing device is about 350 to 600 rpm, preferably about 500 to 600 rpm.
　解砕処理は、１回行ってもよく、２回以上繰り返し行ってもよい。 The crushing treatment may be performed once, or may be performed repeatedly two or more times.
　本発明によれば、工程（１）で得られた固体凝集物を工程（２）の解砕処理に付して、乾燥工程を経ることなく、直接的にナノカーボン配合凝集物を提供することができる。したがって、一実施態様によれば、本発明の方法は、乾燥処理工程を含まない。本発明の製造方法は、乾燥工程経ずに簡便に実施しうることから、短時間でナノカーボン配合凝集物を効率的に取得する上で有利である。 According to the present invention, the solid aggregates obtained in step (1) are subjected to the crushing treatment in step (2) to directly provide nanocarbon-blended aggregates without going through a drying step. can be done. Therefore, according to one embodiment, the method of the present invention does not include a drying step. Since the production method of the present invention can be easily carried out without a drying step, it is advantageous in efficiently obtaining nanocarbon-containing aggregates in a short period of time.
［ナノカーボン配合凝集物］
　本発明の一実施形態によれば、上記方法により得られたナノカーボン配合凝集物が提供される。本発明の好ましい実施形態によれば、ナノカーボン配合凝集物は非乾燥状態の製品（保管物、包装品等）として提供される。 [Nanocarbon compound aggregate]
According to one embodiment of the present invention, there is provided a nanocarbon-containing agglomerate obtained by the above method. According to a preferred embodiment of the present invention, the nanocarbon-loaded agglomerate is provided as a non-dried product (storage, packaging, etc.).
　本発明のナノカーボン配合凝集物は硬度が１０ｇ以下に調整されることから、優れた分散性およびハンドリング性を発揮する上で有利である。本発明において「硬度」とは、ＪＩＳ　Ｋ　６２１９－３に準拠して測定された硬度を意味する。ナノカーボン配合凝集物の硬度は２０ｇ以下の範囲内であればよいが、好ましくは５～１５ｇであり、より好ましくは５～１０ｇである。 The hardness of the nanocarbon-containing agglomerates of the present invention is adjusted to 10 g or less, which is advantageous in exhibiting excellent dispersibility and handleability. In the present invention, "hardness" means hardness measured according to JIS K 6219-3. The hardness of the nanocarbon-containing agglomerates may be within a range of 20 g or less, preferably 5 to 15 g, more preferably 5 to 10 g.
　また、本発明の一実施形態によれば、ナノカーボン配合凝集物の嵩密度は、好ましくは０．５～２．３ｇ／ｃｍ３であり、より好ましくは０．８～２．０ｇ／ｃｍ３であり、さらに好ましくは０．８～１．５ｇ／ｃｍ３である。本発明の製造方法により得られるナノカーボン配合凝集物は、上記のように嵩密度が非常に高く、従って、例えば合成樹脂等への混錬工程において、貯蔵タンク内でのブリッジの発生防止や供給時の自動計量化が可能となり、輸送や在庫コストの低減化にもつながる等のメリットもある。 Further, according to one embodiment of the present invention, the bulk density of the nanocarbon-blended aggregates is preferably 0.5-2.3 g/cm 3 , more preferably 0.8-2.0 g/cm 3 . and more preferably 0.8 to 1.5 g/cm 3 . The nanocarbon-blended agglomerate obtained by the production method of the present invention has a very high bulk density as described above, therefore, for example, in the kneading step of synthetic resin etc., it is possible to prevent the occurrence of bridges in the storage tank and supply It also has the advantage of enabling automatic weighing of time and reducing transportation and inventory costs.
　本発明の一実施形態によれば、ナノカーボン配合凝集物は、粒状である。ナノカーボン配合凝集物の平均粒径は、好ましくは０．１５～２．０ｍｍであり、より好ましくは０．２５～１．８ｍｍであり、さらに好ましくは０．２５～１．０ｍｍである。なお、平均粒径とは、ナノカーボン配合凝集物の顕微鏡観察により、ランダムに抽出した１００個の凝集物のそれぞれについて粒径を算出し、平均した値をいうものとする。 According to one embodiment of the present invention, the nanocarbon-containing aggregates are granular. The average particle diameter of the nanocarbon-blended aggregates is preferably 0.15-2.0 mm, more preferably 0.25-1.8 mm, still more preferably 0.25-1.0 mm. Note that the average particle size is the average value obtained by calculating the particle size of each of 100 randomly extracted aggregates by microscopic observation of the nanocarbon-blended aggregates.
　また、本発明のナノカーボン配合凝集物は、優れた分散性を奏しうることから、粒度のバラツキを好適に抑制した集合体として提供することができる。したがって、本発明の一実施形態よれば、ナノカーボン配合凝集物は組成物として提供される。 In addition, since the nanocarbon-containing agglomerate of the present invention can exhibit excellent dispersibility, it can be provided as an aggregate in which variation in particle size is suitably suppressed. Thus, according to one embodiment of the present invention, nanocarbon-loaded agglomerates are provided as compositions.
　本発明の別の好ましい実施形態によれば、ナノカーボン配合凝集物において、ＪＩＳ　Ｋ　６２１９－１：２００５（ゴム用カーボンブラック－造粒粒子の特性－第１部：微粉の求め方）に準拠して測定されるナノカーボン配合凝集物の粒度（Ｒ）は、例えば、０．１～５％であり、好ましくは０．２～３％であり、より好ましくは０．２～１．５％である。 According to another preferred embodiment of the present invention, in the nanocarbon blended aggregate, JIS K 6219-1: 2005 (Carbon black for rubber-Characteristics of granulated particles-Part 1: How to determine fine powder) The particle size (R) of the nanocarbon-blended aggregate measured by is, for example, 0.1 to 5%, preferably 0.2 to 3%, more preferably 0.2 to 1.5%. be.
　なお、上記粒度（Ｒ）は、以下の式に基づき算出することができる。
Figure JPOXMLDOC01-appb-M000007
 　Ｒ：粒度（％）
　Ｅ：ふるい面上のナノカーボンの質量（ｇ）
　Ｂ：試料(全成分を含んだもの)の質量（ｇ） The particle size (R) can be calculated based on the following formula.
Figure JPOXMLDOC01-appb-M000007
 R: particle size (%)
E: mass of nanocarbon on the sieve surface (g)
B: Mass (g) of sample (containing all components)
　また、本発明の一実施態様によれば、以下が提供される。
［１］ナノカーボン配合凝集物の製造方法であって、
（１）ナノカーボン１００質量部に対して、０．１～１０質量部のバインダー剤および４３～２３３質量部の液媒体を含浸させて固体凝集物を得る工程、および
（２）上記固体凝集物を解砕処理してナノカーボン配合凝集物を得る工程、
を含んでなり、
　ＪＩＳ　Ｋ　６２１９－３に準拠して測定される上記ナノカーボン配合凝集の硬度が２０ｇ以下である、方法。
［２］上記ナノカーボンが、カーボンナノチューブおよびグラフェンから選択される少なくとも一つのものである、［１］に記載の方法。
［３］上記バインダー剤が、高分子界面活性剤である、［１］または［２］に記載の方法。
［４］上記バインダー剤が、ポリオキシアルキレン鎖を有するグラフト型ポリマー、アミン系ポリマーおよびセルロース系ポリマー、クエン酸、および炭酸水素ナトリウムからなる群から選択される少なくとも一つのものである、［１］～［３］のいずれかに記載の方法。
［５］上記液媒体が、有機溶剤および水から選択される少なくとも一つのものである、［１］～［４］のいずれかに記載の方法。
［６］上記工程（１）が、
　（１ａ）上記バインダー剤と上記液媒体を含有するバインダー液を準備する工程、および
　（１ｂ）上記バインダー液をナノカーボンに含浸させて上記固体凝集物を得る工程
を含んでなる、［１］～［５］のいずれかに記載の方法。
［７］上記工程（１ｂ）が、減圧雰囲気、加圧雰囲気およびそれらを組み合わせからなる群から選択される条件下で実施される、［６］に記載の方法。
［８］上記減圧雰囲気が５０～５Ｐａである、［７］に記載の方法。
［９］上記加圧雰囲気が０．１～５ＭＰａである、［７］または［８］に記載の方法。
［１０］工程（２）における解砕処理が、剪断装置を用いて実施される、［１］～［９］のいずれかに記載の方法。
［１１］上記ナノカーボン配合凝集物が非乾燥状態で提供される、［１］～［１０］のいずれかに記載の方法。
［１２］上記ナノカーボン配合凝集物の嵩密度が、０．８～２．０ｇ／ｃｍ３である、［１］～［１１］のいずれかに記載の方法。
［１３］上記ナノカーボン配合凝集物の平均粒径が、０．１５～２．０ｍｍである、［１］～［１２］のいずれかに記載の方法。
［１４］　［１］～［１３］のいずれかに記載の方法により得られた、ナノカーボン配合凝集物。 Also, according to one embodiment of the present invention, the following are provided.
[1] A method for producing a nanocarbon-blended aggregate,
(1) A step of impregnating 100 parts by mass of nanocarbon with 0.1 to 10 parts by mass of a binder agent and 43 to 233 parts by mass of a liquid medium to obtain a solid aggregate, and (2) the solid aggregate. A step of crushing to obtain a nanocarbon-blended aggregate,
comprising
A method, wherein the hardness of the nanocarbon-blended aggregate measured in accordance with JIS K 6219-3 is 20 g or less.
[2] The method according to [1], wherein the nanocarbon is at least one selected from carbon nanotubes and graphene.
[3] The method according to [1] or [2], wherein the binder is a polymeric surfactant.
[4] The binder agent is at least one selected from the group consisting of a graft type polymer having a polyoxyalkylene chain, an amine-based polymer and a cellulose-based polymer, citric acid, and sodium bicarbonate [1] The method according to any one of to [3].
[5] The method according to any one of [1] to [4], wherein the liquid medium is at least one selected from organic solvents and water.
[6] The above step (1) is
(1a) a step of preparing a binder liquid containing the binder agent and the liquid medium; and (1b) a step of impregnating the nanocarbon with the binder liquid to obtain the solid aggregate, [1] to The method according to any one of [5].
[7] The method according to [6], wherein the step (1b) is performed under conditions selected from the group consisting of a reduced pressure atmosphere, a pressurized atmosphere and a combination thereof.
[8] The method according to [7], wherein the reduced pressure atmosphere is 50 to 5 Pa.
[9] The method according to [7] or [8], wherein the pressurized atmosphere is 0.1 to 5 MPa.
[10] The method according to any one of [1] to [9], wherein the crushing treatment in step (2) is performed using a shearing device.
[11] The method according to any one of [1] to [10], wherein the nanocarbon-blended aggregate is provided in a non-dried state.
[12] The method according to any one of [1] to [11], wherein the nanocarbon-containing aggregate has a bulk density of 0.8 to 2.0 g/cm 3 .
[13] The method according to any one of [1] to [12], wherein the nanocarbon-blended aggregate has an average particle size of 0.15 to 2.0 mm.
[14] A nanocarbon-containing agglomerate obtained by the method according to any one of [1] to [13].
　以下、本発明を実施例により具体的に説明する。なお、本発明はこれらの実施例に限定されるものではない。なお、特段の記載のない限り、本明細書における単位および測定方法は、日本工業規格（ＪＩＳ）の規定に従う。 The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, units and measurement methods in this specification conform to the Japanese Industrial Standards (JIS).
　以下の実験に使用したＣＮＴ（商品名：Ｋ－Ｎａｎｏｓ－１００Ｐ，１００Ｔ，２１０Ｔ，３００Ｔ、５００Ｔ、Ｋｕｍｈｏ　Ｐｅｔｒｏｃｈｅｍｉｃａｌ社製）の物性は、表１に示される通りであった。 Table 1 shows the physical properties of the CNTs (trade names: K-Nanos-100P, 100T, 210T, 300T, 500T, manufactured by Kumho Petrochemical) used in the following experiments.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
［参考例１］
　傾斜型撹拌槽（ＰＴ４０ＳＭＶ、マゼラー社製）内に粉体ナノカーボン（ＣＮＴ）２ｋｇを仕込み、減圧した。次いで、液媒体（プロセスオイル、日本サン石油社製）を傾斜型撹拌槽内のＣＮＴに対して２ｋｇを滴下した。滴下終了後には、撹拌羽根を回転させたまま減圧および加圧操作を繰り返し行い、ＣＮＴに液媒体が浸透するのを促進させて固体凝集物を得た。 [Reference example 1]
2 kg of powdered nanocarbon (CNT) was placed in an inclined stirring tank (PT40SMV, manufactured by Mazeler) and the pressure was reduced. Next, 2 kg of a liquid medium (process oil, manufactured by Nippon Sun Oil Co., Ltd.) was added dropwise to the CNTs in the inclined stirring tank. After the dropwise addition was completed, pressure reduction and pressure operations were repeated while the stirring blade was being rotated to promote permeation of the liquid medium into the CNTs and obtain solid aggregates.
　次に、得られた固体凝集物を、多段式のロータリーカッターミルにより連続的に剪断破砕処理し、目的とするＣＮＴ配合凝集物を得た。 Next, the obtained solid agglomerate was continuously sheared and crushed by a multi-stage rotary cutter mill to obtain the desired CNT-blended agglomerate.
　ＣＮＴ配合凝集物について、以下の手法により物性（嵩密度、炭素含有率、平均粒子径、粒度、粒子の硬度）を測定した。 The physical properties (bulk density, carbon content, average particle size, particle size, particle hardness) of the CNT-blended agglomerates were measured by the following methods.
（嵩密度）
　嵩密度は、ＪＩＳ　Ｋ　６２１９に規定されるカーボンブラックの嵩密度の測定法に準拠して求めた。 (The bulk density)
The bulk density was obtained according to the method for measuring the bulk density of carbon black specified in JIS K 6219.
（炭素含有率）
　炭素含有率は、ＪＩＳ　Ｋ　６２１８－２に準拠して測定された灰分（％）を１００％から差し引くことにより求めた。 (carbon content)
The carbon content was obtained by subtracting the ash content (%) measured according to JIS K 6218-2 from 100%.
（平均粒子径）
　走査型電子顕微鏡（ＳＥＭ）により、ＣＮＴ配合凝集物の形態観察を実施した。観察は３００倍のＳＥＭ画像を用いて、任意に１００個のＣＮＴ配合凝集物の外径を計測し、その数平均値をもってＣＮＴ配合凝集物の平均粒径（ｍｍ）とした。 (Average particle size)
The morphology of the CNT-blended aggregates was observed by scanning electron microscopy (SEM). Observation was performed by using a 300-fold SEM image, measuring the outer diameter of 100 CNT-blended aggregates at random, and taking the number average value as the average particle size (mm) of the CNT-blended aggregates.
（粒度）
　また、ＪＩＳ　Ｋ　６２１９－１：２００５に準拠してＣＮＴ配合凝集物の粒度（Ｒ）を、以下の式に基づき算出した。
Figure JPOXMLDOC01-appb-M000009
 　Ｒ：粒度（％）
　Ｅ：ふるい面上のナノカーボンの質量（ｇ）
　Ｂ：試料(全成分を含んだもの)の質量（ｇ） (particle size)
In addition, the particle size (R) of the CNT blended aggregate was calculated based on the following formula according to JIS K 6219-1:2005.
Figure JPOXMLDOC01-appb-M000009
 R: particle size (%)
E: mass of nanocarbon on the sieve surface (g)
B: Mass (g) of sample (containing all components)
（粒子の硬度）
　粒子の硬度は、ＪＩＳ　Ｋ　６２１９－３（カーボンブラック－造粒粒子の硬さの求め方）に準拠して測定した。 (Particle hardness)
The hardness of the particles was measured according to JIS K 6219-3 (Carbon black-Determination of hardness of granulated particles).
　上記測定の結果は表２に示される通りであった。
Figure JPOXMLDOC01-appb-T000010
 The results of the above measurements were as shown in Table 2.
Figure JPOXMLDOC01-appb-T000010
　得られたＣＮＴ配合凝集物のシートを、端部から２ｍｍ幅で切片を切り出し、切断面を原子間力顕微鏡（ＭＦＰ－３Ｄ－ＳＡ－Ｊ、オックスフォード・インストゥルメンツ社製）を用いて、スキャンサイズ４０μｍ×４０μｍにてＡＣモード（タッピングモード）にて観察（１００倍）した。ＡＦＭ写真を図１に示す。 A 2 mm wide section is cut from the edge of the sheet of the obtained CNT-blended aggregate, and the cut surface is scanned using an atomic force microscope (MFP-3D-SA-J, manufactured by Oxford Instruments). It was observed (100 times) in AC mode (tapping mode) at a size of 40 μm×40 μm. An AFM photograph is shown in FIG.
［実施例１］
　傾斜型撹拌槽（ＰＴ４０ＳＭＶ、マゼラー社製）内に粉体ナノカーボン（ＣＮＴ）２Ｋｇを仕込み、減圧した。次に、斜坑型撹拌槽（ＳＴ－Ｊ－ＡＳＣ－３６、新東社製）中で、液媒体（プロセスオイル、日本サン石油社製）と、バインダー剤（マリアリム　ＡＫＭ０５３１、日油社製）とを撹拌（１００ｒｐｍ）してバインダー液（バインダー剤濃度１０質量％、４ｇ）を調製し、減圧雰囲気（１０Ｐａ）にてバインダー液を撹拌しながら傾斜型撹拌槽内のＣＮＴに対して滴下した。滴下終了後には、撹拌羽根を回転させたまま減圧および加圧操作を繰り返し行い、ＣＮＴに対するバインダー液の浸透を促進させ、軟凝集物を得た。
　得られたＣＮＴ配合凝集物について、上記と同様にして評価を行った。ＡＦＭ観察を行った。ＡＦＭ写真を図２に示す。 [Example 1]
2 kg of powdered nanocarbon (CNT) was placed in an inclined stirring tank (PT40SMV, manufactured by Masellar), and the pressure was reduced. Next, in an inclined shaft type stirring tank (ST-J-ASC-36, manufactured by Shinto Corporation), a liquid medium (process oil, manufactured by Nippon Sun Oil Co., Ltd.) and a binder agent (Malialim AKM0531, manufactured by NOF Corporation). was stirred (100 rpm) to prepare a binder solution (binder concentration: 10% by mass, 4 g), and the binder solution was added dropwise to the CNTs in an inclined stirring vessel while being stirred in a reduced pressure atmosphere (10 Pa). After completion of dropping, pressure reduction and pressurization operations were repeated while the stirring blade was being rotated to promote permeation of the binder liquid into the CNTs and obtain soft aggregates.
The obtained CNT-blended aggregate was evaluated in the same manner as described above. AFM observation was performed. An AFM photograph is shown in FIG.
［実施例２］
　バインダー剤として、ポリエチレンワックス（バインダー剤濃度１０質量％）に変更した以外は実施例１と同様にしてＣＮＴ配合凝集物を製造し、上記と同様にしてＡＦＭ観察を行った。 [Example 2]
A CNT-blended agglomerate was produced in the same manner as in Example 1 except that the binder was changed to polyethylene wax (with a binder concentration of 10% by mass), and AFM observation was performed in the same manner as described above.
［参考例２］
　下記表３に示す各成分を下記表に従って配合した混練物を製造し、上記と同様にしてＡＦＭ観察を行った。
Figure JPOXMLDOC01-appb-T000011
 [Reference example 2]
A kneaded material was prepared by blending each component shown in Table 3 below according to the table below, and AFM observation was performed in the same manner as above.
Figure JPOXMLDOC01-appb-T000011
［参考例３］
　下記表４に示す各成分を下記表に従って配合した混練物を製造し、上記と同様にしてＡＦＭ観察を行った。
Figure JPOXMLDOC01-appb-T000012
 [Reference example 3]
A kneaded product was prepared by blending each component shown in Table 4 below according to the table below, and AFM observation was performed in the same manner as above.
Figure JPOXMLDOC01-appb-T000012
　実施例１～２のＣＮＴ配合凝集物、および参考例１～３の混練物のそれぞれのＡＦＭ観察写真から、任意の５箇所における凝集塊の大きさと個数を数え、その平均値を求めた。凝集塊の分布を図３に示す。図３から、実施例１のＣＮＴ配合凝集物中の凝集塊の大きさは３～６０μｍであることがわかる。 From the AFM observation photographs of the CNT-containing aggregates of Examples 1 and 2 and the kneaded materials of Reference Examples 1 and 3, the size and number of aggregates were counted at any five locations, and the average value was obtained. The distribution of aggregates is shown in FIG. From FIG. 3, it can be seen that the size of the aggregates in the CNT-blended aggregates of Example 1 is 3 to 60 μm.
　以上に示される通り、実施例のＣＮＴ配合凝集物の粒子の硬度は１０ｇ以下であり、硬度粒度分布が狭かった。実施例のＣＮＴ配合凝集物では、粒子の硬度が低レベルに抑制され、その結果バラツキが抑制され、分散性が向上しているものと考えられる。 As shown above, the hardness of the particles of the CNT-blended aggregates of Examples was 10 g or less, and the hardness particle size distribution was narrow. In the CNT-blended agglomerates of Examples, the hardness of the particles is suppressed to a low level, and as a result, it is considered that the dispersion is suppressed and the dispersibility is improved.
　実施例１では、乾燥工程を行う必要がないことから、造粒工程における焼き締まりによる粒子の硬度上昇を回避され、ＣＮＴ配合凝集物の粒子の分散性の向上に寄与しているものと考えられる。また、実施例１では、閉鎖系内で、嵩密度が高く飛散性のＣＮＴ配合凝集物を連続的、効率的に生成することから、ＣＮＴの飛散を防止することができ、安全に対するリスクを抑制できると考えられる。 In Example 1, since it is not necessary to perform the drying process, it is possible to avoid an increase in the hardness of the particles due to densification in the granulation process, which is considered to contribute to the improvement of the dispersibility of the particles of the CNT-blended aggregates. . In addition, in Example 1, CNT-blended agglomerates with high bulk density and dispersibility are continuously and efficiently produced in a closed system, so CNT dispersal can be prevented, and safety risks can be suppressed. It is possible.
　本発明によれば、分散性が良好であり、嵩密度が高く飛散性の低いナノカーボン配合凝集物を効率的に製造することができる。また、本発明によれば、ナノカーボン配合凝集物の分散性を向上させ、加工性・ハンドリング性等の作業性を著しく向上させることができる。また、本発明によれば、閉鎖系の固相状態で配合処理を実施し、さらに連続的な解砕処理によりナノカーボン配合凝集物粒子を製造できることから、環境負荷を低減する上で有利である。また、本発明によれば、大掛かりな設備を必要とせず、粒度分布の良好なナノカーボン配合凝集物を低原価で迅速に量産できることから、工業生産上特に有利である。 According to the present invention, it is possible to efficiently produce a nanocarbon-containing agglomerate that has good dispersibility, high bulk density, and low scattering properties. Moreover, according to the present invention, the dispersibility of the nanocarbon-containing aggregate can be improved, and the workability such as workability and handleability can be significantly improved. In addition, according to the present invention, the blending treatment is performed in a closed system in a solid state, and the nanocarbon-blended agglomerate particles can be produced by continuous pulverization treatment, which is advantageous in terms of reducing the environmental load. . Moreover, according to the present invention, nanocarbon-blended aggregates with good particle size distribution can be rapidly mass-produced at low cost without the need for large-scale equipment, which is particularly advantageous in terms of industrial production.

Claims (14)

  1. 　ナノカーボン配合凝集物の製造方法であって、
    （１）ナノカーボン１００質量部に対して、０．１～１０質量部のバインダー剤および４３～２３３質量部の液媒体を含浸させて固体凝集物を得る工程、および
    （２）前記固体凝集物を解砕処理してナノカーボン配合凝集物を得る工程、
    を含んでなり、
    　ＪＩＳ　Ｋ　６２１９－３に準拠して測定される前記ナノカーボン配合凝集物の硬度が２０ｇ以下である、方法。     A method for producing nanocarbon-blended aggregates,
    (1) A step of impregnating 100 parts by mass of nanocarbon with 0.1 to 10 parts by mass of a binder agent and 43 to 233 parts by mass of a liquid medium to obtain a solid aggregate, and (2) the solid aggregate. A step of crushing to obtain a nanocarbon-blended aggregate,
    comprising
    The method, wherein the hardness of the nanocarbon-blended agglomerate measured according to JIS K 6219-3 is 20 g or less.
  2. 　前記ナノカーボンが、カーボンナノチューブおよびグラフェンから選択される少なくとも一つのものである、請求項１に記載の方法。 The method according to claim 1, wherein the nanocarbon is at least one selected from carbon nanotubes and graphene.
  3. 　前記バインダー剤が界面活性剤である、請求項１または２に記載の方法。 The method according to claim 1 or 2, wherein the binder agent is a surfactant.
  4. 　前記バインダー剤が、ポリオキシアルキレン鎖を有するグラフト型ポリマー、アミン系ポリマーおよびセルロース系ポリマー、クエン酸、および炭酸水素ナトリウムからなる群から選択される少なくとも一つのものである、請求項１～３のいずれか一項に記載の方法。 Claims 1 to 3, wherein the binder agent is at least one selected from the group consisting of a graft type polymer having a polyoxyalkylene chain, an amine-based polymer and a cellulose-based polymer, citric acid, and sodium hydrogen carbonate. A method according to any one of paragraphs.
  5. 　前記液媒体が、有機溶剤および水から選択される少なくとも一つのものである、請求項１～４のいずれか一項に記載の方法。 The method according to any one of claims 1 to 4, wherein the liquid medium is at least one selected from organic solvents and water.
  6. 　前記工程（１）が、
    　（１ａ）前記バインダー剤と前記液媒体を含有するバインダー液を準備する工程、および
    　（１ｂ）前記バインダー液をナノカーボンに含浸させて前記固体凝集物を得る工程
    を含んでなる、請求項１～５のいずれか一項に記載の方法。     The step (1) is
    (1a) a step of preparing a binder liquid containing the binder agent and the liquid medium; and (1b) a step of impregnating nanocarbon with the binder liquid to obtain the solid aggregate. 6. The method of any one of 5.
  7. 　前記工程（１ｂ）が、減圧雰囲気、加圧雰囲気およびそれらを組み合わせからなる群から選択される条件下で実施される、請求項６に記載の方法。 The method according to claim 6, wherein said step (1b) is carried out under conditions selected from the group consisting of a reduced pressure atmosphere, a pressurized atmosphere and combinations thereof.
  8. 　前記減圧雰囲気が５～５０Ｐａである、請求項７に記載の方法。 The method according to claim 7, wherein the reduced pressure atmosphere is 5 to 50 Pa.
  9. 　前記加圧雰囲気が０．１～５ＭＰａである、請求項７または８に記載の方法。 The method according to claim 7 or 8, wherein the pressurized atmosphere is 0.1 to 5 MPa.
  10. 　工程（２）における解砕処理が、剪断装置を用いて実施される、請求項１～９のいずれか一項に記載の方法。 The method according to any one of claims 1 to 9, wherein the crushing treatment in step (2) is performed using a shearing device.
  11. 　前記ナノカーボン配合凝集物が非乾燥状態で提供される、請求項１～１０のいずれか一項に記載の方法。 The method according to any one of claims 1 to 10, wherein the nanocarbon-blended aggregate is provided in a non-dried state.
  12. 　前記ナノカーボン配合凝集物の嵩密度が、０．８～２．０ｇ／ｃｍ３である、請求項１～１１のいずれか一項に記載の方法。 The method according to any one of claims 1 to 11, wherein the bulk density of said nanocarbon-blended agglomerates is 0.8 to 2.0 g/cm 3 .
  13. 　前記ナノカーボン配合凝集物の平均粒径が、０．１５～２．０ｍｍである、請求項１～１２のいずれか一項に記載の方法。 The method according to any one of claims 1 to 12, wherein the nanocarbon-blended aggregate has an average particle size of 0.15 to 2.0 mm.
  14. 　請求項１～１３のいずれか一項に記載の方法により得られた、ナノカーボン配合凝集物。 A nanocarbon-containing aggregate obtained by the method according to any one of claims 1 to 13.
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