WO2020100842A1 - カーボンナノチューブ粒状物およびその製造方法 - Google Patents

カーボンナノチューブ粒状物およびその製造方法 Download PDF

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WO2020100842A1
WO2020100842A1 PCT/JP2019/044213 JP2019044213W WO2020100842A1 WO 2020100842 A1 WO2020100842 A1 WO 2020100842A1 JP 2019044213 W JP2019044213 W JP 2019044213W WO 2020100842 A1 WO2020100842 A1 WO 2020100842A1
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cnt
resin
less
carbon nanotube
mass
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French (fr)
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久　英之
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株式会社ＤＲ．ｇｏｏ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • the present invention relates to a carbon nanotube granular material and a method for producing the same.
  • the CNT manufacturing method includes an arc discharge type, a catalytic gas phase manufacturing method, a laser ablation method and other methods, but recently, the catalytic gas phase manufacturing method has become the mainstream.
  • CNTs are blended with various synthetic resins, rubbers and the like to impart electrical conductivity, high elasticity, high strength, thermal conductivity and the like.
  • CNTs there are concerns about safety, lack of dispersibility because the CNTs are tubular and are entangled with each other, and dispersability is poor, and handling is difficult. There is.
  • CB carbon black
  • pan-type granulation method pan-type granulation method
  • drum-type granulation method screw extrusion-type granulation method
  • stirring-type granulation method or compression.
  • Granulation is performed by a granulation method such as a molding granulation method.
  • Patent Document 3 is a CNT aggregate containing a rosin resin, which is a natural water-soluble resin. Since the rosin resin used is a natural product, it is a material whose production volume and price fluctuate greatly depending on the weather and labor problems in the production area. Therefore, in the paper manufacturing industry, which uses a lot of rosin resin as a sizing agent, the conversion to synthetic system (petroleum resin) with stable quality, price, and supply / demand is rapidly progressing. Further, as the effect of the invention, it is said that the wettability of CNTs is improved, the kneading is low, the scattering can be suppressed, and the dispersibility is excellent, but the data showing this effect is not described in Patent Document 3.
  • a rosin resin which is a natural water-soluble resin. Since the rosin resin used is a natural product, it is a material whose production volume and price fluctuate greatly depending on the weather and labor problems in the production area. Therefore, in the paper manufacturing industry, which uses
  • the scattering property referred to in Patent Document 3 refers to all the dust particles scattered in the atmosphere, and is different from the inhalable dust amount consisting of particles of 10 ⁇ m or less, which is the object of the present invention. Further, since the granulated product of Patent Document 3 has a columnar shape, a bridge is likely to be formed in a hopper or the like when the granulated product is used, and the flow is bad.
  • Patent Document 4 strongly disperses an aqueous resin and CNT with an ultrasonic disperser or a bead mill disperser to loosen CNT aggregates, coat the surface with the aqueous resin, and then further add a resin (heat Although it is a method of treating CNTs in which a plastic resin or a thermosetting resin is added and deposited, the content of CNTs in the aqueous resin is 10 mass% or less.
  • the final shape is a paste, a dried solid (chip), or a crushed shape, and all the dried products are amorphous particles.
  • the irregular-shaped particles are filled with the irregular-shaped particles, not only the voids become large and the packing density becomes low, so that the packing amount in the packaging material decreases, but also the fluidity and the handling property in the hopper and the like are poor.
  • this method includes (i) a step of dispersing CNT powder in water, (ii) a step of dissolving a binder polymer in a solvent, (iii) a step of adding the CNT dispersed in water in the above (i) step to the above (ii) step.
  • Granulating by adding the binder polymer solution obtained in step by step, (iv) draining the granules obtained in step (iii) above, (v) air-drying the drained granules or 50 ° C or less (Vii) vacuum drying the pre-dried granules, (vii) then sieving the granules and packaging.
  • a wastewater treatment step is required, so that there are various steps, and the above (i) step, (iii) step, and ( v) Each step requires several hours to several tens of hours. Therefore, this method has a problem that it is lacking in productivity and energy saving and labor saving.
  • the present invention can be produced without using an organic solvent, has appropriate hardness and particle size, and has a high bulk density, and can reduce the amount of inhalable dust consisting of particles of 10 ⁇ m or less, and It is intended to provide a manufacturing method thereof.
  • the carbon nanotube granular material of the present invention contains a synthetic water-soluble resin and carbon nanotubes, and the blending amount of the carbon nanotubes is 200 parts by mass or more and 5000 parts by mass or more with respect to 100 parts by mass of the synthetic water-soluble resin. It is characterized by the following.
  • the synthetic water-soluble resin is preferably at least one selected from the group consisting of polyacrylamide, polyethylene oxide, polyvinyl alcohol, polyethyleneimine, and polyvinylpyrrolidone.
  • the carbon nanotube has a fiber diameter of 0.3 nm or more and 200 nm or less and the carbon nanotube has a fiber length of 0.1 ⁇ m or more and 2000 ⁇ m or less.
  • the amount of inhalable (respirable) dust composed of particles of 10 ⁇ m or less is preferably 0.2 mg / m 3 or less.
  • the first method for producing carbon nanotube granules according to the present invention comprises the steps of dissolving a synthetic water-soluble resin in water to prepare an aqueous resin binder solution, and adding 200 parts by mass or more and 5000 parts by mass or less of carbon nanotubes to 100 parts by weight. Part of the aqueous solution of the resin binder containing a part by weight of the synthetic water-soluble resin is added little by little, and granulated to obtain a granulated product, and the granulated product is dried to form carbon nanotube particles. And a step of obtaining a product.
  • the present invention it is possible to produce without using an organic solvent, have appropriate hardness and particle size, have a high bulk density, and reduce the amount of inhalable dust composed of particles of 10 ⁇ m or less.
  • An object and a manufacturing method thereof can be provided.
  • 1 is a schematic diagram showing a reoccurring dust amount measuring device for measuring an inhalable dust amount consisting of particles of 10 ⁇ m or less.
  • 3 is a photograph showing a dried granulated product in the process of producing the CNT granular product of Example 1.
  • 3 is a photograph showing the CNT granules obtained in Example 1.
  • 5 is a photograph showing the CNT granules obtained in Example 2.
  • 5 is a photograph showing the CNT granules obtained in Comparative Example 1. It is a photograph showing a CNT granular material obtained in Comparative Example 2, and is a photograph taken from the side. It is a photograph showing a CNT granular material obtained in Comparative Example 2, and is a photograph of a cut surface.
  • the synthetic water-soluble resin used in the present embodiment is not a natural resin but a resin obtained by chemical synthesis and a resin that is soluble in water.
  • the synthetic water-soluble resin is preferably a resin obtained by a polymerization reaction. Examples of the polymerization reaction include chain polymerization, sequential polymerization, living polymerization and the like.
  • the natural resin derived from plants is pine resin (rosin), lacquer, dammar, mastic, and the like.
  • the natural resin derived from animals is shellac, gelatin, casein and the like.
  • Examples of synthetic water-soluble resins include polyacrylamide (SP value 14.2), polyethylene oxide, polyvinyl alcohol (SP value 12.6), polyethyleneimine, and polyvinylpyrrolidone (SP value 12.8).
  • polyacrylamide SP value 14.2
  • polyethylene oxide polyvinyl alcohol
  • SP value 12.6 polyvinyl alcohol
  • SP value 12.8 polyvinylpyrrolidone
  • SP value 12.8 polyvinylpyrrolidone
  • polyvinylpyrrolidone is particularly preferable. These may be used alone or in combination of two or more.
  • the concentration becomes lower than 0.4% by mass the adhesive force between the CNT particles tends to be weakened, and as the concentration becomes higher than 5% by mass, the aqueous resin permeates the inside of the CNT aggregate, It is not preferable because it tends to be difficult to diffuse.
  • concentration of the synthetic water-soluble resin becomes lower than 0.1% by mass or becomes thicker than 10% by mass, these tendencies become stronger, which is not preferable.
  • the ratio of preliminarily diluting the synthetic water-soluble resin with water confirm the optimum amount of water required for granulation in a preliminary test, and make a low-concentration resin binder aqueous solution that completely dissolves the synthetic water-soluble resin with that amount of water. It is preferable to determine by.
  • This resin binder aqueous solution is added to CNTs in a stirring state by a fixed amount by a metering pump or the like. For quantitative addition, if a nozzle capable of atomizing spray is used at the tip, a uniform granulated product can be easily obtained.
  • the resin binder aqueous solution containing 100 parts by mass of the synthetic water-soluble resin is added little by little to 200 parts by mass or more and 5000 parts by mass or less of the CNT, and the mixture is granulated to form a granulated product.
  • the following effects can be obtained by adding the resin binder aqueous solution little by little with the compounding amount of CNT to the synthetic water-soluble resin being within the above range.
  • a synthetic water-soluble resin can be efficiently permeated into the aggregate of CNTs to granulate a granulated product having an appropriate particle size and hardness.
  • the hardness of dried CNT granules can be maintained at an appropriate level, powdering and scattering properties during handling can be reduced, and further, when used for resins, inks, paints, batteries, etc.
  • the dispersibility can be made suitable.
  • the blending amount of CNT is more preferably 300 parts by mass or more and 3000 parts by mass or less with respect to 100 parts by mass of the synthetic water-soluble resin (calculated as solid content). If it is less than 300 parts by mass, the granulated product tends to be hard and the dispersibility tends to be poor, and if it exceeds 3000 parts by mass, pulverization and scattering amount at the time of handling increase, which is not preferable in terms of safety. There is a tendency. Further, if the content of CNT is less than 200 parts by mass or more than 5000 parts by mass, these tendencies are remarkable, which is not preferable.
  • a spherical granulated product can be obtained by spray-adding an aqueous resin binder aqueous solution diluted with water little by little and in a mist state to the CNTs in a stirring state, while also considering the permeation rate into the CNTs.
  • the granulation method is a method in which the aqueous resin is added little by little to the CNTs in a stirring state, and the granulation is performed by batch method or continuous method. In the case of the batch method, a low-concentration aqueous resin solution, which is weighed according to the particle size of the target substance, is sprayed in a fixed amount.
  • the amount of water with respect to CNT in the granulation step is preferably 5 times or more and 8 times or less, more preferably 5.5 times or more and 7.5 times or less.
  • the water content is 5 times or less, there is a large amount of powdery CNTs, and it tends to be difficult to form a granulated product.
  • the granulated product will be considerably wetted, and if this is sized, it will become a large granulated product (pachinko balls (diameter 11 mm) or more) and spherical granules of 4 mm or less that are easy to handle. This is not preferable because it tends to be difficult to obtain a product.
  • the CNT a single-layer CNT in which one carbon film (graphene sheet) is wound in a cylindrical shape, a two-layer CNT in which two graphene sheets are concentrically wound, and a plurality of graphene sheets are concentrically wound.
  • the single-layer CNT, the double-layer CNT, and the multi-layer CNT may be used alone or in combination of two or more.
  • the purity of CNT is preferably at least 80% or higher.
  • fullerenes, graphite and amorphous carbon are simultaneously produced as by-products, and catalytic metals such as nickel, iron, cobalt and yttrium also remain.
  • the purification method is not particularly limited, but examples thereof include oxidation treatment with sulfuric acid and nitric acid, halogen gas treatment, heat treatment at 2000 ° C. to 3000 ° C., and ultrasonic treatment. It is also preferable to perform separation and removal with a filter at the same time from the viewpoint of improving the purity.
  • the average fiber diameter and length of CNT are not particularly limited and can be appropriately selected according to the application.
  • the fiber diameter is usually 0.3 nm or more and 200 nm or less, preferably 1 nm or more and 100 nm or less.
  • the fiber length is usually 0.1 ⁇ m or more and 2000 ⁇ m, and preferably 1 ⁇ m or more and 1000 ⁇ m or less.
  • the fiber length exceeds 1000 ⁇ m, the entanglement of the fibers becomes stronger, so that not only the number of poorly dispersed lumps increases but also the number of cut fibers during kneading and dispersion tends to be unfavorable.
  • the fiber length is smaller than 0.1 ⁇ m or exceeds 2000 ⁇ m, these tendencies are further increased, which is not preferable.
  • Wet granulation is used as the granulation method.
  • Wet granulation includes rolling granulation, fluidized bed granulation, stirring granulation, compression granulation, extrusion granulation, crush granulation, and the like, based on the principle of the granulation method.
  • the stirring granulation method or the tumbling granulation method is preferable. This is because the apparatus can be easily made compact, the granulation time can be shortened, and the versatility is excellent.
  • the equipment used for stirring granulation can be roughly classified into a batch type and a continuous type, and as a representative of the batch type, a Henschel type stirring granulator or an intensive mixer, and as a continuous type, a twin screw is used for the production.
  • a biaxial pin type granulator for granulating can be used.
  • Henschel type Hi-speed mixer series of Artechnica Co., Ltd., SPG series of Technopaudal Co., Ltd., FM mixer of Nippon Coke Industry Co., Ltd., SMB and SM series of Kawata Co., Ltd. or Paulex Co., Ltd. VG series and the like.
  • the intensive mixer include Maschinenfabrik Gustav Irish (Germany).
  • twin-spin type there is Dow Pelletizer of Shin-Nichinan Co., Ltd. When manufacturing on a small scale, a food processor, a household mixer, or an ultra-small laboratory Henschel mixer is suitable.
  • CNT powder is quantitatively charged from a charging port into a device rotating at a stirring speed of 500 to 3000 rpm, preferably 1000 to 2000 rpm.
  • An aqueous resin solution is added from an injection port in the latter stage of the injection port for granulation, (3) a granulated product is taken out from the ejection port, and dried in a drying step (4).
  • Granulation performance is adjusted by the residence time in the granulator. The longer the residence time, the more spherical the granules can be obtained.
  • a plurality of pin type granulators may be continuously installed in two stages or three stages.
  • the mixture is stirred at 300 to 2500 rpm, preferably 500 to 2000 rpm, and the aqueous resin solution is added thereto.
  • Granules are obtained by adding little by little as quantitatively as possible, observing when the desired particle size is reached, taking out and drying.
  • the rolling granulator there are a pan type granulator, a drum type granulator, a horizontal vibrating pan type granulator, a vibration stirring type granulator, a vibrating bed type granulator and the like.
  • the most commonly used rolling granulators are the pan-type granulator and the drum-type granulator.
  • the bread-type granulator is preferred because of its simple structure, easy operation, visible granulation state, and easy maintenance.
  • the granulated product is granulated using a rolling granulator to obtain a granulated product.
  • a rolling granulator to obtain a granulated product.
  • a step in which several or several tens of primary particles are combined to form a nucleus (2) A step in which the particles collide with other particles or nuclei centering on the nucleus and become larger while adhering (3) Finally, the particle becomes larger
  • the spherical particles are further rolled and subjected to frictional force and the gravity of the particles themselves, so that the inside becomes dense and the surface becomes smooth.
  • CNT most of the spaces between the particles are filled with air. Therefore, the bulk density is extremely low.
  • kumano kano nano 100P has a bulk density of 0.015 g / mL. In such a powder having an extremely low bulk density, particle nuclei are not formed even if the powder is rolled as it is.
  • a common method is to add water to this to form a sticky film on the particle surface, and strengthen the contact and adhesion with surrounding particles to form nuclei for granulation.
  • CNTs have crystallites developed and the surface of the particles has few functional groups that are compatible with water, even if water is added, the water will not be repelled and the adhesive will not function. Therefore, the rolling granulation method using a pan type, a drum type, or the like as a container has not been utilized as a CNT granulating machine.
  • the present inventor transferred a granulated product (granulated product obtained in the granulation step) produced in advance with a wet stirring granulator with slightly less water than usual to a tumbling granulator, It was found that by doing so, spherical granules having a smooth surface can be obtained.
  • the water content of the granulated product in the granulation step is preferably 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less, based on 100% by mass of the granulated product.
  • the sized granules are dried to obtain CNT granules.
  • a vacuum dryer or a hot air dryer is used for drying.
  • a hot air dryer can be used as the hot air dryer, a vibration / fluid dryer, a fluid dryer, a box dryer, a dryer dryer or the like can be used.
  • the vacuum (decompression) dryer a vacuum tray dryer, a vacuum outer mixer type dryer, a box type dryer, or the like can be used.
  • the drying temperature is preferably a temperature at which the resin used as the binder does not deteriorate, an optimum temperature or maximum temperature exists depending on the type of synthetic water-soluble resin.
  • the drying temperature is 40 ° C or higher and 200 ° C or lower, preferably 50 ° C or higher and 150 ° C or lower, and more preferably 60 ° C or higher and 100 ° C or lower.
  • the drying time is usually 1 hour or more and 20 hours or less, preferably 2 hours or more and 10 hours or less, though it depends on the drying temperature.
  • a step of sieving the dried sized product with an ASTM sieve standard and 60 mesh (opening 0.25 mm) may be added.
  • the carbon nanotube granular material of the present embodiment contains a synthetic water-soluble resin and CNT, and the compounding amount of CNT is 200 parts by mass or more and 5000 parts by mass or less with respect to 100 parts by mass of the synthetic water-soluble resin. It is a thing.
  • the carbon nanotube granular material is preferably spherical.
  • the CNT granules of this embodiment can be produced, for example, by the above-described method for producing carbon nanotube granules of this embodiment. Further, the synthetic water-soluble resin and CNT are the same as those used in the method for producing the carbon nanotube granular material of the present embodiment described above.
  • the amount of inhalable (respirable) dust composed of particles of 10 ⁇ m or less is preferably 0.2 mg / m 3 or less.
  • the inhalable dust amount is more preferably 0.1 mg / m 3 or less.
  • the inhalable dust amount is 0.2 mg / m 3 or less, the following effects can be obtained. (1) Since the inhalability of particles of 10 ⁇ m or less is 0.2 mg / m 3 or less, preferably 0.1 mg / m 3 , the load on the working environment can be reduced and the safety can be significantly increased. (2) The characteristic of the inhalable dust amount is related to the hardness of the granulated product, but it varies depending on the type of the binder, the amount of the adhering substance, or the granulation method even if the hardness is the same. Then, when wet granulation is performed using a synthetic water-soluble resin and then granulated by a rolling granulator, the amount of inhalable dust can be particularly reduced.
  • the particle diameter of the CNT granules of the present embodiment is preferably 0.25 mm or more (on ASTM 60 mesh) and 4 mm or less (on ASTM 5 mesh). Further, this particle diameter is more preferably 0.3 mm or more (on the ASTM 50 mesh) and 2.83 mm or less (on the ASTM 7 mesh). As the particle size becomes smaller than 0.3 mm, the fluidity from the hopper or the like decreases, automatic metering becomes difficult, and the amount of CNT particles scattered tends to increase in the use environment.
  • the particle size of the CNT particles can be determined by placing the CNT particles together with a measure and observing the particles with an optical microscope. Further, generally, it is measured in accordance with JIS K6219-4 "How to obtain size distribution of granulated particles".
  • the hardness of particles having a particle diameter of 1 mm is preferably 10 g or more and 25 g or less.
  • the hardness of the CNT granules exceeds 25 g, not only the initial dispersibility but also the final dispersibility tends to be deteriorated when compounding and dispersing in the synthetic resin, rubber, water, solvent, or vehicle.
  • the hardness of the CNT granules becomes smaller than 10 g, powdering tends to occur at the time of packaging, transportation, stocking, compounding and kneading, and the like, which tends to cause environmental pollution, which is not preferable.
  • the hardness of the CNT granules can be measured according to the method for determining the hardness of granulated particles, JIS-K6219-3A method. There are manual and automatic measuring devices, and either one may be selected.
  • the shape is spherical, and the hardness of the particles having a particle diameter of 1 mm is 10 g or more and 25 g or less, the following effects can be obtained.
  • the particle size of the CNT granules is 0.25 mm or more and 4 mm or less, 0.3 mm or more and 2.83 mm or less, and the hardness of the particles having a particle size of 1 mm is 10 g or more and 25 g or less. It is possible to prevent the formation of a bridge in the hopper or the like due to an object and to prevent the pipes from being blocked during idling.
  • the CNT granules of this embodiment can be used by blending with various base resins, rubbers, vehicles, etc. and kneading.
  • the composition obtained by kneading the CNT granules is used as various products, for example, a semiconductor tray, a transparent conductive film, or an antistatic molding or a conductive molding used for cars and the like.
  • the base resin include thermoplastic resins and thermosetting resins.
  • thermoplastic resin examples include polyolefin resins (polypropylene, polyethylene, etc.), polystyrene, rubber-modified impact-resistant polystyrene, ABS resin, PVC resin, polyamide resin, polyester resin, polyacetal resin, polycarbonate resin, and polysulfone resin. Is mentioned.
  • thermosetting resins include unsaturated polyester resins, vinyl ester resins, epoxy resins, phenol resins, and polyimide resins.
  • the CNT particles of the present embodiment can be dispersed in a vehicle such as water and a solvent and used as a conductive ink, a conductive paint, a capacitor, a conductive auxiliary agent for a lithium ion battery, or a material for a fuel cell.
  • the CNT granules of the present embodiment can be compounded with rubbers such as SBR, BR, NR, IR, NBR, EPDM, urethane rubber, and silicone rubber, and applied to tires or various rubber products.
  • a sample having a diameter of 3 mm is prepared from this sheet using a punching blade, and pressed for 5 minutes by a press machine heated to 160 ° C. to form a thin film through which light of a fluorescent lamp transmits.
  • the dispersibility is evaluated by observing this thin film with an optical microscope.
  • CNT powder having the best dispersibility (Kanos100P manufactured by KUMHO Co., Ltd.) is 10 points, and the worst example 1 is 1 point.
  • the initial dispersibility will be supplemented.
  • Particles exist in an aggregated state, and the form of aggregation is formed by aggregated particles (aggregates) as hard aggregates of primary particles, soft aggregated particles (agglomerates), and soft aggregated particles (flocculates) with loose bonds. ing.
  • the initial dispersibility referred to here is an evaluation of the process of crushing the entire flocculate and a part of the agglomerates, and in the case of CNT granules, crushing of the granulated particles and the two components that constitute this. This is an evaluation that examines the degree of disintegration (unraveling) of secondary aggregation.
  • the CNTs having poor initial dispersibility have poor final dispersibility when the resin is melted in a shaver shaver state when it is kneaded with a twin-screw kneader or the like and it is difficult to take a share, for example, when polyethylene resin or the like is used. Further, when used in water or a solvent system, this tendency appears remarkably, and it is an extremely important evaluation method in evaluating the dispersibility of a material used for kneading having a relatively small shear.
  • the amount of CNT particles scattered (the amount of inhalable dust composed of particles of 10 ⁇ m or less) can be 0.2 mg / m 3 or less, and the risk of environmental pollution can be extremely reduced. Furthermore, CNT granules having excellent initial dispersibility can be obtained. Reducing the amount of inhalable dust is related to the hardness of the granulated product, but even with the same hardness, after granulating with a low-concentration water-soluble resin liquid as a binder, additional granulation is added with a rolling granulator. This is probably the result of sizing.
  • the “Industrial Accident Law and Fire Defense Law” reduces the risk of fire, (ii) does not require a licensed person to handle dangerous materials (work chief), (iii) does not require various protective equipment, ( iv) No need to measure work environment every 6 months, (v) No special health check, (vi) Reduced hazard to human body, and (vii) Special hazardous materials for storing pre-dried products, solvents, etc. It has the advantage that no storage space is required. In this way, simplification is achieved in many aspects, and energy and labor can be saved.
  • the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope of achieving the object of the present invention are included in the present invention.
  • the true sphere is formed by two steps of a granulation step of obtaining a granulated product and a granulation step of granulating the granulated product obtained in the granulation step to obtain a granulated product.
  • a spherical granulated product close to the above was produced, the present invention is not limited to this.
  • the sizing process can be omitted.
  • An intensive mixer is preferable to a Henschel-type stirring granulator as a granulator that approaches a true sphere by a single granulation step.
  • Example 1 In a 2 L SUS container, 480 g of ion-exchanged water heated to about 50 ° C. and a synthetic water-soluble resin (polyvinylpyrrolidone (PVP), “Pittscor K-30” manufactured by Daiichi Kogyo Co., Ltd., solid content 95%) As described above, 9.35 g (number-average molecular weight of 10,000) (8.89 g in terms of solid content) was charged and stirred for 5 minutes with a homomixer to completely dissolve the resin and prepare a resin binder aqueous solution.
  • PVP polyvinylpyrrolidone
  • Pittscor K-30 manufactured by Daiichi Kogyo Co., Ltd.
  • the spraying was performed in a fine mist state by attaching an empty cone nozzle KB (spraying flow rate of 2 to 107 L / hour) manufactured by Ikeuchi Co., Ltd. to the tip of the hose from the metering pump.
  • the amount of water in this granulation is 6.0 times the amount of CNT.
  • the resin amount with respect to CNT is 10.0% (the compounding amount of CNT is 900 parts by mass with respect to 100 parts by mass of resin).
  • the rotation speed of the Henschel mixer was lowered to the minimum and the mixture was further stirred for 2 minutes to obtain a wet granulated product (water content 85.7%).
  • the temperature inside the Henschel mixer after the granulation was about 70 ° C., and almost no granules were attached to the wall of the mixer. This may be related to the use of hot water at 50 ° C.
  • a part of the wet granulated product was dried with a hot air dryer at 90 ° C. until the water content was 1% or less, and a photograph thereof was taken. This photograph is shown in FIG. Next, this wet granulated product was transferred to a pan-type granulator for granulation and sizing.
  • the pan-type granulator uses a 500 mm diameter type manufactured by Mitsufuku Industry Co., Ltd., and while rotating at 10 to 45 rpm, the wet granulated product is gradually added over a period of about 10 minutes to make sure that the shape of the granule is true. When it became a ball, it was stopped to obtain a sized product. Then, it was dried with a hot air dryer at 90 ° C. until the water content became 1% or less, to obtain CNT granules. A photograph of the obtained CNT granules was taken. This photograph is shown in FIG.
  • Example 2 The wet granulated product obtained in the same manner as in Example 1 was dried with a hot air dryer at 90 ° C. until the water content was 10% or less, transferred to a pan-type granulator, and granulated and sized. ..
  • the pan-type granulator uses a 500 mm diameter type manufactured by Mitsufuku Industry Co., Ltd., puts the entire amount of the wet granulated product while rotating at 40 rpm, and stops when the shape of the particle becomes a sphere, A sized product was obtained. Then, it was dried with a hot air dryer at 90 ° C. until the water content became 1% or less, to obtain CNT granules. A photograph of the obtained CNT granules was taken. This photograph is shown in FIG.
  • Example 3 The amount of ion-exchanged water in the resin binder aqueous solution was changed to 560 g, and the amount of polyvinylpyrrolidone was changed to 4.43 g (4.21 g in terms of solid content, and the amount of resin relative to CNT was 5.0%). CNT granules were obtained in the same manner as in Example 2 except for the above. The amount of water in this granulation is 7 times the amount of CNT, and the amount of water in the obtained wet granulated product is 87.5%.
  • Example 4 The amount of ion-exchanged water in the aqueous resin binder solution was changed to 560 g, and the amount of polyvinylpyrrolidone was changed to 2.60 g (2.47 g in terms of solid content, and the amount of resin relative to CNT was 3.0%).
  • CNT granules were obtained in the same manner as in Example 2 except for the above. The amount of water in this granulation is 7 times the amount of CNT, and the amount of water in the obtained wet granulated product is 87.5%.
  • Example 5 instead of polyvinylpyrrolidone, polyethyleneimine (PEI, "SP-018” manufactured by Nippon Shokubai Co., Ltd., molecular weight 1800, solid content of 98% or more) 9.07 g (solid content converted to 8.89 g, resin for CNT) CNT granules were obtained in the same manner as in Example 2, except that the amount was 10.0%. The amount of water in this granulation is 6 times the amount of CNTs, and the amount of water in the obtained wet granulated product is 85.7%.
  • PEI polyethyleneimine
  • SP-018 manufactured by Nippon Shokubai Co., Ltd., molecular weight 1800, solid content of 98% or more
  • Example 6 CNT granules were obtained in the same manner as in Example 1 except that an intensive mixer (Schwnfabrik Gustaf Irish Co., Ltd.) was used as an apparatus used for stirring granulation instead of the Henschel mixer.
  • the amount of water in this granulation is 6.1 times the amount of CNT.
  • the blade of the stirrer was changed to a screw type, and while stirring at about 1000 rpm, the whole amount of the resin binder solution was dropped little by little, and then 276 g of toluene was added while observing the granulation property.
  • After removing water from the obtained granules with a 60 mesh sieve filtered water was collected and treated at a wastewater treatment plant), it was air-dried in a draft for 10 hours, and then dried in a vacuum dryer set at 70 ° C for 8 hours. Then, water and toluene were completely removed (water content was 1% or less) to obtain CNT particles.
  • the obtained CNT granules were spherical and the particle size was 0.5 to 3 mm.
  • a photograph of the obtained CNT granules was taken. This photograph is shown in FIG.
  • Example 2 A wet type wet process was performed in the same manner as in Example 3 except that a water-soluble rosin-based resin (natural resin rosin added with ethylene oxide, “REO-30” manufactured by Harima Kasei Co., Ltd.) was used instead of polyvinylpyrrolidone. A granulated product was obtained. The compounding amount of REO-30 with respect to 80 g of CNT powder was 4.2 g in terms of solid content (the amount of resin with respect to CNT was 5%). Next, a multi-gran MG-55-2 manufactured by DALTON was used to obtain a cylindrical granulated product having a diameter of 4 mm. Then, it was dried with a hot air dryer at 90 ° C.
  • a water-soluble rosin-based resin natural resin rosin added with ethylene oxide, “REO-30” manufactured by Harima Kasei Co., Ltd.
  • FIG. 6 (A) is a photograph taken from the side
  • FIG. 6 (B) is a photograph taken of a cut surface.
  • the spraying was performed in a fine mist state by attaching an empty cone nozzle KB (spraying flow rate of 2 to 107 L / hour) manufactured by Ikeuchi Co., Ltd. to the tip of the hose from the metering pump.
  • an empty cone nozzle KB spraying flow rate of 2 to 107 L / hour
  • synthetic water-soluble resin polyvinylpyrrolidone (PVP), “Pitscol K-30” manufactured by Daiichi Kogyo Co., Ltd., solid content 95% or more, number average molecular weight 10000
  • the amount of water in this granulation is 6.0 times the amount of CNT.
  • the resin amount with respect to CNT is 10.0% (the compounding amount of CNT is 900 parts by mass with respect to 100 parts by mass of resin).
  • the rotation speed of the Henschel mixer was lowered to the minimum and the mixture was further stirred for 2 minutes to obtain a wet granulated product.
  • the temperature inside the Henschel mixer after granulation was about 30 ° C. Next, this wet granulated product was transferred to a pan-type granulator for granulation and sizing.
  • the pan-type granulator uses a 500 mm diameter type manufactured by Mitsufuku Industry Co., Ltd., and while rotating at 10 to 45 rpm, the wet granulated product is gradually added over a period of about 10 minutes to make sure that the shape of the granule is true. When it became a ball, it was stopped to obtain a sized product. Then, it was dried with a hot air dryer at 90 ° C. until the water content became 1% or less, to obtain CNT granules.
  • the sample amount was changed to 5 levels, the amount of each scattering was calculated, and it was graphed, and the dust amount when the sample amount was 270 mg was adopted as the inhalable dust amount consisting of particles of 10 ⁇ m or less from the graph. did.
  • the numerical value compared with the result of the reference example 1 which is a CNT powder is also shown together.

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JP5057513B2 (ja) 2007-09-06 2012-10-24 大日精化工業株式会社 カーボンナノチューブ樹脂組成物、カーボンナノチューブ分散組成物、それらの使用方法およびそれらを使用した物品
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JP2007023149A (ja) * 2005-07-15 2007-02-01 National Institute Of Advanced Industrial & Technology 導電性が制御されたカーボンナノチューブ分散ポリイミド
WO2009008516A1 (ja) * 2007-07-11 2009-01-15 Mikuni Shikiso Kabushiki Kaisha カーボンナノチューブの造粒物およびその製造方法
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