WO2013021797A1 - Fil à torsion de nanotubes de carbone et son procédé de fabrication - Google Patents

Fil à torsion de nanotubes de carbone et son procédé de fabrication Download PDF

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Publication number
WO2013021797A1
WO2013021797A1 PCT/JP2012/068297 JP2012068297W WO2013021797A1 WO 2013021797 A1 WO2013021797 A1 WO 2013021797A1 JP 2012068297 W JP2012068297 W JP 2012068297W WO 2013021797 A1 WO2013021797 A1 WO 2013021797A1
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Prior art keywords
carbon nanotube
twisted yarn
nanotube twisted
yarn
liquid
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PCT/JP2012/068297
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English (en)
Japanese (ja)
Inventor
幸司 喜多
正樹 西村
赤井　智幸
晃明 松葉
里佐 宇都宮
松本　均
Original Assignee
地方独立行政法人大阪府立産業技術総合研究所
日新電機株式会社
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Application filed by 地方独立行政法人大阪府立産業技術総合研究所, 日新電機株式会社 filed Critical 地方独立行政法人大阪府立産業技術総合研究所
Priority to JP2013527947A priority Critical patent/JP5994087B2/ja
Publication of WO2013021797A1 publication Critical patent/WO2013021797A1/fr

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    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/16—Yarns or threads made from mineral substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
    • D10B2101/122—Nanocarbons

Definitions

  • the present invention relates to a carbon nanotube twisted yarn and a method for producing the same.
  • Carbon nanotubes are said to be excellent in mechanical properties, electrical properties, thermal properties, etc., and are expected to be used and applied in various industries including field emission displays and conductive fillers. Of these, carbon nanotube twisted yarns obtained by spinning carbon nanotube fibers are expected to be developed into conductive wires by utilizing the conductivity of carbon nanotubes.
  • Patent Document 1 Non-Patent Documents 1 and 2.
  • Patent Document 1 discloses a process of focusing discontinuous carbon nanofibers generated from a carbon source gas and a catalyst metal source gas supplied together with a carrier gas from one end of a furnace core tube in a discharge tube disposed in the furnace core tube. And a method of producing a carbon nanofiber sliver yarn having a step of twisting the yarn gathered inside or outside the discharge pipe.
  • Non-Patent Document 1 carbon nanotubes are grown in high density and high orientation on a substrate by chemical vapor deposition, and a toothpick spindle (weight) is attached to the tip of the motor rotation shaft, and the tip of the spindle In a state where a plurality of carbon nanotubes are connected to each other, a method of forming a twisted yarn made of carbon nanotubes by rotating the spindle and separating the tip of the spindle from the substrate on which the aggregate of carbon nanotubes has grown is described. Yes.
  • Non-Patent Document 2 a carbon source (a mixture of acetone and ethanol) and a catalyst (ferrocene and thiophene) and a carrier gas are supplied together with a carrier gas from the upper part of a heated gas flow reactor, and the generated carbon nanotube aggregate is supplied to the reactor. It describes a method for producing continuous multi-walled carbon nanotube yarns by shrinking with water, drying with an infrared heater, and winding after being taken out.
  • Non-Patent Document 1 or 2 has insufficient mechanical properties (tensile strength and elongation), and is not suitable for practical use.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a carbon nanotube twisted yarn excellent in mechanical properties and a method for producing the same.
  • the present inventors have found that there is a gap between the carbon nanotube bundles constituting the carbon nanotube twisted yarn, and this gap inhibits the interaction between the carbon nanotube bundles, and the dynamics.
  • the carbon nanotube bundle can be efficiently agglomerated by recognizing that the improvement in properties is hindered and applying a pressure of 500 kgf / cm 2 (49 MPa) or more to the carbon nanotube twisted yarn in the liquid.
  • the present inventors have found that the interaction between the carbon nanotube bundles is enhanced, and as a result, the mechanical properties of the carbon nanotube twisted yarn are improved.
  • the present inventors have completed the present invention. It came.
  • this invention provides the following carbon nanotube twisted-yarn and its manufacturing method.
  • a method for producing a carbon nanotube twisted yarn comprising twisting a carbon nanotube yarn and then applying a pressure of 500 kgf / cm 2 or more in a liquid.
  • the liquid is at least one selected from the group consisting of water, lower alcohols having 1 to 5 carbon atoms, acetone, diethyl ether, chloroform, dichloromethane, ethyl acetate, and tetrahydrofuran.
  • a method for producing carbon nanotube twisted yarn comprising twisting a carbon nanotube yarn and then applying a pressure of 500 kgf / cm 2 or more in a liquid.
  • Item 4 The method for producing a carbon nanotube twisted yarn according to Item 3, wherein the liquid is water. 5. 5. The method for producing a carbon nanotube twisted yarn according to any one of the above items 1 to 4, wherein the carbon nanotube twisted yarn subjected to a pressure of 500 kgf / cm 2 or more in a liquid is further twisted. 6). Item 6. The method for producing a carbon nanotube twisted yarn according to Item 5, wherein the number of twists to be added is 1,000 to 5,000 T / m. 7). 7. The method for producing a carbon nanotube twisted yarn according to any one of Items 1 to 6, wherein the carbon nanotube twisted yarn is treated with a liquid before pressure is applied in the liquid. 8).
  • a carbon nanotube twisted yarn excellent in mechanical properties and a method for producing the same can be provided.
  • a carbon nanotube twisted yarn having mechanical properties suitable for practical use can be produced, and the obtained carbon nanotube twisted yarn has a particularly high elongation rate, so that it can be used as a reinforcing material, a conductor, a heat conductor, etc. Is possible.
  • the carbon nanotube twisted yarn production method of the present invention is characterized in that after twisting a carbon nanotube yarn, a pressure of 500 kg / cm 2 or more is applied in a liquid.
  • a pressure of 500 kg / cm 2 or more is applied in a liquid.
  • high pressure liquid process the process of applying a pressure of 500 kg / cm 2 or more in the liquid may be referred to as “high pressure liquid process”.
  • the handling properties are improved, the carbon nanotube bundles constituting the carbon nanotube twisted yarn are efficiently aggregated, and the carbon nanotube bundles are Since the interaction can be strengthened, a carbon nanotube twisted yarn excellent in mechanical properties can be produced.
  • the present invention mainly specifies a post-process performed after the carbon nanotube twisted yarn is formed. Therefore, as long as a yarn composed of carbon nanotubes is twisted, it can be used in the present invention regardless of the type and form of carbon nanotubes and the method of producing twisted yarns.
  • the carbon nanotubes constituting the twisted yarn may be single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes, or a mixture thereof. Further, these carbon nanotubes may have any form as long as they can be formed into yarn.
  • a method of making a yarn from the carbon tube and twisting the obtained yarn is not particularly limited, and a known method can be used.
  • a carbon nanotube twisted yarn can be easily formed, and therefore an aggregate obtained by chemical vapor deposition on a substrate is preferable.
  • a carbon nanotube thread (hereinafter referred to as a “carbon nanotube thread”) is formed of carbon nanotubes which are drawn from the aggregate of carbon nanotubes grown on the substrate by chemical vapor deposition and are continuously arranged in one direction. .) And then twisting the carbon nanotube yarn to form a carbon nanotube twisted yarn.
  • the substrate is not limited, and a known or commercially available substrate can be used.
  • a plastic substrate, a glass substrate, a silicon substrate, a metal such as iron or copper, or a metal substrate containing an alloy thereof can be used.
  • a silicon dioxide film may be laminated on the surface of these substrates.
  • the catalyst layer can be preferably formed by evaporating or sputtering iron. Thereby, a carbon nanotube aggregate formed with high density and high orientation can be produced.
  • the carbon nanotubes to be subjected to chemical vapor deposition on the substrate may be single-walled carbon nanotubes, double-walled carbon nanotubes, or multi-walled carbon nanotubes, or a mixture thereof.
  • the form of these carbon nanotubes is not particularly limited, but since it is easy to form a twisted carbon nanotube easily, it is preferably an aggregate formed on a substrate with high density and high orientation.
  • the high density indicates that the bulk density of the carbon nanotubes on the substrate is about 20 mg / cm 3 or more, preferably about 30 mg / cm 3 or more, and more preferably about 50 mg / cm 3 or more. If the bulk density is smaller than this range, the interaction between adjacent carbon nanotube molecules is weakened, and the pull-out property may be deteriorated.
  • High orientation means that the carbon nanotubes are adjacent to each other and are perpendicular to the substrate plane (vertical orientation).
  • An aggregate of carbon nanotubes that are vertically aligned at a high density by chemical vapor deposition in this way is called a carbon nanotube forest or a vertically aligned structure of carbon nanotubes.
  • the height (length) of the carbon nanotubes formed by chemical vapor deposition may be an average of 100 ⁇ m or more, preferably 150 ⁇ m or more, and the number of carbon nanotubes may be one or more, Preferably, there are 1 to 40 layers.
  • the carbon nanotubes used in the present invention can be produced in a highly dense and highly oriented state on a substrate by performing chemical vapor deposition using, for example, a raw material gas for forming the carbon nanotubes.
  • the temperature at the time of chemical vapor deposition may be any temperature, but it is preferably at a high temperature, for example, preferably at about 680 to 800 ° C. Further, the pressure during the vapor phase growth is not limited, but usually it may be performed at atmospheric pressure.
  • the source gas only needs to contain carbon, and usually a hydrocarbon such as acetylene may be used.
  • a hydrocarbon such as acetylene
  • acetylene is preferable.
  • a rare gas such as helium or an inert gas may be used as a carrier gas for conveying the source gas.
  • the carrier gas is used, the ratio of the raw material gas flow rate to the total gas flow rate is about 3 to 7 vol%, preferably about 4.5 to 6 vol%.
  • the reaction time can be appropriately set depending on the production conditions, but may be, for example, about 2 to 5 minutes.
  • the carbon nanotubes are pulled out using a pulling tool, and the obtained carbon nanotube yarn is twisted to form a carbon nanotube twisted yarn.
  • the carbon nanotube aggregate itself may be rotated and twisted, or a roller or the like holding the carbon nanotube yarn may be rotated and twisted. Twisting is preferably performed until the diameter of the obtained carbon nanotube twisted yarn is 0.1 to 1,000 ⁇ m and the twist angle is 5 to 50 °.
  • the strength of the carbon nanotube twisted yarn is related to the diameter and the number of twists (twist angle). As the diameter of the carbon nanotube twisted yarn is thinner, the strength is increased. However, if the carbon nanotube twisted yarn is too thin, the strength (breaking load) is reduced and the handling property is lowered. Therefore, the diameter is preferably 1 to 1,000 ⁇ m. Further, the twist angle is 0 ° to 90 ° depending on the number of twists. However, if the twist angle is too small or too large, the yarn strength decreases. Therefore, the twist angle is preferably about 5 to 50 °. Is preferably adjusted in the range of about 1,000 to 200,000 T / m so that the number of twists (number of twists per meter of yarn: T / m) is about 10 to 40 °.
  • a carbon nanotube twisted yarn having a length of 1 m or more, a yarn diameter of about 0.1 to 1,000 ⁇ m, a twist angle of about 5 to 50 °, and a twist number of about 1,000 to 200,000 T / m is formed. can do.
  • a pressure of 500 kgf / cm 2 or more is applied in the liquid to the carbon nanotube twisted yarn formed as described above.
  • the carbon nanotube bundle which comprises a carbon nanotube twisted yarn aggregates efficiently, and the interaction (Van der Waals force, frictional force, etc.) between carbon nanotube bundles becomes strong.
  • the mechanical properties of the carbon nanotube twisted yarn can be improved.
  • the liquid in which the carbon nanotube twisted yarn is immersed is preferably a highly volatile liquid (easily volatile liquid) from the viewpoint of being rich in quick drying.
  • the readily volatile liquid include water, lower alcohols having 1 to 5 carbon atoms (methanol, ethanol, propanol, butanol, pentanol), acetone, diethyl ether, chloroform, dichloromethane, ethyl acetate, tetrahydrofuran and the like. These can be used alone or in admixture of two or more. Or it may be an aqueous solution.
  • water is more preferable from the viewpoint of safety (toxicity and flammability).
  • crosslinking agent a compound having at least one crosslinkable group in the molecule can be used.
  • the crosslinkable group include ethylenically unsaturated groups such as vinyl group, allyl group, butenyl group, acryloyl group, acryloyloxy group, acrylamide group, methacryloyl group, methacryloyloxy group, methacrylamide group, vinyl ether group, and vinylamino group.
  • a crosslinkable group having a small ring such as a cyclopropyl group, a cyclobutyl group, an epoxy group, a glycidyl group, an oxetane group, a diketene group or an episulfide group.
  • an acryloyloxy group and a methacryloyloxy group are preferable.
  • Monofunctional cross-linking agents containing one acryloyloxy group or methacryloyloxy group in the molecule include, for example, benzyl acrylate, phenoxyethyl acrylate, polypropylene glycol acrylate, nonanediol acrylate, butanediol acrylate, hexanediol acrylate, tris (2-acryloyl Oxyethyl) cyanurate, 3-phenoxy-2-propanoyl acrylate, and the like.
  • 1,4-butanediol dimethacrylate 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, nonapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, 2,2-bis [4- (Acryloxydiethoxy) phenyl] propaprop 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether,
  • pentaerythritol trimethacrylate trimethylolpropane trimethacrylate, glycerol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol Hexamethacrylate, caprolactone-modified dipentaerythritol hexaacrylate obtained by reacting acrylic acid with a polyol obtained by adding ⁇ -caprolactone to dipentaerythritol (KAYARAD (registered trademark) DPCA series, Nippon Kayaku Co., Ltd.), 1,1,3 , 3,5,5-Hexa (methacryloylalkylenedioxy) cyclotriphosphazene, tris (acrylate ethyl) isocyan
  • polyfunctional crosslinking agent containing two acryloyloxy groups or methacryloyloxy groups in the molecule and one glycidyl group in the molecule, for example, N, N′-bis (acrylateethyl) -N ′′ -glycidylisocyanuric acid, etc. Is mentioned.
  • any of a monofunctional crosslinking agent containing one crosslinkable group as described above in the molecule, a bifunctional crosslinking agent containing two, or a polyfunctional crosslinking agent containing three or more may be used.
  • a cross-linked structure is not formed unless two or more carbon nanotubes or bundles are present in the immediate vicinity of the crosslinkable group (C ⁇ C bond, etc.).
  • two or more crosslinkable groups (C ⁇ C bond, etc.) are contained in the molecule, two carbon nanotubes may not exist simultaneously around one crosslinkable group.
  • Crosslinking agents containing two groups in the molecule are preferred.
  • crosslinkable groups when crosslinkable groups are present at both ends of the crosslinker molecule, carbon nanotubes that are so far apart can be crosslinked. For the same reason, when three or more crosslinkable groups are included in the crosslinker molecule, the probability of crosslinking between carbon nanotubes existing everywhere increases.
  • the bundles are separated by about 10 angstroms.
  • the distance between the crosslinkable groups is about 5 angstroms, that is, the molecular size of the crosslinking agent is either the major axis or the minor axis. It is desirable to be angstrom (5 ⁇ 10 ⁇ 10 m) or more.
  • crosslinking agents can be used singly or in combination of two or more.
  • the liquid containing the crosslinking agent is preferably in a solution state in which the crosslinking agent is dissolved in the liquid.
  • the concentration of the crosslinking agent in the solution is usually 0.1 to 10 wt%, preferably 0.1 to 5 wt%.
  • the viscosity is such that the crosslinking agent is easily impregnated, and the carbon nanotube twisted yarn can be efficiently impregnated with the crosslinking agent.
  • the crosslinking agent does not dissolve in the liquid, it may be dispersed in the liquid using an appropriate amount of a dispersant or the like.
  • the treatment for applying pressure to the carbon nanotube twisted yarn immersed in the liquid can be performed using, for example, an isotropic pressurizer.
  • the pressure to be applied is usually about 500 kgf / cm 2 or more, preferably about 500 to 5000 kgf / cm 2 , more preferably about 1000 to 4000 kgf / cm 2 .
  • the pressurization time is about 1 second to 1 day, more preferably about 1 minute to 1 hour.
  • the carbon nanotube twisted yarn is taken out of the liquid and dried to remove the liquid.
  • the drying process may be performed under reduced pressure.
  • the vacuum drying treatment can be performed, for example, in a vacuum dryer at a pressure of about 10 5 to 1 Pa, preferably about 10 4 to 1 Pa.
  • the reduced pressure drying time may be about 1 hour to 3 days.
  • the carbon nanotube bundles can be further agglomerated, and the interaction between the carbon nanotube bundles is increased, so that the strength of the obtained carbon nanotube twisted yarn is further increased.
  • the number of times of twisting is not particularly limited as long as it is one or more, but the number of twists is set so that the twist angle of the obtained carbon nanotube twisted yarn is about 5 to 50 °, more preferably about 10 to 40 °. It is preferable to adjust within a range of about 1,000 to 5,000 T / m. Further, the twisting may be added either before or after the vacuum drying treatment.
  • the carbon nanotube twisted yarn when pressure is applied in a liquid to which a cross-linking agent is added, it is preferable to irradiate the carbon nanotube twisted yarn with an electron beam thereafter.
  • the electron beam irradiation may be performed at any stage after the pressure is applied. For example, it can be performed either before or after the vacuum drying treatment or before or after the additional twisting.
  • an irradiation dose of usually 50 to 600 kGy, preferably 50 to 400 kGy may be achieved.
  • the electron beam source for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type may be used. Irradiation is preferably performed under a nitrogen atmosphere.
  • the twisted yarn may be treated with a liquid before the carbon nanotube twisted yarn is subjected to the high-pressure liquid treatment.
  • a liquid By preliminarily attaching a liquid to the surface of the carbon nanotube twisted yarn and drying it, the carbon nanotube bundle near the surface of the carbon nanotube twisted yarn is aggregated in advance, so that the strength of the obtained carbon nanotube twisted yarn can be further increased.
  • the liquid is preferably a highly volatile liquid (easily volatile liquid) from the viewpoint of being rich in quick drying.
  • the readily volatile liquid include water, lower alcohols having 1 to 5 carbon atoms (methanol, ethanol, propanol, butanol, pentanol), acetone, diethyl ether, chloroform, dichloromethane, ethyl acetate, tetrahydrofuran and the like. These can be used alone or in admixture of two or more. Or it may be an aqueous solution.
  • water is more preferable from the viewpoint of safety (toxicity and flammability).
  • a cross-linking agent may be added to the above liquid.
  • the cross-linking agent the same cross-linking agent added to the liquid in the above-described high-pressure liquid treatment can be used.
  • the liquid to which the crosslinking agent is added is preferably a solvent that dissolves the crosslinking agent.
  • the concentration of the crosslinking agent is usually from 0.1 to 10 wt%, preferably from 0.1 to 5 wt%.
  • the crosslinking agent does not dissolve in the liquid, it may be dispersed in the liquid using an appropriate amount of a dispersant or the like.
  • the treatment with the liquid can be performed by any method that can attach the liquid to the twisted yarn.
  • the atomized liquid may be sprayed on the twisted yarn using a spraying device, or the twisted yarn may be passed through the liquid filled in the container.
  • the carbon nanotubes are pulled out from the aggregate of carbon nanotubes grown on the substrate by chemical vapor deposition, twisted to form a twisted yarn, and then a pressure of 500 kg / cm 2 or more is applied in the liquid to apply the carbon nanotube twisted yarn.
  • a manufacturing method will be described with reference to the accompanying drawings.
  • FIG. 1 is a schematic configuration diagram illustrating an example of a basic configuration of a carbon nanotube twisted yarn manufacturing apparatus that can be used in a carbon nanotube twisted yarn manufacturing method.
  • the carbon nanotube twisted yarn manufacturing apparatus 1 is a device that manufactures a carbon nanotube twisted yarn from an aggregate of carbon nanotubes grown by chemical vapor deposition on a substrate.
  • FIG. 1 shows a substrate fixing means 2, a twisting means 3, and The manufacturing apparatus 1 provided with the winding means 4 is shown.
  • the substrate fixing means 2 is a fixing base 21 for fixing the substrate Z on which the carbon nanotube aggregate c formed by chemical vapor deposition is formed.
  • the substrate Z is bonded by using a commercially available double-sided tape.
  • the board is fixed.
  • the carbon nanotube aggregate c formed on the substrate Z is an aggregate in which carbon nanotubes are grown with high density and high orientation by the chemical vapor deposition method described above.
  • the bulk density of the carbon nanotube aggregate is 30 mg / cm 3 or more, and the height is 150 ⁇ m or more.
  • the carbon nanotubes are continuously pulled out from the substrate Z in the state of the carbon nanotube yarn Y. It is.
  • the drawing is performed using an apparatus (drawing tool) for pulling out the carbon nanotubes from the substrate Z in the state of the carbon nanotube yarn Y.
  • the drawing tool 5 having the ultrathin shaft portion 51 as shown in FIG. 2 is used. be able to.
  • the carbon nanotube yarn Y refers to a carbon nanotube drawn out from the carbon nanotube aggregate c formed on the substrate Z and continuously connected in one direction.
  • a sheet having a sheet state of 1 m and a thickness of 10 nm to 1 cm may be used.
  • a twisting device 31 is used as the twisting means 3.
  • the twisting device 31 is directly connected to the fixing base 21 of the substrate fixing means 2, and the substrate Z fixed to the fixing base 21 of the substrate fixing means 2 is pulled out in the drawing direction of the carbon nanotube yarn Y (in the figure, the arrow A And a motor (not shown) that is driven to rotate around the same rotation axis as the “A direction”).
  • the motor of the twisting device 31 By rotating the motor of the twisting device 31, the carbon nanotube yarn Y drawn from the substrate Z is twisted, and the carbon nanotube twisted yarn X is manufactured.
  • the winding means 4 includes a winding bobbin 41 around which the carbon nanotube twisted yarn X is wound, and a drive motor (not shown) that rotationally drives the winding bobbin 41.
  • the rotation axis of the take-up bobbin 41 is set to be parallel to an axis perpendicular to the drawing direction (A direction) of the carbon nanotube drawn from the substrate Z.
  • the winding bobbin 41 rotates to wind up the carbon nanotube twisted yarn X, the carbon nanotube yarn Y is pulled out from the substrate Z.
  • the winding bobbin 41 is preferably traversed.
  • anti-slip processing may be applied to the surface of the winding bobbin 41.
  • the method of anti-slip processing is not limited, and examples thereof include rubber lining, resin coating, satin finish, and embossing.
  • a pressure of 500 kgf / cm 2 or more is applied to the carbon nanotube twisted yarn X in a liquid.
  • the carbon nanotube twisted yarn X is passed through the tube 61 of the high-pressure liquid treatment tool 6, the liquid L1 is poured, the carbon nanotube twisted yarn X is immersed in the liquid L1, and plugs 62 are attached to both ends of the tube.
  • the high-pressure liquid treatment tool 6 is installed in an isotropic pressurizing device, and a pressure of 500 kgf / cm 2 or more is applied to the carbon nanotube twisted yarn X.
  • the material of the tube 61 is preferably silicon, rubber, polypropylene, polyvinyl chloride, Teflon (registered trademark), etc., but silicon is more preferable from the viewpoint of flexibility and chemical resistance.
  • the liquid L1 in which the carbon nanotube twisted yarn is immersed is preferably a highly volatile liquid (easily volatile liquid) from the viewpoint of rich quick drying.
  • the readily volatile liquid include water, lower alcohols having 1 to 5 carbon atoms (methanol, ethanol, propanol, butanol, pentanol), acetone, diethyl ether, chloroform, dichloromethane, ethyl acetate, tetrahydrofuran and the like. These can be used alone or in admixture of two or more. Or it may be an aqueous solution.
  • the liquid it is particularly preferable to use water from the viewpoint of safety (toxicity and flammability).
  • crosslinking agent examples include ethylenically unsaturated groups such as vinyl group, allyl group, butenyl group, acryloyl group, acryloyloxy group, acrylamide group, methacryloyl group, methacryloyloxy group, methacrylamide group, vinyl ether group and vinylamino group;
  • a compound having at least one crosslinkable group in the molecule such as a crosslinkable group having a small ring such as a cyclopropyl group, a cyclobutyl group, an epoxy group, a glycidyl group, an oxetane group, a diketene group, and an episulfide group can be used.
  • a monofunctional crosslinking agent containing one acryloyloxy group or methacryloyloxy group in the molecule for example, benzyl acrylate, phenoxyethyl acrylate, polypropylene glycol acrylate, nonanediol acrylate, tris (2-acryloyloxyethyl) cyanurate) , 3-phenoxy-2-propanoyl acrylate, etc.
  • bifunctional crosslinking agents containing two acryloyloxy groups or methacryloyloxy groups in the molecule for example, 1,4-butanediol dimethacrylate, neopentylglycol dimethacrylate, ethylene Glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate Methacrylate, polyethylene glycol dimethacrylate, trip
  • the concentration of the crosslinking agent in the solution is usually 0.1 to 10 wt%, preferably 0.1 to 5 wt%. %.
  • the carbon nanotube twisted immersed in liquid the process for applying a pressure, for example, in the isotropic pressure device, pressure, 500 kgf / cm 2 of about or more, preferably 500 ⁇ 6000kgf / cm 2, more preferably about 1000 and ⁇ 4000 kgf / cm 2 or so, the pressing time, about 1 second to 1 day, more preferably, to 1 minute to 1 hour or so.
  • a pressure for example, in the isotropic pressure device
  • the carbon nanotube twisted yarn is taken out of the liquid and dried to remove the liquid.
  • the drying process may be performed under reduced pressure.
  • the vacuum drying treatment can be performed, for example, in a vacuum dryer at a pressure of about 10 5 to 1 Pa, preferably about 10 4 to 1 Pa.
  • the reduced pressure drying time may be about 1 hour to 3 days.
  • the carbon nanotube twisted yarn X1 thus obtained has been subjected to high-pressure liquid treatment, the carbon nanotube bundles constituting the carbon nanotube twisted yarn are efficiently aggregated to increase the interaction between the carbon nanotube bundles. Excellent characteristics.
  • the carbon nanotube twisted yarn fixing means 7 and the twisting means 8 shown in FIG. 4 are used.
  • One end of the carbon nanotube twisted yarn X ⁇ b> 1 is fixed to the fixing base 71 of the carbon nanotube twisted yarn fixing means 7.
  • the twisting device 81 of the twisting means 8 includes a spindle and a motor (not shown) that rotationally drives the spindle.
  • the other end of the carbon nanotube twisted yarn X1 is fixed to the spindle of the twisting device 81, and the motor is driven to add a twist to the carbon nanotube twisted yarn X1.
  • the number of times of twisting is not particularly limited as long as it is 1 or more, but the number of twists is 1,000 to 5,000 T / m so that the twist angle of the obtained carbon nanotube twisted yarn is about 5 to 50 °. It is preferable to adjust within a range. Further, the additional twisting may be performed either before or after the vacuum drying treatment.
  • the carbon nanotube twisted yarn X fixed at both ends to the fixing base 72 of the carbon nanotube twisted yarn fixing means 7 ′ is put in the sample chamber in the electron beam irradiation apparatus provided with the electron beam irradiation means 10. It can be installed and irradiated with an electron beam.
  • a commercially available double-sided tape or a liquid adhesive may be used for fixing the carbon nanotube twisted yarn X to the fixing base 72.
  • an apparatus including an irradiation unit and a power supply unit can be used.
  • the irradiation unit is a part that generates an electron beam. Thermal electrons generated by the filament in the vacuum chamber are extracted by a grid, and a high voltage is applied to accelerate the electrons.
  • the power supply unit includes a high voltage power supply and a filament power supply.
  • the inside of the vacuum chamber is usually kept at 10 ⁇ 2 to 10 ⁇ 5 Pa.
  • the carbon nanotube twisted yarn is irradiated with an electron beam in a sample chamber filled with an inert gas, generally nitrogen.
  • the inside of the sample chamber is usually kept at 20 to 100 ° C., more preferably 20 to 60 ° C.
  • the electron beam irradiation may be performed at any stage before or after the vacuum drying treatment, or before or after the additional twisting, as long as the pressure is applied.
  • FIG. 6 is a schematic configuration diagram showing another example of the basic configuration of the carbon nanotube twisted yarn manufacturing apparatus that can be used in the carbon nanotube twisted yarn manufacturing method. By using this apparatus, it is possible to perform liquid treatment while twisting and winding the carbon nanotube yarn.
  • the carbon nanotube twisted yarn manufacturing apparatus 1 ′ includes a substrate fixing means 2, a twisting means 3, a winding means 4, and a liquid passing means 9 as shown in FIG.
  • the substrate fixing means 2, the twisting means 3 and the winding means 4 are the same as those in FIG.
  • the liquid passing means 9 By disposing the liquid passing means 9 between the substrate fixing means 2 and the twisting means 3 and the winding means 4, the liquid L2 passes before the carbon nanotube twisted yarn X is wound.
  • the carbon nanotube bundles near the surface of the carbon nanotube twisted yarn X aggregate in advance, and a carbon nanotube yarn suitable for high-pressure liquid treatment is produced.
  • a cross-linking agent may be added to the liquid L2.
  • the cross-linking agent the same cross-linking agent added to the liquid in the above-described high-pressure liquid treatment can be used.
  • a method for producing a carbon nanotube twisted yarn using the carbon nanotube twisted yarn production apparatus 1 and applying an ultrahigh pressure to the obtained carbon nanotube twisted yarn in a liquid will be described below.
  • the substrate Z on which the carbon nanotube aggregate c subjected to chemical vapor deposition is formed is fixed to the substrate fixing means 2 in FIG.
  • the drawer 5 has an ultrathin shaft portion 51, and the material thereof is iron, aluminum, stainless steel, plastic, wood, glass, etc., and is not particularly limited.
  • the drawer 5 only needs to have an appropriate frictional resistance with respect to the carbon nanotubes, and in order to cause friction to the drawer 5, the surface of the drawer 5 is finely formed by forming grooves and / or embossing. It is desirable to form a simple protrusion.
  • the diameter of the ultrathin shaft portion 51 of the drawer 5 is determined depending on the average height of the carbon nanotubes grown on the substrate Z.
  • the diameter is preferably about 1/3 or less of the average height of the carbon nanotubes. If the diameter of the carbon nanotube is about 1/3 or less, when the drawing tool 5 makes one rotation in the aggregate of carbon nanotubes on the substrate Z, the diameter of the carbon nanotube will be around one or more rounds. To pull out carbon nanotubes with a high probability, it is important that they are tight for more than one round.
  • a micro drill with a blade diameter of 0.03 mm or more is commercially available, and can be used for the drawer 5.
  • the ultrathin shaft portion 51 of the drawer 5 is attached to the substrate Z.
  • the carbon nanotube c growing above is pierced and entered.
  • the depth of entry is preferably 0.01 mm or more.
  • the height position at which the ultrathin shaft portion 51 of the extraction tool 5 is pierced is preferably a height of 1 ⁇ 2 or less of the average height of the carbon nanotubes c growing on the substrate Z.
  • the drawer 5 may be rotating or may stop rotating. The entry is stopped when the ultrathin shaft portion 51 of the drawer 5 has entered 0.01 mm or more.
  • the drawer 5 With the drawer 5 remaining in this place, the drawer 5 is rotated at 1 to 1,000 rpm for 1 to 5 minutes to grip the carbon nanotube, and then the rotation is stopped and the drawer 5 is retracted.
  • the carbon nanotube yarn is fixed to the take-up bobbin 41 by moving the take-up unit 4 to the take-up bobbin 41 of the take-up device.
  • the spinning of the carbon nanotube twisted yarn is started by driving the twisting means 3 (twisting device 31) and the winding means 4 (winding bobbin 41).
  • the number of rotations of the twisting means 3 can be adjusted between 100 and 10,000 rpm, for example. If the rotational speed is too small, the number of twists that can be imparted to the carbon nanotube twisted yarn is too small, which is not preferable because the yarn strength of the carbon nanotube twisted yarn is insufficient. On the other hand, if the rotational speed is too high, the number of twists imparted to the carbon nanotube yarn is too high, and therefore the yarn strength is lowered.
  • the carbon nanotube twisted yarn X twisted by the twisting means 3 is wound up by the winding bobbin 41 of the winding means 4.
  • the rotation speed of the winding means 4 can be adjusted, for example, between 0.005 and 30 m / min. If the winding speed is too low, productivity is poor and it is not practical. On the other hand, if the winding speed is too high, thread breakage may occur in the middle, which is not preferable.
  • a continuous carbon nanotube twisted yarn X having a diameter of about 0.1 to 1,000 ⁇ m and a twist angle of about 5 to 50 ° can be produced.
  • the carbon nanotube twisted yarn X is passed through the silicon tube, the liquid is poured, the carbon nanotube twisted yarn X is immersed in the liquid, and both ends of the tube A high-pressure liquid treatment tool 6 plugged in is used.
  • the high-pressure liquid treatment tool 6 is installed in an isotropic pressurizing device that uses water pressure to cause the carbon nanotube twisted yarn X to act on the carbon nanotube twisted yarn X in a liquid.
  • the pressure is about 500 to 6000 kgf / cm 2 and the pressurizing time is about 1 minute to 1 hour.
  • the twisted carbon nanotube yarn is taken out from the liquid and dried to remove the liquid.
  • the pressure is about 10 4 to 1 Pa and the time is reduced to about 1 hour to 3 days.
  • the carbon nanotube bundles By performing additional twisting on the carbon nanotube twisted yarn subjected to a pressure of 500 kgf / cm 2 or more in the liquid, the carbon nanotube bundles can be further aggregated, and the interaction between the carbon nanotube bundles is increased.
  • the strength of the obtained carbon nanotube twisted yarn is improved.
  • the number of times of twisting is not particularly limited as long as it is 1 or more, but the number of twists is 1,000 to 5,000 T / m so that the twist angle of the obtained carbon nanotube twisted yarn is about 5 to 50 °. It is preferable to adjust within a range. Further, the additional twisting may be performed either before or after the vacuum drying treatment.
  • the carbon nanotube twisted yarn X twisted by the twisting means 3 is subjected to a pressure of 500 kgf / cm 2 or more in a liquid containing a crosslinking agent, and then subjected to electron beam irradiation, whereby the carbon nanotube bundles And the mechanical properties of the carbon nanotube twisted yarn are further improved.
  • the electron beam irradiation is preferably performed in an amount of 50 to 400 kGy in a nitrogen atmosphere.
  • the electron beam irradiation may be performed at any stage after the pressure is applied.
  • the carbon nanotube twisted yarn manufacturing apparatus 1 that can be used in the present invention and the method for applying a pressure of 500 kgf / cm 2 or more to the carbon nanotube in a liquid have been described.
  • the configuration is not limited to the above embodiment.
  • the carbon nanotube aggregate itself may be rotated and twisted, or a roller or a spindle holding the carbon nanotube yarn is rotated. May be twisted.
  • the carbon nanotube twisted yarn may be contracted in advance by passing the carbon nanotube twisted yarn through the liquid to increase the strength.
  • the carbon nanotube twisted yarn X can be appropriately irradiated with an electron beam, the carbon nanotube twisted yarn X is not fixed to the fixing base 72 as shown in FIG. You may irradiate an electron beam in the state. Further, as shown in FIG. 7, while the carbon nanotube twisted yarn X5 is unwound from one winding bobbin 41, the electron beam irradiation means 10 continuously irradiates the carbon nanotube twisted yarn X5 with the electron beam, and the other winding The take-up bobbin 41 may be wound up.
  • the method for producing a carbon nanotube twisted yarn according to the present embodiment is obtained by applying a pressure of 500 kgf / cm 2 or more in a liquid to the carbon nanotube twisted yarn produced by twisting the carbon nanotube yarn drawn from the carbon nanotube aggregate.
  • the carbon nanotube bundles constituting the carbon nanotube twisted yarn can be efficiently aggregated.
  • the interaction between the carbon nanotube bundles is strengthened, the mechanical characteristics are improved.
  • high-pressure liquid treatment is performed using a liquid containing a crosslinking agent, and then the carbon nanotube twisted yarn is irradiated with an electron beam, the interaction between the carbon nanotube bundles is further enhanced, and the mechanical properties of the carbon nanotube twisted yarn are further improved. Can do.
  • the height of the carbon nanotube aggregate was measured by measuring the height from the substrate surface to the aggregate surface in an SEM photograph obtained by photographing a cross section of the carbon nanotube aggregate at 300 times (see FIG. 8).
  • the bulk density of the carbon nanotube aggregate is obtained by measuring the weight of the substrate with an electronic balance before and after the synthesis, calculating the weight of the carbon nanotube aggregate from the weight difference, and from the weight and the aggregate height measured by the above method. The bulk density was calculated.
  • the diameter of the twisted yarn was measured by taking SEM photographs using a scanning electron microscope “JSM-7401F” manufactured by JEOL Ltd.
  • twisting angle As for the twisting angle, an SEM photograph was taken using a scanning electron microscope “JSM-7401F” manufactured by JEOL Ltd. For example, as shown in FIG. 9, the orientation direction of the wound carbon nanotubes and the central axis of the twisted yarn are formed. The angle was measured as the twist angle.
  • Example 1 Manufacture of carbon nanotube twisted yarn First, a carbon nanotube aggregate was synthesized as follows using a thermal CVD method.
  • Gas replacement in the reaction vessel was performed by repeatedly filling the gas pipe and the reaction vessel of the carbon nanotube synthesizer with an inert gas (helium) and then performing a vacuum operation for evacuation.
  • an inert gas helium
  • a silicon wafer substrate with an oxide film coated with an iron catalyst for carbon nanotube synthesis to a thickness of 20 nm or less was placed in the reaction apparatus, and the inside of the reaction vessel was purged again.
  • an inert gas (helium) at a constant flow rate the catalyst layer was heated to 750 ° C. and held at this temperature for a fixed time.
  • a mixed gas of acetylene gas and helium gas (acetylene gas 3 to 7 vol%) is introduced from a gas introduction hole installed in the flange portion of the reaction vessel and reacted with the catalyst for 2 to 5 minutes, whereby carbon nanotubes are formed on the substrate. Aggregates were formed. Thereafter, the substrate on which the carbon nanotube aggregate was formed was taken out of the reaction tube and cooled to room temperature. The aggregate of carbon nanotubes grown on the substrate had a height of 175 ⁇ m and a bulk density of 45 mg / cm 3 , and was formed with high density and high orientation.
  • a straight portion having a width of 6 mm is formed and defined in a part of the carbon nanotube aggregate obtained as described above.
  • a linear carbon nanotube aggregate (carbon nanotube substrate Z) having a constant width was produced, and these were held by the substrate fixing means 2 shown in FIG.
  • the retractor 5 was moved backward to move the carbon nanotube yarn Y onto the take-up bobbin 41 of the take-up means 4, and the carbon nanotube yarn Y was fixed to the take-up bobbin 41.
  • the carbon nanotube twisted yarn X is unwound from the take-up bobbin 41, and the carbon nanotube twisted yarn X is passed through a silicone tube (inner diameter: 6 mm, outer diameter: 8 mm) having a length of 100 mm. After plugging with a PTFE plug (outer diameter 8 mm, length 30 mm), pouring water and immersing the carbon nanotube twisted yarn X in water, plugging the other end of the silicon tube, and the high-pressure liquid treatment tool 6 Prepared.
  • Example 2 After forming the carbon nanotube twisted yarn X by the same method as in Example 1 (1), the carbon nanotube twisted yarn X was treated with high pressure liquid by the same method as in Example 1 (2) except that the liquid injected into the tube was acetone. Went.
  • Example 3 After forming the carbon nanotube twisted yarn X by the same method as in Example 1 (1), the carbon nanotube twisted yarn X was treated with high pressure liquid by the same method as in Example 1 (2) except that the liquid injected into the tube was dichloromethane. Went.
  • Example 4 After forming the carbon nanotube twisted yarn X by the same method as in Example 1 (1), the high pressure liquid was applied to the carbon nanotube twisted yarn X by the same method as in Example 1 (2) except that the liquid injected into the tube was diethyl ether. Processed.
  • Example 5 A carbon nanotube twisted yarn X having a diameter of 24 ⁇ m and a twist angle of 25 ° was produced in the same manner as in Example 1 (1). When the tensile test was implemented about the produced carbon nanotube twisted-yarn X, tensile strength was 0.18 GPa and elongation rate was 11%.
  • the carbon nanotube twisted yarn X was subjected to high-pressure liquid treatment in the same manner as in Example 1 (2) except that the pressure applied to the carbon nanotube twisted yarn X was 500 kgf / cm 2 .
  • Example 6 The carbon nanotube twisted yarn X was formed by the same method as in Example 5, and then the carbon nanotube twisted yarn was processed in the same manner as in Example 1 (2) except that the pressure applied to the carbon nanotube twisted yarn X was 1,000 kgf / cm 2. X was subjected to high pressure liquid treatment.
  • Example 7 The carbon nanotube twisted yarn X was formed by the same method as in Example 5, and then the carbon nanotube twisted yarn was processed in the same manner as in Example 1 (2) except that the pressure applied to the carbon nanotube twisted yarn X was 2,000 kgf / cm 2. X was subjected to high pressure liquid treatment.
  • Example 8 The carbon nanotube twisted yarn X was formed in the same manner as in Example 5, and then the carbon nanotube twisted yarn was processed in the same manner as in Example 1 (2) except that the pressure applied to the carbon nanotube twisted yarn X was 4,000 kgf / cm 2. X was subjected to high pressure liquid treatment.
  • Example 9 The carbon nanotube twisted yarn X was formed by the same method as in Example 5, and then the carbon nanotube twisted yarn was processed in the same manner as in Example 1 (2) except that the pressure applied to the carbon nanotube twisted yarn X was 6,000 kgf / cm 2. X was subjected to high pressure liquid treatment.
  • Example 10 A carbon nanotube twisted yarn X having a diameter of 26 ⁇ m and a twist angle of 50 ° was produced in the same manner as in Example 1 (1). When the tensile test was implemented about the produced carbon nanotube twisted-yarn X, tensile strength was 0.22 GPa and elongation rate was 16%.
  • the carbon nanotube twisted yarn X was subjected to high-pressure liquid treatment in the same manner as in Example 1 (2) except that the treatment time was 1 minute.
  • Example 11 After forming the carbon nanotube twisted yarn X by the same method as in Example 10, the high pressure liquid treatment was performed on the carbon nanotube twisted yarn X by the same method as in Example 1 (2) except that the treatment time was 10 minutes.
  • Example 12 After forming the carbon nanotube twisted yarn X by the same method as in Example 10, the carbon nanotube twisted yarn X was subjected to high-pressure liquid treatment in the same manner as in Example 1 (2) except that the drying time under reduced pressure was set to 1 day. .
  • Example 13 A carbon nanotube twisted yarn X having a diameter of 23 ⁇ m and a twist angle of 25 ° was produced in the same manner as in Example 1 (1). When the tensile test was implemented about the produced carbon nanotube twisted-yarn X, tensile strength was 0.19 GPa and elongation rate was 15%.
  • the carbon nanotube twisted yarn X was subjected to high-pressure liquid treatment in the same manner as in Example 1 (2).
  • Example 14 One end of the carbon nanotube twisted yarn X1 obtained in Example 13 is fixed to the fixing base 71 of the carbon nanotube twisted yarn fixing means 7 with double-sided tape, and the other end is attached to the twisting device 81 of the twisting means 8.
  • a double-sided tape was fixed to the spindle, and the spindle was rotated by a motor (Electr Emax EL351-IH manufactured by Nakanishi Co., Ltd.) to add a twist to the carbon nanotube twisted yarn X1, thereby producing a carbon nanotube twisted yarn X2.
  • the number of twists added was 5,000 T / m.
  • Example 15 A carbon nanotube twisted yarn X2 was produced in the same manner as in Example 14, except that the twist was added before drying under reduced pressure.
  • Example 16 Manufacture of carbon nanotube twisted yarn
  • the liquid passage means 9 of FIG. 6 (a glass petri dish with a diameter of 3 cm filled with water) is installed, and the carbon nanotube twisted yarn X passes through the water before being wound around the take-up bobbin 41.
  • a carbon nanotube twisted-yarn X3 was produced in the same manner as in Example 1 (1) except that.
  • Example 17 Manufacture of carbon nanotube twisted yarn Other than that the width of the linear portion formed and defined in a part of the carbon nanotube aggregate is 0.8 mm, and that the twisting device 31 is rotated at 4,000 rpm Produced the carbon nanotube twisted-yarn X3 by the same method as Example 16 (1).
  • Example 18 Manufacture of carbon nanotube twisted yarn A carbon nanotube aggregate having a height of 185 ⁇ m and a bulk density of 72 mg / cm 3 is used to crosslink the liquid that passes the carbon nanotube twisted yarn X before being wound around the take-up bobbin 41. Carbon having a diameter of 16 ⁇ m and a twist angle of 25 ° in the same manner as in Example 16 (1) except that a 5 wt% ethanol solution of a chemical agent (KAYARAD (registered trademark) DPCA-30 manufactured by Nippon Kayaku Co., Ltd.) was used. Nanotube twisted yarn X3 was produced. When the tension test was implemented about produced carbon nanotube twisted-yarn X3, tensile strength was 0.60 GPa and elongation rate was 17%.
  • KAYARAD registered trademark
  • DPCA-30 manufactured by Nippon Kayaku Co., Ltd.
  • the carbon nanotube twisted yarn X4 is fixed to a rectangular holder so that the yarn length becomes 1 cm, and an area beam type electron beam irradiation device (EBC300-60 manufactured by NHV Corporation) is used.
  • An electron beam generated at 2 ⁇ 10 ⁇ 5 Pa was irradiated with 200 kGy at 30 ° C. in a nitrogen atmosphere to produce a carbon nanotube twisted yarn X5.
  • Example 19 Manufacture of carbon nanotube twisted yarn Using a carbon nanotube aggregate having a height of 185 ⁇ m and a bulk density of 72 mg / cm 3 , a diameter of 20 ⁇ m and a twist angle of 25 ° were obtained in the same manner as in Example 1 (1). Carbon nanotube twisted yarn X was produced. When the tensile test was implemented about the produced carbon nanotube twisted-yarn X, tensile strength was 0.27 GPa and elongation rate was 15%.
  • twist was added by the same method as Example 14.
  • Example 20 Production of carbon nanotube twisted yarn Carbon nanotube twisted yarn X3 having a diameter of 16 ⁇ m and a twist angle of 25 ° was produced in the same manner as in Example 16 (1). When the tension test was implemented about produced carbon nanotube twisted-yarn X3, tensile strength was 0.60 GPa and elongation rate was 17%.
  • Example 21 About the carbon nanotube twisted-yarn X3 produced by the same method as Example 18 (1), after performing a high pressure liquid process by the same method as Example 19 (2), it dried under reduced pressure and produced carbon nanotube twisted-yarn X4.
  • the carbon nanotube twisted yarn X4 was irradiated with an electron beam in the same manner as in Example 18 (3) to produce a carbon nanotube twisted yarn X5.
  • Example 22 Manufacture of carbon nanotube twisted yarn Other than that the width of the linear portion formed and defined in a part of the carbon nanotube aggregate is 0.8 mm, and that the twisting device 31 is rotated at 4,000 rpm Produced the carbon nanotube twisted-yarn X3 by the same method as Example 20 (1).
  • Example 23 Manufacture of carbon nanotube twisted yarn Other than that the width of the linear portion formed and defined in a part of the carbon nanotube aggregate is 0.8 mm, and that the twisting device 31 is rotated at 4,000 rpm Produced the carbon nanotube twisted-yarn X3 by the same method as Example 18 (1).
  • Comparative Example 1 The carbon nanotube twisted yarn X was produced by the same method as in Example 1 (1), but the high-pressure liquid treatment in Example 1 (2) was not performed.
  • the carbon nanotube twisted yarn X produced by this method had a diameter of 18 ⁇ m and a twist angle of 25 °. Moreover, when the tension test was implemented about this carbon nanotube twisted-yarn X, tensile strength was 0.19 GPa and elongation rate was 10%.
  • Comparative Example 2 A carbon nanotube twisted yarn X having a diameter of 25 ⁇ m and a twist angle of 25 ° was produced in the same manner as in Example 1 (1). When the tensile test was implemented about the produced carbon nanotube twisted-yarn X, tensile strength was 0.18 GPa and elongation rate was 10%.
  • the carbon nanotube twisted yarn X was subjected to high-pressure liquid treatment in the same manner as in Example 1 (2) except that the pressure applied to the carbon nanotube twisted yarn X was atmospheric pressure (about 1 kgf / cm 2 ).
  • the carbon nanotube twisted yarn X1 produced by this method had a diameter of 24 ⁇ m and a twist angle of 20 °. Moreover, when the tension test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.15 GPa and elongation rate was 9%.
  • Comparative Example 3 After forming the carbon nanotube twisted yarn X by the same method as in Example 5, the carbon nanotube twisted yarn X was applied to the carbon nanotube twisted yarn X in the same manner as in Example 1 (2) except that the pressure applied to the carbon nanotube twisted yarn X was 250 kgf / cm 2. High pressure liquid treatment was performed.
  • the carbon nanotube twisted yarn X1 produced by this method had a diameter of 24 ⁇ m and a twist angle of 25 °.
  • tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.18 GPa and elongation rate was 10%.
  • Comparative Example 4 A carbon nanotube twisted yarn X was produced in the same manner as in Example 16 (1) except that it did not pass through water, and the high-pressure liquid treatment of Example 16 (2) was not performed.
  • the carbon nanotube twisted yarn X produced by this method had a diameter of 30 ⁇ m and a twist angle of 20 °. Moreover, when the tension test was implemented about this carbon nanotube twisted-yarn X, tensile strength was 0.12 GPa and elongation rate was 13%.
  • Comparative Example 5 The carbon nanotube twisted yarn X3 was produced by the same method as in Example 17 (1), but the high-pressure liquid treatment of Example 17 (2) was not performed.
  • the carbon nanotube twisted yarn X3 produced by this method had a diameter of 6 ⁇ m and a twist angle of 15 °. Moreover, when the tension test was implemented about this carbon nanotube twisted-yarn X3, tensile strength was 0.76 GPa and elongation rate was 10%.
  • Comparative Example 6 A carbon nanotube twisted yarn X was produced by the same method as in Example 19 (1), but the high-pressure liquid treatment of Example 19 (2), the addition of twist in Example 19 (3), and the electron in Example 19 (4) No irradiation was performed.
  • the carbon nanotube twisted yarn X produced by this method had a diameter of 20 ⁇ m and a twist angle of 25 °. Moreover, when the tension test was implemented about this carbon nanotube twisted-yarn 5, tensile strength was 0.27 GPa and elongation rate was 15%.
  • Comparative Example 7 The carbon nanotube twisted yarn X produced in Comparative Example 6 was subjected to the same method as in Example 19 (4) without performing the high-pressure liquid treatment in Example 19 (2) and adding the twist in Example 19 (3). Was irradiated.
  • the carbon nanotube twisted yarn X5 produced by this method had a diameter of 20 ⁇ m and a twist angle of 25 °. Moreover, when the tension test was implemented about this carbon nanotube twisted-yarn X5, tensile strength was 0.28 GPa and elongation rate was 15%.

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Abstract

La présente invention a pour but de proposer un fil à torsion de nanotubes de carbone ayant d'excellentes caractéristiques mécaniques et un procédé de fabrication du fil à torsion de nanotubes de carbone. La présente invention concerne un procédé de fabrication d'un fil à torsion de nanotubes de carbone, dans lequel, après torsion d'un fil qui est formé de nanotubes de carbone, une pression de 500 kgf/cm2 ou plus est appliquée à celui-ci dans un liquide.
PCT/JP2012/068297 2011-08-10 2012-07-19 Fil à torsion de nanotubes de carbone et son procédé de fabrication WO2013021797A1 (fr)

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JP2016519981A (ja) * 2013-06-04 2016-07-11 イノセラピー インコーポレーテッドＩｎｎｏｔｈｅｒａｐｙ Ｉｎｃ． 生体植込み型電極アセンブリ
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WO2017119307A1 (fr) * 2016-01-05 2017-07-13 リンテック株式会社 Dispositif d'étirage et procédé d'étirage
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JPWO2019083027A1 (ja) * 2017-10-26 2020-12-03 古河電気工業株式会社 カーボンナノチューブ被覆電線
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