JP5994087B2 - Carbon nanotube twisted yarn and method for producing the same - Google Patents

Description

  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, and the like, 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.

  Thus, in recent years, methods for producing carbon nanotube twisted yarn have been proposed (for example, 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.

  In 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.

  In 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.

JP 2001-115348 A

Zhang et al., Science, 306, 1358-1361, 2004 Xiao-Hua Zhong et al., Adv. Mater., 21, 1-5, 2009

  However, the carbon nanotube twisted yarn produced by the method described in Patent Document 1 and 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.

As a result of intensive studies to solve the above problems, 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. As a result of further research based on such knowledge, the present inventors have completed the present invention. It came.

That is, this invention provides the following carbon nanotube twisted-yarn and its manufacturing method.
1. 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.
2. Item ^{2. The} method for producing a carbon nanotube twisted yarn according to Item 1, wherein the pressure is 500 to 5,000 kgf / cm2.
3. Item 3. The item 1 or 2, wherein 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.
4). 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 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). Item 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). The carbon according to any one of the above items 1 to 7, wherein the carbon nanotube yarn is twisted and then subjected to a pressure of 500 kgf / cm ² or more in a liquid containing a crosslinking agent, followed by electron beam irradiation. A method for producing nanotube twisted yarn.
9. The carbon nanotube twisted-yarn manufactured by the method in any one of said item | item 1-8.

  ADVANTAGE OF THE INVENTION According to this invention, the carbon nanotube twisted-yarn excellent in the mechanical characteristic and its manufacturing method can be provided. According to the method of the present invention, 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.

It is a schematic block diagram of the carbon nanotube twisted-yarn manufacturing apparatus 1 which can be used by this invention. It is a schematic diagram for demonstrating the drawing tool for drawing out a carbon nanotube from a board | substrate. It is a schematic block diagram for demonstrating the high pressure liquid processing tool used in order to perform a high pressure process in the liquid. It is a schematic block diagram of the apparatus used in order to add a twist to carbon nanotube twisted yarn. It is a schematic diagram explaining the method of irradiating an electron beam to a carbon nanotube twisted yarn. It is a schematic block diagram of the carbon nanotube twisted-yarn manufacturing apparatus 1 'which can be used by this invention. It is a schematic diagram explaining another aspect of the method of irradiating an electron beam to a carbon nanotube twisted yarn. It is a SEM photograph explaining the measuring method of the height of a carbon nanotube aggregate. It is a SEM photograph explaining the twist angle of a carbon nanotube twisted yarn.

  Hereinafter, the present invention will be described in detail.

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. Hereinafter, 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”.

  According to this method, since the high-pressure liquid treatment is performed after twisting the carbon nanotube yarn, 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 the 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 the twisted yarn. For example, 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.

  Among the forms of carbon nanotubes, a carbon nanotube twisted yarn can be easily formed, and therefore an aggregate obtained by chemical vapor deposition on a substrate is preferable. Hereinafter, 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.

  First, an aggregate of carbon nanotubes formed on a substrate will be described.

  The substrate is not limited, and a known or commercially available substrate can be used. For example, 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. In the present invention, it is particularly preferable to use a substrate in which a silicon dioxide film is formed on a silicon substrate by thermal oxidation or vapor deposition, and a catalyst layer is laminated on the silicon dioxide film. 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, multi-walled carbon nanotubes, or a mixture thereof.

Further, 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).

  The 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 μm or more, preferably 150 μm or more, and the number of carbon nanotubes may be one or more, Preferably 1 to 40 layers.

  The carbon nanotubes used in the present invention can be produced in a highly dense and highly oriented state on the substrate by performing chemical vapor deposition using, for example, a raw material gas for forming the carbon nanotubes.

  The temperature during chemical vapor deposition may be any temperature, but it is particularly preferably high, and for example, it is preferably 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. As the source gas, 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. When 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%.

  Although reaction time can be suitably set according to manufacturing conditions, for example, what is necessary is just to be about 2 to 5 minutes.

  A carbon nanotube is pulled out from the aggregate of carbon nanotubes using a pulling tool, and the obtained carbon nanotube yarn is twisted to form a carbon nanotube twisted yarn. As a method of twisting the carbon nanotube 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. It is preferable to twist until the carbon nanotube twisted yarn obtained has a diameter of 0.1 to 1,000 μm and a twist angle of 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 μm. Moreover, although the twist angle is 0 ° to 90 ° depending on the number of twists, the yarn strength decreases if the twist angle is too small or too large, so the twist angle is preferably about 5 to 50 °. Is preferably adjusted within a range of about 1,000 to 200,000 T / m so that the number of twists (number of twists per 1 m of yarn: T / m) is about 10 to 40 °.

  By the above steps, a carbon nanotube twisted yarn having a length of 1 m or more, a yarn diameter of about 0.1 to 1,000 μm, 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.

In the present invention, for example, a pressure of 500 kgf / cm ² or more is applied in the liquid to the carbon nanotube twisted yarn formed as described above. Thereby, 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. As a result, 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. Examples of 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. As the liquid, water is more preferable from the viewpoint of safety (toxicity and flammability).

  It is preferable to add a crosslinking agent to the liquid in which the carbon nanotube twisted yarn is immersed. By adding a crosslinking agent to the liquid, the interaction between the carbon nanotube bundles can be further enhanced.

  As the crosslinking agent, a compound having one or more crosslinking groups in the molecule can be used. Examples of 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.

  Of these crosslinkable groups, an acryloyloxy group and a methacryloyloxy group are preferred.

  As 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, butanediol acrylate, hexanediol acrylate, tris (2-acryloyl) Oxyethyl) cyanurate, 3-phenoxy-2-propanoyl acrylate, and the like. As a bifunctional crosslinking agent containing two acryloyloxy groups or methacryloyloxy groups in the molecule, 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] propa 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether, and the like. As a polyfunctional crosslinking agent containing three or more acryloyloxy groups or methacryloyloxy groups in the molecule, 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 ε-caprolactone to dipentaerythritol (KAYARAD (registered trademark) DPCA series, Nippon Kayaku Co., Ltd.), 1,1,3 , 3,5,5-hexa (methacryloylalkylenedioxy) cyclotriphosphazene, tris (acrylate ethyl) iso Like null acid.

  As a 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.

  As the crosslinking agent, any of the above-mentioned monofunctional crosslinking agent containing one crosslinking group in the molecule, two bifunctional crosslinking agents, and three or more polyfunctional crosslinking agents may be used. When there is only one crosslinkable group (C═C bond, etc.), 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.). However, when 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. For example, 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.

Although there is no clear data, it is usually expected that the bundles are separated by about 10 angstroms. In order to enter between the carbon nanotubes separated by this degree and to act effectively, 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 that the thickness is angstrom (5 × 10 ⁻¹⁰ m) or more.

  These crosslinking agents can be used alone or in combination of two or more.

  When a crosslinking agent is added to the liquid, it is preferable to use a solvent that dissolves the crosslinking agent as the liquid. That is, 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 from 0.1 to 10 wt%, preferably from 0.1 to 5 wt%. When the concentration of the cross-linking agent is 0.1 to 10 wt%, the viscosity is easily impregnated with the cross-linking agent, and the carbon nanotube twisted yarn can be efficiently impregnated with the cross-linking agent. When 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. Pressure to act is usually 500 kgf / cm ² of about or more, preferably 500~5000kgf / cm ^2, more preferably about, 1000~4000kgf / cm ² approximately. By applying a pressure of about 500 kgf / cm ² or more, the carbon nanotube bundles are aggregated to enhance the interaction between the carbon nanotube bundles, and the strength of the obtained carbon nanotube twisted yarn can be increased. The pressurization time is about 1 second to 1 day, more preferably about 1 minute to 1 hour.

After applying the pressure, 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. Further, the reduced pressure drying time may be about 1 hour to 3 days.

  It is preferable to further twist the carbon nanotube twisted yarn subjected to the high-pressure liquid treatment. By performing additional twisting, 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 1 or more, but the twist number 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.

  In addition, when pressure is applied in a liquid to which a crosslinking agent is added, it is preferable to irradiate the carbon nanotube twisted yarn with an electron beam thereafter. By performing electron beam irradiation, it becomes possible to produce a carbon nanotube twisted yarn having further excellent mechanical properties. 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.

  When irradiating an electron beam, the irradiation amount of 50-600 kGy normally, Preferably 50-400 kGy should just be achieved. As 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. 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. Examples of 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. As the liquid, water is more preferable from the viewpoint of safety (toxicity and flammability).

  A crosslinking agent may be added to the liquid. As the cross-linking agent, the same cross-linking agent added to the liquid in the above-described high-pressure liquid treatment can be used. Also in this case, the liquid to which the crosslinking agent is added is preferably a solvent that dissolves the crosslinking agent. When the liquid containing the crosslinking agent is in the state of a solution in which the crosslinking agent is dissolved in the liquid, The concentration of the crosslinking agent is usually 0.1 to 10 wt%, preferably 0.1 to 5 wt%. When 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.

  For the treatment with the liquid, any method capable of attaching the liquid to the twisted yarn can be used. For example, 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. For example, 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 μm or more.

  By grasping a part of the carbon nanotubes grown on the substrate Z with high density and high orientation and pulling them apart from the aggregate of carbon nanotubes, 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. For example, the drawing tool 5 having the ultrathin shaft portion 51 as shown in FIG. 2 is used. be able to. Here, the carbon nanotube yarn Y refers to one in which carbon nanotubes drawn from the carbon nanotube aggregate c formed on the substrate Z are continuously connected in one direction. What forms the sheet | seat state of 1 m and thickness 10nm-1cm may be sufficient.

  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”). 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. At the same time as 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. In order to wind up the long carbon nanotube twisted yarn X, the winding bobbin 41 is preferably traversed. In order to prevent slipping during winding, 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.

Next, a pressure of 500 kgf / cm ² or more is applied to the carbon nanotube twisted yarn X in a liquid. At this time, for example, as shown in FIG. 3, 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. Use what you have done. 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 being rich in quick drying. Examples of 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. As the liquid, it is particularly preferable to use water from the viewpoint of safety (toxicity and flammability).

  It is preferable to add a crosslinking agent to the liquid L1. Examples of the crosslinking agent 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. . In the present embodiment, a monofunctional crosslinking agent (for example, benzyl acrylate, phenoxyethyl acrylate, polypropylene glycol acrylate, nonanediol acrylate, tris (2-acryloyloxyethyl) cyanurate) containing one acryloyloxy group or methacryloyloxy group in the molecule. , 3-phenoxy-2-propanoyl acrylate, etc.), bifunctional crosslinkers 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, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, nonapropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl ] Propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether), acryloyloxy group or methacryloyloxy group 3 or more polyfunctional crosslinking agents (for example, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate, glycerol trimethacrylate) Caprolactone-modified dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.) KAYARAD (registered trademark) DPCA series), 1,1,3,3,5,5-hexa (methacryloylalkylenedioxy) cyclotriphosphazene, tris (acrylateethyl) isocyanuric acid, etc.), acryloyloxy group or Multifunctional crosslinking agent (N, N′-bis (acrylateethyl) -N ″ -glycidyl isocyanurate containing two methacryloyloxy groups in the molecule and one glycidyl group in the molecule) Acid, etc.). When the liquid L1 containing the crosslinking agent is in a solution state in which the crosslinking agent is dissolved in the liquid L1, 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 ˜4000 kgf / cm ² , and pressurization time is about 1 second to 1 day, more preferably about 1 minute to 1 hour.

After applying the pressure, 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. Further, the reduced pressure drying time may be about 1 hour to 3 days.

  Since 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.

  It is preferable to further twist the carbon nanotube twisted yarn subjected to the high-pressure liquid treatment. In order to apply an additional twist to the carbon nanotube twisted yarn X1, for example, 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.

In addition, when pressure is applied in a liquid to which a crosslinking agent is added, it is preferable to irradiate the carbon nanotube twisted yarn with an electron beam thereafter. For example, as shown in FIG. 5, 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. At this time, 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. As the electron beam irradiation apparatus, 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 illustrating 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.

  As shown in FIG. 6, 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. The substrate fixing means 2, the twisting means 3 and the winding means 4 are the same as those in FIG. 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. As a result, 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. As 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.

  First, a method for pulling out carbon nanotubes formed on the substrate Z and setting the carbon nanotubes in the manufacturing apparatus 1 will be described.

  First, 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 of FIG.

  Next, for example, the carbon nanotubes are pulled out from the side surface of the carbon nanotube aggregate c formed on the substrate Z by using the drawer 5 shown 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.

  In order to pull out the carbon nanotubes from the side surface of the carbon nanotube aggregate c formed on the substrate Z using the drawer 5 having such a structure, first, 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 ½ or less of the average height of the carbon nanotubes c growing on the substrate Z. During this entry, 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. With the drawer 5 remaining in this place, the drawer 5 is rotated at 1 to 1,000 rpm for 1 second to 5 minutes, and after gripping the carbon nanotube, 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.

  Next, 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 rotation speed 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 rotational 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.

  By this method, a continuous carbon nanotube twisted yarn X having a diameter of about 0.1 to 1,000 μm and a twist angle of about 5 to 50 ° can be produced.

Next, in order to apply a pressure of 500 kgf / cm ² or more to the carbon nanotube twisted yarn in the liquid, 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.

After the pressure is applied, the twisted carbon nanotube yarn is taken out from the liquid and dried to remove the liquid. In a vacuum dryer, the pressure is about 10 ⁴ to 1 Pa, and the time is vacuum dried for about 1 hour to 3 days.

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.

In addition, 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 with an electron beam of about 50 to 400 kGy in a nitrogen atmosphere. The electron beam irradiation may be performed at any stage after the pressure is applied.

As described above, 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. For example, when producing carbon nanotube twisted yarn, as a method of twisting the carbon nanotube yarn, the carbon nanotube aggregate itself may be rotated and twisted, or a roller or spindle holding the carbon nanotube yarn is rotated. May be twisted.

  In addition, as shown in FIG. 6, before winding the carbon nanotube twisted yarn onto the winding bobbin, the carbon nanotube twisted yarn may be contracted in advance by passing the carbon nanotube twisted yarn through the liquid to increase the strength.

Further, as shown in FIG. 3, after passing the carbon nanotube twisted yarn through the tube, the liquid was poured and plugged, and a pressure of 500 kgf / cm ² or more was applied, but the carbon nanotube twisted yarn was subjected to 500 kgf / cm ² in the liquid. If the above pressure can be applied, it may not be passed through the tube or plugged depending on the specifications of the isotropic pressure device. Moreover, you may make it act in the state wound by the winding bobbin 41. FIG.

  If 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. As a result, since the interaction between the carbon nanotube bundles is strengthened, the mechanical characteristics are improved. Furthermore, if 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.

  Hereinafter, the present invention will be described in detail using examples. In addition, this invention is not limited to the following Example.

  In addition, the physical-property value in an Example and a comparative example was measured with the following method.

  The height of the carbon nanotube aggregate was measured 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 an SEM photograph using a scanning electron microscope “JSM-7401F” manufactured by JEOL Ltd.

  For the twist angle, an SEM photograph was taken using a scanning electron microscope “JSM-7401F” manufactured by JEOL Ltd., and 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.

Tensile strength was measured when a tensile test was performed at a yarn length of 10 mm and a pulling speed of 1 mm / min using an automatic load tester “MAX-1KN-S” manufactured by Japan Measuring System Co., Ltd. Measure the load and the cross-sectional area of the thread and use the following formula:
Tensile strength (Pa) = Breaking load (N) ÷ Yarn cross-sectional area (m ² )
Thus, the load when the carbon nanotube twisted yarn broke was divided by the cross-sectional area of the yarn. The measurement was performed a plurality of times (2 to 8 times), and the average value was taken as the tensile strength.

Elongation rate is the same as the tensile strength, tensile test is performed, the length of elongation when the carbon nanotube twisted yarn breaks, the following formula:
Elongation rate (%) = 100 × Elongation length (mm) ÷ Initial yarn length (10 mm)
Accordingly, the length obtained by breaking the carbon nanotube twisted yarn by breaking was divided by the initial yarn length (10 mm). The measurement was performed a plurality of times (2 to 8 times), and the average value was defined as the elongation.

Example 1
(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. Next, 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. Next, while flowing 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. Thereafter, 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 reaction vessel flange portion, 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 μm and a bulk density of 45 mg / cm ³ , and was formed with high density and high orientation.

  Using a micro knife (Micro Surgical Blade K-715 made by Feather Safety Razor, tip angle 15 °), 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. Thus, 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.

  With respect to the carbon nanotube substrate Z held by the substrate fixing means 2 in FIG. 1, from the side surface of the carbon nanotube aggregate constituting the carbon nanotube substrate Z, as shown in FIG. 254, the diameter of the thin shaft portion 51 is pierced by 0.1 mm, and then rotated at 1,000 rpm for 1 second to entangle the carbon nanotubes. Further, the carbon nanotube substrate Z is not rotated without rotating the drawer 5. By separating the carbon nanotubes, the carbon nanotubes were continuously pulled out from the carbon nanotube substrate Z, and the carbon nanotube yarn Y was formed.

  By retracting the drawing tool 5, the carbon nanotube yarn Y was moved onto the winding bobbin 41 of the winding means 4, and the carbon nanotube yarn Y was fixed to the winding bobbin 41.

  Next, carbon obtained by twisting the carbon nanotube yarn Y by rotating the winding bobbin 41 of the winding means 4 while rotating the twisting apparatus of the twisting means 3 at 1,000 rpm. The nanotube twisted yarn X was wound at a winding speed of 10 cm / min. The number of twists of the carbon nanotube twisted yarn X at this time is 10,000 T / m.

  By this method, a carbon nanotube twisted yarn X having a diameter of 18 μm and a twist angle of 25 ° was produced. When the tensile test was implemented about the carbon nanotube twisted-yarn X produced through the above process, tensile strength was 0.19 GPa and elongation rate was 10%.

(2) High-pressure liquid treatment Next, 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. This was installed in an isotropic pressurizer (Yamamoto Hydraulic Industry Co., Ltd. Ultra High Pressure Test Capsule R7K-3.5-15-15) using water pressure and treated at a pressure of 5,000 kgf / cm ² for 1 hour. Went. After the treatment, the carbon nanotube twisted yarn X1 was taken out from the silicon tube, and placed in a vacuum drying cabinet (molded vacuum desiccator MVD-100 manufactured by ASONE Co., Ltd.), and a vacuum pump (N810.3FT. Manufactured by KNF Japan Co., Ltd.). 18) and dried under reduced pressure at 10 ⁴ Pa for 3 days.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 15 μm and a twist angle of 20 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.30 GPa and elongation rate was 10%.

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.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 13.7 μm and a twist angle of 30 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.30 GPa and elongation rate was 8%.

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.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 15 μm and a twist angle of 15 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.27 GPa and elongation rate was 9%.

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.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 15 μm and a twist angle of 20 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.23 GPa and elongation rate was 8.5%.

Example 5
A carbon nanotube twisted yarn X having a diameter of 24 μm 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 .

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 22 μm and a twist angle of 24 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.22 GPa and elongation rate was 10%.

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.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 21 μm and a twist angle of 22 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.24 GPa and elongation rate was 9%.

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.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 20 μm and a twist angle of 22 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.26 GPa and elongation rate was 10%.

Example 8
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 4,000 kgf / cm ^2. X was subjected to high pressure liquid treatment.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 18 μm and a twist angle of 20 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.32 GPa and elongation rate was 10%.

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.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 20 μm and a twist angle of 20 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.32 GPa and elongation rate was 10%.

Example 10
A carbon nanotube twisted yarn X having a diameter of 26 μm 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%.

  About this carbon nanotube twisted-yarn X, the carbon nanotube twisted-yarn X was high-pressure-liquid-processed by the same method as Example 1 (2) except having made processing time into 1 minute.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 23 μm and a twist angle of 30 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.28 GPa and elongation rate was 13%.

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.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 23 μm and a twist angle of 30 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.28 GPa and elongation rate was 12%.

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. .

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 23 μm and a twist angle of 30 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.28 GPa and elongation rate was 15%.

Example 13
A carbon nanotube twisted yarn X having a diameter of 23 μm 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%.

  About this carbon nanotube twisted-yarn X, the high pressure liquid process was performed to the carbon nanotube twisted-yarn X by the same method as Example 1 (2).

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 18 μm and a twist angle of 15 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.27 GPa and elongation rate was 12%.

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.), whereby a twist was added to the carbon nanotube twisted yarn X1 to produce a carbon nanotube twisted yarn X2. The number of twists added was 5,000 T / m.

  By this method, a carbon nanotube twisted yarn X2 having a diameter of 16 μm and a twist angle of 20 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X2, tensile strength was 0.53 GPa and elongation rate was 17%.

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.

  By this method, a carbon nanotube twisted yarn X2 having a diameter of 15 μm and a twist angle of 20 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X2, tensile strength was 0.51 GPa and elongation rate was 16%.

Example 16
(1) 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.

(2) High-pressure liquid treatment Next, the carbon nanotube twisted yarn X3 was subjected to a high-pressure liquid treatment in the same manner as in Example 1 (2), and then dried under reduced pressure to produce a carbon nanotube twisted yarn X4.

  By this method, a carbon nanotube twisted yarn X4 having a diameter of 17 μm and a twist angle of 13 ° was obtained. When the tension test was implemented about this carbon nanotube twisted-yarn X4, tensile strength was 0.65 GPa and elongation rate was 17%.

Example 17
(1) 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).

(2) High-pressure liquid treatment Next, the carbon nanotube twisted yarn X3 was subjected to a high-pressure liquid treatment in the same manner as in Example 1 (2), and then dried under reduced pressure to produce a carbon nanotube twisted yarn X4.

  By this method, a carbon nanotube twisted yarn X4 having a diameter of 5.5 μm and a twist angle of 15 ° was obtained. When the tension test was implemented about this carbon nanotube twisted-yarn X4, tensile strength was 1.23 GPa and elongation rate was 8%.

Example 18
(1) Manufacture of carbon nanotube twisted yarn A carbon nanotube aggregate having a height of 185 μm 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 μm 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%.

(2) High-pressure liquid treatment Next, the carbon nanotube twisted yarn X3 was subjected to a high-pressure liquid treatment in the same manner as in Example 1 (2), and then dried under reduced pressure to produce a carbon nanotube twisted yarn X4.

  By this method, a carbon nanotube twisted yarn X4 having a diameter of 14 μm and a twist angle of 25 ° was obtained. When the tension test was implemented about this carbon nanotube twisted-yarn X4, tensile strength was 0.80 GPa and elongation rate was 15%.

(3) Electron beam irradiation Next, 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 prepare carbon nanotube twisted yarn X5.

  By this method, a carbon nanotube twisted yarn X5 having a diameter of 14 μm and a twist angle of 25 ° was obtained. When the tension test was implemented about this carbon nanotube twisted-yarn X5, tensile strength was 1.08 GPa and elongation rate was 13%.

Example 19
(1) Manufacture of carbon nanotube twisted yarn Using a carbon nanotube aggregate having a height of 185 μm and a bulk density of 72 mg / cm ³ , a diameter of 20 μm 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%.

(2) High-pressure liquid treatment Next, with respect to the carbon nanotube twisted yarn X, the liquid at the time of the high-pressure liquid treatment was changed to a 5 wt% ethanol solution of a crosslinking agent (KAYARAD (registered trademark) DPCA-30 manufactured by Nippon Kayaku Co., Ltd.). After performing the high-pressure liquid treatment in the same manner as in Example 1 (2), drying under reduced pressure was performed to produce carbon nanotube twisted yarn X1.

  By this method, a carbon nanotube twisted yarn X1 having a diameter of 17 μm and a twist angle of 20 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X1, tensile strength was 0.37 GPa and elongation rate was 14%.

(3) Addition of twist About the carbon nanotube twisted-yarn X1, twist was added by the same method as Example 14.

  By this method, a carbon nanotube twisted yarn X2 having a diameter of 15 μm and a twist angle of 25 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X2, tensile strength was 0.54 GPa and elongation rate was 16%.

(4) Electron Beam Irradiation Next, the carbon nanotube twisted yarn X2 was irradiated with an electron beam in the same manner as in Example 18 (3) to prepare a carbon nanotube twisted yarn X5.

  By this method, a carbon nanotube twisted yarn X5 having a diameter of 15 μm and a twist angle of 25 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X5, tensile strength was 0.90 GPa and elongation rate was 12%.

Example 20
(1) Production of carbon nanotube twisted yarn Carbon nanotube twisted yarn X3 having a diameter of 16 μm 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%.

(2) High-pressure liquid treatment Next, the carbon nanotube twisted yarn X3 was subjected to a high-pressure liquid treatment in the same manner as in Example 19 (2), and then dried under reduced pressure to produce a carbon nanotube twisted yarn X4.

  By this method, a carbon nanotube twisted yarn X4 having a diameter of 14 μm and a twist angle of 25 ° was obtained. When the tension test was implemented about this carbon nanotube twisted-yarn X4, tensile strength was 0.85 GPa and elongation rate was 15%.

(3) Electron Beam Irradiation Next, 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.

  By this method, a carbon nanotube twisted yarn X5 having a diameter of 14 μm and a twist angle of 25 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X5, tensile strength was 1.23 GPa and elongation rate was 10%.

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.

  By this method, a carbon nanotube twisted yarn X4 having a diameter of 14 μm and a twist angle of 25 ° was obtained. When the tension test was implemented about this carbon nanotube twisted-yarn X4, tensile strength was 0.82 GPa and elongation rate was 15%.

  Next, about carbon nanotube twisted-yarn X4, the electron beam was irradiated by the same method as Example 18 (3), and carbon nanotube twisted-yarn X5 was produced.

  By this method, a carbon nanotube twisted yarn X5 having a diameter of 14 μm and a twist angle of 25 ° was obtained. When the tension test was implemented about this carbon nanotube twisted-yarn X5, tensile strength was 1.17 GPa and elongation rate was 10%.

Example 22
(1) 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).

  By this method, a carbon nanotube twisted yarn X3 having a diameter of 6 μm and a twist angle of 25 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X3, tensile strength was 1.10 GPa and elongation rate was 10%.

(2) High-pressure liquid treatment Next, the carbon nanotube twisted yarn X3 was subjected to a high-pressure liquid treatment in the same manner as in Example 19 (2), and then dried under reduced pressure to produce a carbon nanotube twisted yarn X4.

  By this method, a carbon nanotube twisted yarn X4 having a diameter of 5 μm and a twist angle of 20 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X4, tensile strength was 1.58 GPa and elongation rate was 8%.

(3) Electron Beam Irradiation Next, the carbon nanotube twisted yarn X4 was irradiated with an electron beam in the same manner as in Example 18 (4) to produce a carbon nanotube twisted yarn X5.

  By this method, a carbon nanotube twisted yarn X5 having a diameter of 5 μm and a twist angle of 20 ° was obtained. When the tension test was implemented about this carbon nanotube twisted-yarn X5, tensile strength was 2.02 GPa and elongation rate was 6%.

Example 23
(1) 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).

  By this method, a carbon nanotube twisted yarn X3 having a diameter of 6 μm and a twist angle of 25 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X3, tensile strength was 1.10 GPa and elongation rate was 10%.

(2) High-pressure liquid treatment Next, the carbon nanotube twisted yarn X3 was subjected to a high-pressure liquid treatment in the same manner as in Example 19 (2), and then dried under reduced pressure to produce a carbon nanotube twisted yarn X4.

  By this method, a carbon nanotube twisted yarn X4 having a diameter of 5 μm and a twist angle of 20 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X4, tensile strength was 1.60 GPa and elongation rate was 8%.

(3) Electron Beam Irradiation Next, the carbon nanotube twisted yarn X4 was irradiated with an electron beam in the same manner as in Example 18 (4) to produce a carbon nanotube twisted yarn X5.

  By this method, a carbon nanotube twisted yarn X5 having a diameter of 5 μm and a twist angle of 20 ° was obtained. When the tensile test was implemented about this carbon nanotube twisted-yarn X5, tensile strength was 2.04 GPa and elongation rate was 6%.

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 μm 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 μm 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 μm 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 μm and a twist angle of 25 °. When the 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 μm 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 μm 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 μm 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 μm 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%.

DESCRIPTION OF SYMBOLS 1, 1 'Carbon nanotube twisted-yarn manufacturing apparatus 2 Substrate fixing means 3 Twisting means 4 Winding means 5 Pull-out tool 6 High pressure liquid processing means 7, 7' Carbon nanotube twisted yarn fixing means 8 Twisting means 9 Liquid passing means 10 Electron beam irradiation means

Claims (8)

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. Wherein the pressure is a 500~5,000kgf / cm ^2, the method of manufacturing the carbon nanotube twisted according to claim 1.   3. The liquid according to claim 1, wherein the liquid is at least one selected from the group consisting of water, a lower alcohol having 1 to 5 carbon atoms, acetone, diethyl ether, chloroform, dichloromethane, ethyl acetate, and tetrahydrofuran. A method for producing carbon nanotube twisted yarn.   The method for producing a carbon nanotube twisted yarn according to claim 3, wherein the liquid is water. The method for producing a carbon nanotube twisted yarn according to any one of claims 1 to 4, wherein a twist is further applied to the carbon nanotube twisted yarn subjected to a pressure of 500 kgf / cm ² or more in a liquid.   The method for producing a twisted carbon nanotube according to claim 5, wherein the number of twists to be added is 1,000 to 5,000 T / m.   The method for producing a carbon nanotube twisted yarn according to any one of claims 1 to 6, wherein the carbon nanotube twisted yarn is treated with a liquid before pressure is applied in the liquid. The carbon according to any one of claims 1 to 7, wherein after twisting a yarn made of carbon nanotubes, a pressure of 500 kgf / cm ² or more is applied in a liquid containing a crosslinking agent, followed by electron beam irradiation. A method for producing nanotube twisted yarn.

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