JP4900619B2 - Method and apparatus for continuously producing fine carbon fiber twisted yarn - Google Patents

Description

The present invention relates to a method and an apparatus for continuously producing twisted yarn from fine carbon fibers obtained by chemical vapor deposition.

  Fine carbon fibers are excellent in electrical characteristics, mechanical characteristics, and the like, and are expected to be used and applied in various industries such as field emission displays and conductive fillers.

  In recent years, fine carbon fibers made of carbon nanotubes and carbon nanotube sheets using the same have been proposed (Patent Document 1 and Non-Patent Documents 1 and 2).

  Non-Patent Document 1 discloses a method of forming fine carbon fiber twisted yarns from an aggregate of fine carbon fibers grown in a high density and high orientation on a substrate by chemical vapor deposition.

  In Patent Document 1 and Non-Patent Document 2, a fine carbon fiber sheet or a fine carbon fiber rope can be formed from an aggregate of fine carbon fibers grown on a substrate with high density and high orientation by a chemical vapor deposition method. Is disclosed.

  The above-mentioned fine carbon fiber twisted yarn and sheet are expected to be used for new applications because of their non-existing forms, and are expected to be applied to various industries.

  In industrial applications, it is essential that the fine carbon fiber twisted yarns and sheets as described above are continuously and uniformly produced and wound. The tension when pulling out the fine carbon material fiber from the substrate is usually as small as 0.05 to 0.5 mN. If this value is exceeded for some reason, thread breakage easily occurs. This fineness is the greatest problem to be overcome in producing fine carbon material twisted yarn.

  In Non-Patent Document 1, a spindle made by a toothpick is attached to the tip of a rotating shaft of a motor, and a plurality of fine carbon fibers are connected to the tip of the spindle. Fine carbon fiber twisted yarn is manufactured by separating from the carbon fiber aggregate substrate. However, in this method, since the length of the fine carbon fiber twisted yarn that can be produced is equal to the movable distance of the motor, the length of the fine carbon fiber twisted yarn that can be produced at one time is fundamentally limited. For this reason, when the distance between the spindle for twisting and the substrate of the fine carbon fiber becomes large, unstable swinging of the drawn fine carbon fiber twisted yarn induces instability in the process, resulting in frequent yarn breakage. There is a concern that spots due to changes in the twist transmission state may occur in the twisted yarn.

On the other hand, examples of the method used for spinning natural fibers include a ring spinning method and a flyer spinning method. Although these methods can continuously produce twisted yarns, the fine carbon fibers handled in the present invention are very fine and thus are vulnerable to friction, and it has been difficult to use a conventional method of receiving friction in the process. Therefore, as long as such a method is used, it has been difficult to apply to the industry. (See Non-Patent Document 3)
International Publication WO2005 / 102924 Pamphlet Chang et al., “Multifunctional carbon nanotube fibers by miniaturizing ancient technology”, Science magazine, USA, published by the American Association for the Advancement of Science, November 19, 2004, 306, 1358-1361 (Zhang et al. ,, Science, AAAS, “Multifunctional Carbon Nanotube Yarns by Downsizing an Ancient Technology”, VOL 306, 1358-1361, 19 November 2004) Chang et al., “Tough and Transparent Multifunctional Carbon Nanotube Sheet”, Science Magazine, USA, American Society for the Advancement of Science, August 19, 2005, 309, 1215-1219 (Zhang et al., Science, AAAS , “Strong, Trasnsparent, Multifunctional, Carbon Nanotube sheets”, 309, 1215-1219, 19 August 2005) Authors: Hideo Tsujito et al., Basic Textile Engineering [II], Japan Textile Machinery Society, issued December 20, 1966, 249 pages

This invention is made | formed in view of the said situation, and it aims at providing the method and apparatus suitable for manufacturing the twisted yarn of a fine carbon fiber continuously.

  In order to achieve the above object, a method for producing a fine carbon fiber twisted yarn according to the present invention includes a growth step of chemical vapor deposition of an aggregate of fine carbon fibers on a substrate, and the fine carbon fibers from the aggregate on the substrate. A winding step of continuously pulling out and winding on a bobbin, and rotating at least one of the substrate and the bobbin to continuously pull out from the aggregate of fine carbon fibers on the substrate and wind up on the bobbin. A twisting step of twisting the fine carbon fiber to be formed to form a fine carbon fiber twisted yarn, wherein the twisting step and the winding step are performed simultaneously.

  The method of twisting the fine carbon fibers in the twisting step is by rotating the substrate, and the twisting step prepares a plurality of substrates having the fine carbon fiber aggregate, The plurality of substrates are further rotated around a common rotation axis while twisting the fine carbon fibers drawn from the aggregate by rotating each substrate around a rotation axis passing therethrough to form a fine carbon fiber twisted yarn. The fine carbon fiber twisted yarns may be further twisted together.

  In addition, the method further includes a recovery step of recovering the breakage of the fine carbon fiber twisted yarn, and the recovery step pierces the ultrafine shaft-shaped portion of the drawing tool having the ultrafine shaft-shaped portion on the side surface of the aggregate of the fine carbon fibers. After that, the fine carbon fiber is attached to the ultra-thin shaft portion, and the fine carbon fiber is pulled out from the substrate without being twisted, or the substrate or the drawing tool is rotated to be drawn out as a twisted yarn of the fine carbon fiber and drawn out. The ends of the carbon fiber are superposed on one end of the fine carbon fiber twisted yarn already wound on the bobbin, and then the twisted portion is twisted to connect the two twisted yarns, which are connected to the ultra-thin shaft portion of the drawing tool. The two twisted yarns may be connected by separating the fine carbon fiber twisted yarn from the drawing tool.

  A connection step of connecting each fine carbon fiber twisted yarn wound around a pair of bobbins, wherein the connecting step pulls out the other end of the first twisted yarn, one end of which is wound around the first bobbin; By overlapping the other end of the first twisted yarn on the other end of the second twisted yarn, one end of which is wound around the second bobbin, twisting the overlapped portion and connecting the two twisted yarns, 2 You may make it connect the twisted yarn of a fine carbon fiber of a book.

  The overlap portion of the two twisted yarns to be connected is covered with a wide sheet-like fine carbon fiber drawn from a substrate subjected to chemical vapor deposition, and then twisted on the overlap portion. You may connect by multiplying.

  After applying a liquid selected from alcohol having 1 to 5 carbon atoms, acetone, tetrahydrofuran, dimethylformamide, dimethylacetamide, ethyl acetate, acetonitrile, or water to the overlapped portion, the overlapped portion is twisted. It is preferable to multiply.

  Further, in the growth step, fine carbon fibers are grown so that the average length (L) is 0.02 mm or more, and in the twisting step, the diameter (D) is set to D <(L / π). The ultrathin shaft portion is pierced into the side surface of the aggregate of the fine carbon fibers grown on the substrate while rotating the extraction tool having the extra fine shaft portion or without rotating the extraction tool. You may include the process of making it approach and drawing out fine carbon fiber, rotating the said drawing tool by predetermined rotation speed.

  Furthermore, the method for producing a fine carbon fiber twisted yarn according to the present invention includes a growth step of chemical vapor deposition of an aggregate of fine carbon fibers on a substrate, and continuous fine carbon fibers from the aggregate of fine carbon fibers on the substrate. The fine carbon fiber is twisted to form a fine carbon fiber twisted yarn by rotating the bobbin while rotating the bobbin, and the fine carbon fiber twisted yarn drawn and twisted is wound around the bobbin A winding step, and in the pulling and twisting step, a first arrangement along which a winding rotation axis extends in a direction in which the fine carbon fibers are pulled out, and a direction in which the fine carbon fibers are pulled out and a winding rotation A bobbin capable of changing the arrangement between the second arrangement where the axes intersect is used, and the bobbin is wound around the winding axis while the fine carbon fiber is connected to one end of the bobbin in the first arrangement. , While moving the at least one of the substrate and the bobbin away from each other, twisting while pulling out the fine carbon fibers from the aggregate of fine carbon fibers on the substrate, in the winding step, After the bobbin is stopped and rotated to the second arrangement, the bobbin is rotated around the winding rotation axis, and the substrate and the bobbin are synchronized with the bobbin rotation. By moving at least one of the substrate and the bobbin so as to reduce the distance, the fine carbon fiber twisted yarn drawn and twisted in the second step is wound around the bobbin, and the draw-twisting step and the The winding process is performed alternately.

  Further, the present invention is a fine carbon fiber twisted yarn comprising fine carbon fibers having a diameter of 1 to 100 nm produced by any one of the above methods, the surface twist angle is 10 to 50 °, and the tensile strength is 200 MPa or more. A fine carbon fiber twisted yarn is provided.

  Furthermore, in order to achieve the above object, the present invention is an apparatus for continuously producing twisted yarns of fine carbon fibers from an aggregate of fine carbon fibers grown on a substrate by chemical vapor deposition, which holds the substrate. A substrate holding unit, a bobbin for driving the fine carbon fiber twisted yarn, and a fine carbon fiber drawn from the assembly on the substrate held by the substrate holding unit and wound on the bobbin is twisted. And a twisting mechanism for rotating at least one of the substrate holding portion and the bobbin in conjunction with a bobbin winding drive.

  The substrate holding portion has a rotation axis of the holding portion directed toward a peripheral edge of the bobbin so as to avoid interference between the fine carbon fibers drawn from the aggregate on the substrate and the substrate, and the substrate Is preferably configured to be held non-parallel to the rotation axis of the holding portion.

  The apparatus for producing a fine carbon fiber twisted yarn according to the present invention includes a support that supports a plurality of the substrate holders, and a fine carbon fiber drawn from each of the aggregates on the substrate held by each substrate holder. A plurality of first driving units that rotationally drive each of the plurality of substrate holding units to twist the substrate, and a second driving unit that rotationally drives the support to further twist the fine carbon fiber twisted yarns. It is preferable to have.

  Furthermore, it is preferable that the apparatus for producing fine carbon fiber twisted yarn according to the present invention includes a windshield in the vicinity of the drawing position of the fine carbon fiber from the substrate.

  The apparatus for producing fine carbon fiber twisted yarn according to the present invention further includes a monitoring device that monitors whether the fine carbon fibers on the substrate are broken or the fine carbon fibers are pulled out from the substrate, and the monitoring device includes the fine carbon fibers. An imaging device for photographing fine carbon fiber twisted yarn pulled out from a substrate while applying a twist existing between a substrate subjected to chemical vapor deposition and a bobbin, and enlarges image data obtained by the imaging device on a screen It is preferable to include a display that displays the image and a determination unit that scans the image data of the image displayed on the display and determines that the yarn is broken when the number of pixels constituting the twisted yarn decreases.

  In addition, the apparatus for producing fine carbon fiber twisted yarn according to the present invention includes an extraction tool having an ultra-thin shaft-like portion for piercing the side surface of the aggregate of fine carbon fibers grown on the substrate and pulling out the fine carbon fibers. A rotation drive device that rotates the drawing tool about an axis, and the diameter (D) of the ultrafine shaft-shaped portion of the drawing tool is the average length (L of the fine carbon fibers grown on the substrate) ) Is preferably set to D <(L / π).

  It is preferable that the drawing tool has at least one of a circumferential groove, a spiral groove, and a protrusion on the outer peripheral surface of the ultrafine shaft-like portion.

  Further, the present invention is an apparatus for continuously producing a fine carbon fiber twisted yarn from an assembly of fine carbon fibers chemically vapor-deposited on a substrate, the substrate holding unit holding the substrate, and the fine A bobbin for winding and driving a carbon fiber twisted yarn, and the bobbin has a tapered end portion for connecting the fine carbon fiber formed at one end in the winding rotation axis direction, and the tapered end portion is A first arrangement in which the winding rotation axis is directed in the direction in which the fine carbon fibers are drawn out toward the substrate holding portion, and a second arrangement in which the winding carbon rotation axis intersects with the direction in which the fine carbon fibers are drawn out. It is possible to change the arrangement, and at least one of the bobbin and the substrate holding part is provided so as to reciprocate so as to approach or separate from each other.

  According to the present invention, by rotating at least one of the substrate on which the aggregate of fine carbon fibers is formed and the bobbin, twisting the fine carbon fiber drawn from the aggregate and winding the fine carbon fiber on the bobbin, A fiber twist yarn can be manufactured continuously.

It is a SEM photograph which expands and enlarges 500 times the silicon substrate which grew the carbon nanotube with high density and high orientation. It is a side view which shows 1st Embodiment of the manufacturing apparatus of the fine carbon fiber twisted yarn which concerns on this invention. FIG. 3 is a front view of the apparatus of FIG. 2. It is sectional drawing which expands and shows a part of FIG. It is a SEM photograph which expands 1000 times the twisted yarn of the carbon nanotube manufactured by the apparatus of FIG. It is a top view which shows the apparatus of FIG. 1 simplified, and the drawing tool which recovers a thread break. It is a side view which expands and shows a part of FIG. It is explanatory drawing for demonstrating the method to recover the thread breakage of a fine carbon fiber twisted yarn. It is explanatory drawing for demonstrating the connection method of the fine carbon fiber twisted yarn on two bobbins. It is a top view which expands and shows the drawing-out state of a sheet-like fine carbon fiber. It is a perspective view which shows notionally 2nd Embodiment of the manufacturing apparatus of the fine carbon fiber twisted yarn which concerns on this invention. In the apparatus shown in FIG. 11, it is a perspective view which shows the aspect which has arrange | positioned the board | substrate with which the aggregate | assembly of the fine carbon fiber was grown vertically. It is a SEM photograph which expands 5000 times and shows the twisted yarn manufactured by pulling out fine carbon fiber from four substrates with the apparatus shown in FIG. It is a side view which shows 3rd Embodiment of the manufacturing apparatus of the fine carbon fiber twisted yarn which concerns on this invention. It is a XV-XV view of the apparatus of FIG. It is XVI-XVI sectional drawing of FIG. It is a top view which shows 4th Embodiment of the manufacturing apparatus of the fine carbon fiber twisted yarn which concerns on this invention. FIG. 18 is a side view of the apparatus of FIG. 17. It is a top view which shows the other operating state of the apparatus of FIG. FIG. 18 is a side view of the apparatus of FIG. 17.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1A, 1B, 1C, 1D ... Manufacturing apparatus of fine carbon fiber twisted yarn 2 Substrate holding device 3 Bobbin 4 Winding device 5 Substrate 6 Substrate holding portion 7 First driving portion 18 Windshield 19 Twist yarn guide 20 Support 21 Extractor 21a Extra fine shaft Shaped portion 30 Substrate holding device 31 Tapered end portion 32 Bobbin 33 Winding device 34 First drive portion C Aggregation of fine carbon fibers

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below with reference to the drawings. In addition, the same code | symbol was attached | subjected to the same component through all the drawings and all the embodiments.

  The present invention relates to a method and an apparatus for continuously producing a fine carbon fiber twisted yarn from an aggregate of fine carbon fibers grown on a substrate by chemical vapor deposition.

  The aggregate | assembly of the fine carbon fiber formed on a board | substrate is demonstrated in detail below.

  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 substrate containing a metal such as iron or copper or 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 an iron-coated laminated silicon substrate obtained by evaporating or sputtering iron on a silicon substrate on which a silicon dioxide film is deposited by thermal oxidation or vapor deposition. Thereby, a carbon nanotube aggregate formed with high density and high orientation can be produced.

  The fine carbon fibers to be chemically vapor-grown on the substrate are vapor-grown carbon fibers such as single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and carbon fibers.

  The form of these fine carbon fibers is not particularly limited, but for reasons such as easy formation of fine carbon fiber twisted yarns, it is preferably an aggregate formed with high density and high orientation on the substrate. It is desirable to be.

The high density means that the bulk density of the carbon nanotubes on the substrate is 1-1000 mg / cm ³ , preferably 10-500 mg / cm ³ , more preferably 10-100 mg / cm ³ . 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. When the bulk density is larger than this range, a large amount of carbon nanotubes are pulled out at the time of pulling out, which will be described later, and there is a possibility that long fibers having a uniform thickness cannot be obtained.

  High orientation means that fine carbon fibers are adjacent to each other and stand perpendicular to the substrate plane. Specifically, the order parameter (OP) represented by the following formula (1) is in the range of 0.70 to 1.0 (preferably 0.90 to 0.99).

Formula 1

(However, θj represents an angle formed between the molecular axis of an arbitrary carbon nanotube formed on the substrate and the substrate. <Cos ² (90-θj)> represents all the angles formed on the substrate. (The average value for carbon nanotubes is shown.)
Such an assembly of fine carbon fibers that are vertically aligned at a high density by chemical vapor deposition is called a carbon nanotube forest or a vertically aligned structure of carbon nanotubes. The length of the fine carbon fiber formed by chemical vapor deposition may be 0.02 mm or more on average, preferably 0.03 mm or more, and more preferably 0.05 mm or more. The average diameter of the fine carbon fiber material is not limited, and is usually 0.5 to 100 nm, preferably about 1 nm to 100 nm, and more preferably about 5 to 50 nm.

  The temperature at the time of vapor phase growth may be any temperature, but it is particularly preferably high temperature, for example, about 600 to 1000 ° C. The pressure at the time of vapor phase growth is not limited, but usually it may be performed at atmospheric pressure. The gas used for vapor phase growth may contain carbon, but usually a hydrocarbon such as acetylene may be used. A rare gas such as helium may be used as the carrier gas. Although reaction time can be suitably set according to manufacturing conditions, it should just be about 3 minutes-2 hours, for example.

  A photograph of the aggregate of carbon nanotubes, which are fine carbon fibers formed on the substrate as described above, is shown in FIG. FIG. 1 is an SEM photograph at a magnification of 500 times, showing that fine carbon fibers are vertically aligned at high density on a substrate. A part of an aggregate of carbon nanotubes grown with high density and high orientation on a substrate, that is, an aggregate of carbon nanotubes by holding multiple fine carbon fibers with tweezers or connecting them to the tip of a thin needle-like object By pulling away from the body, the carbon nanotubes are pulled out from the substrate as a continuous filament. Although the mechanism by which such a phenomenon occurs is not always clear, by properly twisting the filamentary carbon nanotubes drawn out in this way, it becomes possible to continuously draw out without breaking the yarn.

  Next, 1st Embodiment of the manufacturing apparatus of the fine carbon fiber twisted yarn which concerns on this invention is described with reference to FIGS. The fine carbon fiber twisted yarn manufacturing apparatus 1A according to the first embodiment includes a substrate holding unit 6 that holds the substrate 5 and a bobbin 3 that winds and drives the fine carbon fiber twisted yarn as shown in FIGS. .

  Furthermore, the substrate holding device 2 including the substrate holding unit 6 includes a first drive unit 7 that rotates the substrate holding unit 6. The first drive unit 7 is interlocked with the winding drive of the bobbin 3. In this way, the fine carbon fiber drawn from the assembly C on the substrate 5 and wound on the bobbin 3 is twisted by rotating the first drive unit 7 in conjunction with the winding drive of the bobbin 3. A twisting mechanism is configured.

  As shown in FIG. 4, the substrate holding unit 6 can be configured by connecting a pair of holding pieces 6 a and 6 b with bolts 8. The holding pieces 6a and 6b are formed so that the holding surface has a predetermined inclination angle α (FIG. 4) so as to hold the substrate 5 non-parallel to the rotation axis X.

  By holding the substrate 5 non-parallel to the rotation axis X, the fine carbon fiber twisted yarn drawn from the fine carbon fiber aggregate C on the substrate 5 and the substrate 5 are prevented from interfering with each other. It can be produced stably. Further, in order to prevent such interference, when the substrate holding unit 6 holds the substrate with an inclination with respect to the rotation axis X, the substrate holding unit 6 rotates the substrate holding unit 6 as shown in FIG. The axis X is preferably directed toward the peripheral edge of the bobbin 3. If the holding pieces 6a and 6b have a plurality of holding surface inclination angles, the mounting angle of the substrate 5 can be changed by replacing the holding pieces 6a and 6b as necessary.

  In the winding device 4 including the bobbin 3, a drive motor 10 that rotationally drives the bobbin 3 is supported by the slider 11. The slider 11 is slidably supported on a rail 12 extending in a direction perpendicular to the rotation axis X of the substrate holding unit 6 and is connected to a linear actuator 13 and a connecting plate 14. The linear actuator 13 includes a drive motor 15, a transmission belt 16, a screw shaft 17 supported by bearings 17 a and 17 b, and a nut body (not shown) screwed into the screw shaft 17. Are connected to the connecting plate 14. Then, by rotating the drive motor 15 forward and backward, the slider 11 reciprocates on the rail 12 as the screw shaft 17 rotates forward and backward. In this way, the bobbin 3 can be traversed.

  As described above, the twisted fine carbon fiber twisted yarn is pulled out by the bobbin 3 by pulling out the yarn while rotating the fine carbon fiber continuously drawn from the aggregate of the fine carbon fibers on the substrate 5. The winding method is used. As a result, the drawn fine carbon fiber twisted yarn can be stably and continuously wound around the bobbin 3 without receiving friction.

  In the fine carbon fiber twisted yarn manufacturing apparatus 1A, it is preferable that the distance from the drawing position of the fine carbon fiber on the substrate 5 to the entry position to the bobbin 3 is in the range of 10 mm to 1000 mm. If this distance is too short, the rotating delivery part and the take-up part interfere with each other so that it cannot be taken up. On the other hand, if this distance is too long, the process stability becomes poor due to the oscillation of the fine carbon fiber twisted yarn existing between the delivery part and the take-up part, which is not preferable.

  In the present invention, in order to twist the fine carbon fibers, the substrate 5 on which the aggregate of fine carbon fibers is formed is rotated at a high speed. It is important that the fine carbon fibers at the corners of the substrate 5 are slightly scraped so that the substrate 5 does not come off, the substrate is exposed, and the exposed portion of the substrate is held and fixed securely.

  In order to rotate the substrate 5 at a high speed, the first drive unit 7 is preferably a high-frequency motor capable of rotating at a high speed, preferably 1 to 60000 rpm. If the rotational speed is too small, the number of twists that can be applied to the fine carbon fiber twisted yarn is too small, and the yarn strength of the fine carbon fiber twisted yarn is insufficient, which is not preferable. On the other hand, when the rotational speed is too large, the drawing stability of the fine carbon fiber twisted yarn from the aggregate of fine carbon fibers is lowered, which is not preferable.

  In a preferred embodiment of the fine carbon fiber twisted yarn manufacturing apparatus 1A, a windshield 18 is provided in the vicinity of the fine carbon fiber delivery port. In the manufacturing apparatus of the present invention, the substrate on which the fine carbon fibers are formed on the delivery side rotates at a high speed, so that damage to the fine carbon fibers due to air resistance is large. Therefore, by providing a windshield, when the fine carbon fiber rotates at a high speed, the air is provided in the windshield 18 so that damage to the fine carbon fiber can be suppressed. The windshield 18 is preferably a transparent part in order to monitor the breakage of the fine carbon fiber twisted yarn or the pulled state of the fine carbon fiber twisted yarn by a stroboscope or the like.

  The winding device 4 preferably has a winding speed of the bobbin 3 of 0.005 to 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, the number of twists that can be applied to the fine carbon fiber twisted yarn is too small, which is not preferable because the yarn strength of the fine carbon fiber twisted yarn is insufficient.

  As shown in FIG. 2, the fine carbon fiber twisted yarn manufacturing apparatus 1 </ b> A can traverse the bobbin 3 while providing the twisted yarn guide 19 fixed to the substrate holding device 2. Normally, when winding a yarn around a bobbin, a traverse guide provided on the winding device side reciprocates left and right (traverse), thereby winding the yarn uniformly around the bobbin. However, in this method, since the friction between the guide and the yarn is large, in the case of an ultrafine fine carbon fiber twisted yarn as obtained in the present invention, a method with less friction is desired. Therefore, in this embodiment, the friction between the fine carbon fiber twisted yarn and the twisted yarn guide 19 can be reduced by traversing the bobbin 3 of the winding device while fixing the twisted yarn guide 19 so as not to move. it can. The twisted yarn guide 19 is preferably a satin specification in order to reduce friction as much as possible. Or if a pulley is used as a twisted yarn guide, the friction between the yarn and the twisted yarn guide can be further reduced.

  In the fine carbon fiber twisted yarn manufacturing apparatus 1 </ b> A, it is preferable that the surface of the bobbin 3 is subjected to surface processing for preventing slipping during winding. Thereby, further process stability can be realized. In addition, the surface processing method to a bobbin is not specifically limited, The method of giving a mirror surface process, rubber lining, etc. are mentioned.

  The SEM photograph (1000 times) of the fine carbon fiber twisted yarn manufactured with said apparatus is shown in FIG. The twist angle of the twisted yarn is determined by the number of twists per unit length. The twist angle of the twisted yarn is adjusted by the substrate holding device 2 that holds the substrate 5 in the twisted yarn manufacturing apparatus 1A on the fine carbon back and the rotational speed of the bobbin 3. The inventors have found that there is a relationship between twist angle and twist strength. A twist angle in this range is preferable because a good strength is exhibited when the twist angle is 10 to 50 °. Therefore, the rotation driving of the substrate holding device 2 and the bobbin winding driving are interlocked so that the twist angle is 10 to 50 °.

  The fine carbon fiber twisted yarn manufacturing apparatus 1A can be equipped with a yarn breakage detector, although not shown. For example, an ultrafine carbon material twisted yarn pulled out from the substrate 5 while being twisted between the substrate 5 on which the fine carbon fiber is grown and the bobbin 3 is photographed by an imaging device such as a CCD, and the captured image data is displayed on the display screen. The image data of the projected video is captured and scanned in a computer, and the number of pixels is counted. At this time, the difference in color (darkness) between the background and the twisted yarn can be used to detect yarn breakage when the number of pixels constituting the twisted yarn decreases. More specifically, the twisted yarn is enlarged and displayed on the display screen, and an image is taken into the computer every 15 seconds. In this case, for example, the fine carbon fiber twisted yarn appears blackish brown and the background appears light brown. Therefore, this is converted to gray scale. For example, when conversion is performed with 256 gradations, 100 or less is set to black and a portion with fine carbon fiber twisted yarn is used, and 101 or more is set as a background portion without fine carbon fiber twisted yarn and the total number of pixels on the screen is scanned and counted. Such binarization is performed for determination. It is desirable to enlarge the ratio of the area of the twisted yarn in the image to be 5% or more. If thread breakage occurs, the twisted yarn area in the screen will be smaller than usual. If the area of the twisted yarn portion is reduced continuously for two screens, it is possible to detect yarn breakage without making a mistake with uneven thickness of the twisted yarn. Of course, the thread breakage can be detected by looking at the screen in real time.

  Here, a preferred example from when the fine carbon fibers are first drawn out from the aggregate of fine carbon fibers on the substrate and passed to the bobbin 3 will be described. For convenience of explanation, the illustration is simplified.

  As shown in FIGS. 6 and 7, the apparatus for producing fine carbon fiber twisted yarn includes an extraction tool 21 having an ultrathin shaft portion 21 a that draws out the fine carbon fibers from the side surface of the aggregate C of fine carbon fibers on the substrate 5, and a drawing tool. A motor 22 for rotating the output tool 21 around its axis 21X can be provided as an accessory.

  The material of the drawer 21 having the ultrathin shaft portion 21a is iron, aluminum, stainless steel, an alloy such as tungsten-carbide, plastic, wood, glass or the like, and is not particularly limited. The drawing tool 21 only needs to have an appropriate friction resistance with respect to the fine carbon fiber, and in order to cause friction to the drawing tool, a circumferential groove, a spiral groove, an embossing on the outer peripheral surface of the ultrafine shaft portion 21a. It is desirable to have fine protrusions by processing or the like.

  The diameter of the ultrafine shaft portion 21a is determined depending on the average length of the fine carbon fibers grown on the substrate. As described above, the average length (L) of the fine carbon fibers of the fine carbon fiber aggregate C formed on the substrate 5 used in the present invention is 0.02 mm or more.

  With respect to the average length (L) of the fine carbon fibers on the substrate 5, the shaft diameter or diameter (D) of the ultrathin shaft portion 21a is preferably D <(L / π). If the diameter is D <(L / π), it is calculated that the drawing tool is tightly wound around the very thin shaft portion 21a when the drawing tool rotates once in the fine carbon fiber aggregate on the substrate. . To pull out fine carbon fiber with high probability, it is important to keep it tight for more than one lap. Micro drills having a blade diameter of 0.05 mm or more are commercially available, and can be used as a drawing tool.

  The ultrathin shaft portion 21a of the drawing tool 21 is pierced from the side surface of the aggregate C of fine carbon fibers growing on the substrate 5, and is made to enter. The depth of entry is preferably 0.01 mm or more. The height position at which the extraction tool 21 is pierced is preferably a height of ½ or less of the average length of fine carbon fibers growing on the substrate 5. At the time of this entry, the drawing tool 21 may be rotating, or the rotation may be stopped. The entry is stopped when the ultra-thin shaft portion 21a of the extraction tool 21 enters 0.01 mm or more. With the drawing tool 21 indwelled at this location, the ultrathin shaft portion 21a of the drawing tool 21 is rotated about its axis. After the extractor 21 is rotated at 1 to 1000 rpm for 1 second to 5 minutes, the extractor 21 is separated from the substrate 5 while being rotated at 1 to 1000 rpm, and the fine carbon fibers are pulled out from the aggregate C. Then, after the drawing tool 21 is moved onto the bobbin 3, the movement and rotation of the drawing tool 21 are stopped and stopped.

  After contacting the bobbin 3 with the fine carbon fiber twisted yarn drawn from the aggregate on the substrate 5 as described above, the bobbin 3 is started to rotate, and the substrate is rotated to twist and start spinning. it can.

  The tension when pulling out the fine carbon material fiber from the substrate is usually 0.05 to 0.5 mN. When this value is exceeded, thread breakage easily occurs. Therefore, if yarn breakage occurs during prevention, it is extremely difficult to connect both ends of the two fine carbon material twisted yarns broken by hand in the same manner as usual, for example, handling cotton fibers. . Then, next, the connection method of the twisted yarn when the yarn breakage occurs during the spinning of the fine carbon fiber twisted yarn will be described with reference to FIG.

  First, as shown in FIG. 8 (a), the ultrathin shaft portion 21a of the drawing tool 21 is inserted into the aggregate C of fine carbon fibers growing on the substrate 5, and again in the above-described manner. The fine carbon fiber T1 is pulled out without being twisted, or the drawing tool 21 is rotated to bring the twisted yarn of the fine carbon fiber T1 to the top of the bobbin 3. It is also possible to stop the rotation of the drawing tool 21 and rotate the substrate 5 to draw out the twisted yarn of the fine carbon fiber. In this way, the fine carbon fiber twisted yarn drawn from the aggregate of the fine carbon fibers on the substrate 5 by the drawing tool 21 is drawn to the upper position of the bobbin 3 and tensioned tightly.

  Next, as shown in FIG. 8 (b), the fine carbon fiber twisted yarn T2 remaining on the bobbin 3 is gently pulled out with a tapered tweezers or the like, and is finely connected to the drawing tool 21 and tightened. Gently place on the carbon fiber twisted yarn T1.

  When the drawing tool 21 and the substrate 5 are stationary, by rotating either of them gently here, as shown in FIG. 8C, the fine carbon fiber twisted yarn T2 that has been hand-drawn from the top of the bobbin. Engage one end and connect. The number of rotations of the drawing tool 21 or the substrate 5 at this time is 1 to 1000 rpm, and if the rotation is too fast, the broken ends of the fine carbon fiber twisted yarn T <b> 2 drawn from the bobbin 3 will be repelled. It is better to rotate slowly at the beginning and gradually rotate at a higher speed.

  Thereafter, when the drawing tool 21 is rotating, the rotation is stopped and the substrate 5 is rotated at a desired number of rotations. At the same time, the fine carbon fiber twisted yarn T1 connected to the drawing tool 21 is cut and separated from the drawing tool (FIG. 8 (d)), and the spinning is resumed by rotating the bobbin 3 to make a long fine carbon fiber twisted yarn. Can be manufactured.

  Next, a method of connecting the fine carbon fiber twisted yarn wound around two bobbins to form one long twisted yarn will be described with reference to FIG.

  As shown in FIG. 9, the other end of the twisted yarn Ta, one end of which is wound around the bobbin 3a, is pulled out, and a light weight 11a made of paper is connected to the pulled-out tip and tensioned tightly through the guide 10a. On the other hand, the other end of the twisted yarn Tb, one end of which is wound around another bobbin 3b, is similarly pulled out, and a light weight 11b made of paper is connected to the pulled-out tip, and is tensioned through the guide 10b. The twisted yarn Ta and the twisted yarn Tb are overlapped between the guides 10a and 10b, the bobbin 3b is rotated around the twisted yarn, and the overlapping portion of the twisted yarns Ta and Tb is twisted to form one long fine carbon fiber. Can be produced.

  The rotation speed of the bobbin 3b at this time is preferably about 1 to 1000 rpm, and it is desirable to rotate slowly at the beginning. After twisting the overlapping portion of the twisted yarns Ta and Tb, the unwinding rotation of the bobbin 3a and the winding rotation of the bobbin 3b are synchronized, and the fine carbon fiber twisted yarn is sent from the bobbin 3a to the bobbin 3b and wound by the bobbin 3b. take.

  In order to further strengthen the joining of the two fine carbon fiber twisted yarns at the overlapping portion of the twisted yarns Ta and Tb, as shown in FIG. It is also very effective to draw out the fine carbon fiber TS that is in the form of a wide sheet and squeeze the drawn sheet against the overlapping portion of the twisted yarns Ta and Tb. The dimension of the fine carbon fiber sheet is preferably 1 mm wide x 1 mm long.

  Also, applying a liquid to the overlapping portion of the two fine carbon fiber twisted yarns Ta and Tb is very effective in improving the connection strength of the overlapping portion. When a liquid is applied to the overlapped portion of the twisted yarns Ta and Tb, the separated single yarns of fine carbon fibers are aggregated and tightened to increase the binding force. Thereafter, the overlapping portion of the fine carbon fibers is twisted and wound as described above. The liquid to be used preferably has polarity, and a liquid having a dielectric constant of 5 or more is preferably used. Examples thereof include alcohols having 1 to 5 carbon atoms, acetone, tetrahydrofuran, dimethylformamide, dimethylacetamide, water, ethyl acetate, and acetonitrile. Among these, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, ethyl acetate, and acetonitrile are preferable.

  Next, 2nd Embodiment of the manufacturing apparatus of the fine carbon fiber twisted yarn which concerns on this invention is described with reference to FIGS.

  In the fine carbon fiber twisted yarn manufacturing apparatus 1B of the second embodiment, as schematically shown in FIG. 11, the substrate holding device 2 includes a support body 20 that supports a plurality of substrate holding portions 6, and a plurality of holding portions 6. A first drive unit (not shown) that rotationally drives each of the two and a second drive unit (not shown) that rotationally drives the support 20, and further twist two or more fine carbon fiber twisted yarns together Can be matched.

  Usually, when producing a yarn in which two or more yarns are further twisted, two or more yarns once wound on a bobbin are prepared, and an external force is applied while unwinding the yarn to add a twist. However, in this method, since the yarn is wound around the bobbin once, the productivity is not expected, and a frictional force is applied to the yarn to add twist. There is a problem that cannot be applied.

  In order to overcome such a problem, in the apparatus of the present invention, two or more substrates 5 arranged on the same surface of the support 20 are respectively rotated about the first drive shaft 6c, and at the same time, the support By rotating and driving 20, the substrate 5 is rotated around the axis G in a rotation common to the substrates 5. As a result, two or more fine carbon fiber twisted yarns are more efficient and minimize damage to the yarn compared to the case where the yarn is wound around a bobbin and then a plurality of them are prepared and twisted later. Yarns twisted together can be produced.

  In addition, as shown in the second embodiment, until the fine carbon fiber twisted yarns are twisted together, by configuring the fine carbon fiber twisted yarn to be drawn upward from below, the sag of the fine carbon fiber twisted yarn is reduced, And since the tension | tensile_strength added to the fine carbon fiber twist yarn between a sending-out part and a winding-up part can always be kept constant, the further process stability is realizable. The fine carbon fiber twisted yarn may be pulled out from above. Moreover, the board | substrate 5 can also be arrange | positioned vertically with respect to the support body 20, as shown in FIG.

  FIG. 13 shows an SEM photograph (5,000 times) of the fine carbon fiber twisted yarn produced by the fine carbon fiber twisted yarn manufacturing apparatus 1B of the second embodiment.

  Next, 3rd Embodiment of the manufacturing apparatus of the fine carbon fiber twisted yarn which concerns on this invention is described with reference to FIGS. Although the said 1st, 2nd embodiment showed the example of the apparatus which twists a fine carbon fiber by rotating a board | substrate holding part, in 3rd Embodiment and 4th Embodiment which are demonstrated below, a bobbin is rotated. The example of the apparatus which twists a fine carbon fiber by making it show is shown.

  A fine carbon fiber twisted yarn manufacturing apparatus 1C according to the third embodiment includes a substrate holding device 2 having a substrate holding portion 6 and a winding device 4C having a bobbin 3 as shown in FIGS.

  The winding device 4C supports the bobbin 3 so as to be rotatable around the winding rotation axis, engages with the ring gear 23 having teeth on the outer peripheral surface, and the outer peripheral teeth of the ring gear 23, and drives the ring gear 23 to rotate. A gear 24, a pinion gear 25 fixed to the rotating shaft 3 a of the bobbin 3, and a face gear 26 that meshes with the pinion gear 25 and imparts winding rotation to the bobbin 3. In the illustrated example, the ring gear 23 is rotatably supported by a main body portion 41 of the winding device 4C via a bearing or the like, as shown in FIG.

  In the third embodiment, when the motor 24 a is activated to drive the drive gear 24, the ring gear 23 rotates clockwise in FIG. 15, and the bobbin 3 together with the ring gear 23 is rotated by the rotation of the ring gear 23. When the pinion gear 25 and the face gear 26 mesh with each other, the bobbin 3 is rotated in the direction of the arrow Y around the rotation axis 3a of the bobbin 3. The bobbin 3 is provided with a winding rotation by the rotation in the arrow Y direction, and at the same time, a rotation for twisting by the rotation in the arrow X direction. In this way, a twisting mechanism is configured in which the bobbin 3 is rotationally driven in the direction of the arrow X and twisted in conjunction with the winding drive of the bobbin 3 in the direction of the arrow Y. Also in this case, the winding drive of the bobbin 3 in the arrow Y direction and the rotational drive of the bobbin 3 in the arrow X direction are interlocked so that the twist angle becomes 10 to 50 °.

  Next, 4th Embodiment of the manufacturing apparatus of the fine carbon fiber twisted yarn which concerns on this invention is described with reference to FIGS.

  The fine carbon fiber manufacturing apparatus 1D of the fourth embodiment includes a substrate holding device 30 including a substrate holding portion 30a and a winding device 33 including a bobbin 32.

  The winding device 33 has a first drive unit 34 for winding and rotating the bobbin 32. Further, the winding device 33 includes a tapered end portion 31 for connecting a fine carbon fiber to the tip of the bobbin 32 in the winding rotation axis A direction. Further, the bobbin 32 is rotatably arranged around an axis B (FIG. 18) substantially orthogonal to the rotation axis A, and the tapered end portion 31 faces the substrate holding portion 30a so that the fine carbon fiber is drawn out. The first arrangement (FIGS. 17 and 18) along the winding rotation axis A and the second arrangement (FIGS. 19 and 20) in which the direction in which the fine carbon fiber is drawn out and the winding rotation axis A intersect can be changed. It has become.

  The substrate holding device 30 supports the substrate holding portion 30a by a linear actuator or the like so as to reciprocate, whereby the substrate holding portion 30a approaches the winding device 33 or moves away from the winding device 33. . The winding device 33 can be reciprocally movable so as to approach or separate from the substrate holding portion 30a.

  In the first arrangement shown in FIGS. 17 and 18, the fine carbon fiber twisted yarn manufacturing apparatus 1 </ b> D of the fourth embodiment rotates the bobbin 32 around the winding axis A with the fine carbon fiber connected to one end of the bobbin 32. Then, the substrate 5 is moved in a direction away from the bobbin 32 to twist the fine carbon fiber T while pulling out the fine carbon fiber T from the aggregate of the fine carbon fibers on the substrate 5.

  Next, in a state where the rotation of the bobbin 32 is stopped, the bobbin 32 is rearranged to the second arrangement shown in FIGS. 19 and 20, and then the bobbin 32 is rotated again around the winding rotation axis A and the bobbin The fine carbon fiber twisted yarn drawn out and twisted is wound around the bobbin 32 by moving the substrate 5 so that the distance between the substrate 5 and the bobbin 32 is shortened in synchronization with the rotation of the bobbin 32.

  As described above, a long fine carbon fiber twisted yarn can be wound on the bobbin 32 by alternately performing the step of drawing and twisting and the step of winding.

  In the fine carbon fiber manufacturing apparatus 1D, the reciprocating distance of the substrate holding portion 3a is such that the distance from the drawing position of the aggregate of fine carbon fibers on the substrate 5 to the tip 31 is in the range of 1 mm to 1000 mm. Is preferably set. If this distance is too short, the productivity is substantially poor. On the other hand, if this distance is too long, the process stability becomes poor due to the swinging of the fine carbon fiber twisted yarn itself existing between the tapered end portion 31 and the fine carbon fiber on the substrate 5, which is not preferable.

  Similarly to the first embodiment, in the fourth embodiment, the rotation speed of the first drive unit 34 is preferably 1 to 60000 rpm, and the winding speed of the winding device 33 is 0.005 to 30 m. / Min is preferred.

  Furthermore, in the case of the fourth embodiment, the fine carbon fiber twisted yarn manufacturing apparatus is such that the first drive unit 34 is on the lower side, the substrate holding device 30 is on the upper side, and the direction in which the fine carbon fibers are drawn out is the vertical direction. 1D can be placed. Thereby, since the tension | tensile_strength added to the fine carbon fiber twisted yarn between a sending-out part and a winding-up part can always be kept constant, without producing sagging of fine carbon fiber twisted yarn, the further process stability is realizable.

  The fine carbon fiber twisted yarn obtained in the present invention may be used as it is or may contain a binder or the like. By including a binder or the like, the fine carbon fiber twisted yarn can be made even stronger. The binder is not limited as long as it binds the fine carbon material twisted yarn, and examples thereof include polyvinyl alcohol. In addition, the fine carbon fiber twisted yarn of the present invention or those containing a binder may be tied into a rope, or may be processed into a woven fabric or a knitted fabric. By providing this binder, even if the fine carbon material twisted yarn wound on the bobbin is wound in a plurality of stages, the upper and lower twisted yarns are entangled and can be rewound without breaking.

  The present invention is not limited to the above embodiment, and various modifications can be made. For example, in the above embodiment, the apparatus for twisting the fine carbon fiber by rotating either the substrate holding part or the bobbin is exemplified, but the substrate may be combined by combining the first embodiment and the third embodiment. It is also possible to twist the fine carbon fiber twisted yarn by rotating both the holding portion and the bobbin. In the fourth embodiment, the end of the bobbin 32 can be replaced with the tapered end portion 31 to be a very thin shaft portion 21a.

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

Example 1
By sputtering iron on a silicon substrate (commercial product, 1 cm ² ), a silicon substrate on which an iron film having a thickness of 4 nm was laminated was manufactured.

  This substrate was placed in a thermal CVD apparatus, and a carbon nanotube aggregate was formed in a substrate shape by performing a thermal CVD method. The gas supplied into the thermal CVD was a mixed gas of acetylene gas and helium gas (acetylene gas 5.77 vol%). The thermal CVD conditions were temperature: 700 ° C., pressure: atmospheric pressure, acetylene gas concentration increase rate in the initial stage: 0.10 vol% / second, and reaction time: 10 minutes.

Using this substrate, acetylene gas and helium gas were supplied into a thermal CVD apparatus, and the carbon nanotubes of Example 1 were grown on the substrate by chemical vapor deposition. The grown carbon nanotubes have an average length of 190 μm and a thickness of about 15.3 nm, and the aggregate of carbon nanotubes on the substrate is formed with a high density and high orientation with a bulk density of 40 mg / cm ² and an order parameter of 0.94. It was in the state of a carbon nanotube aggregate.

  A part of the carbon nanotubes are scraped from the carbon nanotube substrate obtained as described above, and a silicon portion necessary for holding the substrate is exposed, and the fine carbon fiber twisted yarn manufacturing apparatus of the first embodiment (FIGS. 2 and 3). The substrate was held by the substrate holding device 2 of FIG. At this time, the angle (α) formed between the silicon substrate and the rotation axis of the substrate holding portion was 15 °. Further, the distance from the drawing position to the entry position to the winding bobbin was 50 mm.

  The substrate attached as described above is wound at a winding speed of 0.1 m / min while rotating at 8000 rpm, and a continuous twisted wound body having a twist number of 80000 T / m over 25 m is obtained. We were able to make it. At this time, the winding bobbin was slowly traversed within a range of 15 cm with a length of 15 cm and a diameter of 6 cm so that the wound yarns did not overlap. The twist angle of the wound body was measured. The average value of the twist angle was 48 °, and the tensile strength was 203 MPa. Spinning production was repeated twice more using this substrate, and the tensile strength was 235 and 310 MPa.

Example 2
A twisted yarn was produced using carbon nanotubes grown on a substrate produced in the same manner as in Example 1. The substrate was held by the substrate holding device 2 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 2 and 3) of the first embodiment, and the angle (α) formed by the silicon substrate and the rotation axis of the substrate holding portion was 15 °. Further, the distance from the drawing position to the entry position to the winding bobbin was 50 mm. The substrate can be wound at a winding speed of 0.2 m / min while rotating at 8000 rpm, and a continuous twisted wound body having a twist number of 40000 T / m over 18.2 m can be produced. It was. The twist angle of the wound body was measured. The average value of the twist angle was 25 °, and the tensile strength was 305 MPa. The spinning production was repeated three more times using this substrate, and the tensile strength was 560, 410, 265 MPa.

Example 3
A twisted yarn was produced using carbon nanotubes grown on a substrate produced in the same manner as in Example 1. The substrate was held by the substrate holding device 2 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 2 and 3) of the first embodiment, and the angle (α) formed by the silicon substrate and the rotation axis of the substrate holding portion was 15 °. Further, the distance from the drawing position to the entry position to the winding bobbin was 50 mm. While rotating the substrate at 2000 rpm, the substrate can be wound at a winding speed of 0.1 m / min to produce a continuous twisted wound body having a twist number of 20000 T / m over 20.5 m. It was. The average value of the twist angle was 15 °, and the tensile strength was 320 MPa. When the spinning production was repeated once more using this substrate, the tensile strength was 295 MPa.

Comparative Example 1
A twisted yarn was produced using carbon nanotubes grown on a substrate produced in the same manner as in Example 1. The substrate was held by the substrate holding device 2 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 2 and 3) of the first embodiment, and the angle (α) formed by the silicon substrate and the rotation axis of the substrate holding portion was 15 °. Further, the distance from the drawing position to the entry position to the winding bobbin was 50 mm. The substrate was wound at a winding speed of 1 m / min while rotating at 10000 rpm, and a continuous twisted wound body having a twist number of 10,000 T / m over 16.6 m could be produced. The average value of the twist angle was 8 °, and the tensile strength was 135 MPa. Spinning production was repeated twice more using this substrate, and the tensile strength was 60 MPa.

Comparative Example 2
A twisted yarn was produced using carbon nanotubes grown on a substrate produced in the same manner as in Example 1. The substrate was held by the substrate holding device 2 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 2 and 3) of the first embodiment, and the angle (α) formed by the silicon substrate and the rotation axis of the substrate holding portion was 15 °. Further, the distance from the drawing position to the entry position to the winding bobbin was 50 mm. The substrate is wound at a winding speed of 0.1 m / min while rotating at 10000 rpm, and a wound body of continuous twisted yarns having a twist number of 100,000 T / m over 15.3 m can be produced. It was. The average value of the twist angle was 70 °, and the tensile strength was 90 MPa. The spinning production was repeated four more times using this substrate, and the tensile strength was 40, 50, 100, and 130 MPa.

Example 4
A twisted yarn was produced using carbon nanotubes grown on a substrate produced in the same manner as in Example 1. The average length of the grown carbon nanotubes is 180 μm and the thickness is about 16.6 nm, and the aggregate of carbon nanotubes on the substrate is formed with a high density and high orientation with a bulk density of 20 mg / cm ² and an order parameter of 0.88. It was in the state of a carbon nanotube aggregate. The substrate was held by the substrate holding device 2 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 2 and 3) of the first embodiment, and the angle (α) formed by the silicon substrate and the rotation axis of the substrate holding portion was 15 °. Further, the distance from the drawing position to the entry position to the winding bobbin was 50 mm. The substrate can be wound at a winding speed of 0.5 m / min while rotating at 20000 rpm, and a continuous twisted wound body having a twist number of 40000 T / m over 18.8 m can be produced. It was. The average value of the twist angle was 24 °, and the tensile strength was 360 MPa.

Example 5
A twisted yarn was produced using carbon nanotubes grown on a substrate produced in the same manner as in Example 1. The grown carbon nanotubes have an average length of about 160 μm and a thickness of about 19.0 nm, and the aggregate of carbon nanotubes on the substrate is formed with a high density and high orientation with a bulk density of 60 mg / cm ² and an order parameter of 0.96. It was in the state of a carbon nanotube aggregate. The substrate was held by the substrate holding device 2 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 2 and 3) of the first embodiment, and the angle (α) formed by the silicon substrate and the rotation axis of the substrate holding portion was 15 °. Further, the distance from the drawing position to the entry position to the winding bobbin was 50 mm. The substrate was wound at a winding speed of 1 m / min while rotating at 40000 rpm, and a continuous twisted wound body having a twist number of 40000 T / m over 28.1 m could be produced. The average value of the twist angle was 23 °, and the tensile strength was 325 MPa.

Example 6
A twisted yarn was produced using carbon nanotubes grown on a substrate produced in the same manner as in Example 1. The grown carbon nanotubes have an average length of 175 μm and a thickness of about 10.0 nm, and the aggregate of carbon nanotubes on the substrate is formed with a high density and high orientation with a bulk density of 50 mg / cm ² and an order parameter of 0.95. It was in the state of a carbon nanotube aggregate. The substrate is held by the substrate holding device 2 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 2 and 3) of the first embodiment, and the angle (α) between the silicon substrate and the rotation axis of the substrate holding portion 6 is 15 °. . Further, the distance from the drawing position to the entry position to the winding bobbin was 50 mm. While the substrate is rotated at 4000 rpm, the substrate can be wound at a winding speed of 0.1 m / min, and a wound body of continuous twisted yarns having a twist number of 40000 T / m over 18.5 m can be produced. It was. The average value of the twist angle was 26 °, and the tensile strength was 405 MPa.

Example 7
A twisted yarn was produced using carbon nanotubes grown on a substrate produced in the same manner as in Example 1. The grown carbon nanotubes have an average length of 185 μm and a thickness of about 50.0 nm, and the aggregate of carbon nanotubes on the substrate is formed with a high density and high orientation with a bulk density of 25 mg / cm ² and an order parameter of 0.95. It was in the state of a carbon nanotube aggregate. The substrate was held by the substrate holding device 2 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 2 and 3) of the first embodiment, and the angle formed by the silicon substrate and the rotation axis of the substrate holding portion was 15 °. Further, the distance from the drawing position to the entry position to the winding bobbin was 50 mm. While the substrate is rotated at 400 rpm, the substrate is wound at a winding speed of 0.01 m / min, and a wound body of continuous twisted yarn having a twist number of 40000 T / m over 19.8 m can be produced. It was. The average value of the twist angle was 24 °, and the tensile strength was 345 MPa.

Example 8
A carbon nanotube produced in the same manner as in Example 1 has an average length of 190 μm and a thickness of about 6.3 nm, and the aggregate of carbon nanotubes on the substrate has a bulk density of 40 mg / cm ² and an order parameter of 0.94. The substrate was held by the substrate holding device 30 of the fine carbon fiber manufacturing apparatus 1D (FIGS. 17 to 20) of the fourth embodiment. A part of the carbon nanotube was attached to the rotating tip 31 and then the following unit operations 1 and 2 were alternately repeated twice to produce a twisted yarn having a twist number of 40000 T / m per meter.

  Unit operation 1: As shown in FIGS. 17 and 18, in the state where the rotation axis A of the rotation tip 31 is directed in the moving direction of the carbon nanotube substrate, the motor as the first drive unit 34 is rotated at 4000 rpm while the substrate is rotated. It was moved 50 cm in a direction away from the rotation tip at a speed of 0.1 m / min. After stopping the rotation of the motor and the movement of the substrate, the rotation tip was rotated by 90 ° around the rotation axis B together with the motor, and the arrangement as shown in FIGS.

  Unit operation 2: While rotating the bobbin 32 slowly, the bobbin 32 was moved 50 cm in a direction approaching the carbon nanotube substrate, and the carbon nanotube twisted yarn pulled out by the unit operation 1 was wound around the winding bobbin 32. After winding, the rotation of the motor and the movement of the substrate were stopped, and the rotation tip 31 was rotated by 90 ° together with the motor 34, and was again placed in the state shown in FIGS.

  By repeating the operations of the unit operations 1 and 2 alternately, it was possible to produce a wound body of continuous twisted yarn having a twist number of 40000 T / m over 18.7 m. SEM observation of the produced wound body was performed and the twist angle was measured (however, including the twisted yarn of the portion where the unit operations 1 and 2 were switched). The average value of the twist angle was 27 °, and the tensile strength was 304 MPa.

Example 9
In the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 2 and 3) of the first embodiment, 1 ml of an aqueous solution of 0.0001 wt% of poval is continuously applied to the carbon nanotube twisted yarn drawn from the substrate at a distance of 5 mm from the substrate holding device 2. A twisted yarn was produced in the same manner as in Example 1 except that it was given at a rate of / min. The carbon nanotubes grown on the substrate have an average length of 185 μm and a thickness of about 60.7 nm. The aggregate of carbon nanotubes on the substrate has a bulk density of 25 mg / cm ² and a high density and high order parameter of 0.95. It was in the state of the carbon nanotube aggregate formed by orientation. The substrate is held by the substrate holding device 2, and the angle (α) between the silicon substrate and the rotation axis of the substrate holding part is 15 °. Further, the distance from the drawing position to the entry position to the winding bobbin was 50 mm. The substrate can be wound at a winding speed of 0.2 m / min while rotating at 8000 rpm, and a continuous twisted wound body having a twist number of 40000 T / m over 25.3 m can be produced. It was. The average value of the twist angle was 24 °. At this time, the winding bobbin had a diameter of 3 cm and was wound while being traversed, but the yarn was wound up in a maximum of three stages. When I loosened this thread, it was unraveled without problems.

Comparative Example 3
A twisted yarn was produced in exactly the same manner as in Example 9 except that no poval aqueous solution was applied. When the yarn was loosened after production, the yarn was loosened and stuck where it overlapped on the surface of the take-up bobbin, and it was not possible to unwind it well.

Example 10
In the fine carbon fiber twisted yarn manufacturing apparatus (FIG. 11) of the second embodiment, four substrates on which the same carbon nanotubes as in Example 1 of 1.5 cm × 1.5 cm square are grown on the substrate holding device 2 are placed on the substrate base And fixed vertically. Each substrate was rotated clockwise at 5000 rpm with the center of the substrate platform as the central axis of rotation, and further rotated at 5000 rpm counterclockwise with the center of the platform on which the four substrates were placed as the rotational axis. The wound body was wound at a winding speed of 0.1 m / min, and a continuous wound thread body over 15.3 m could be produced. The produced twisted yarn is shown in the SEM photograph (5,000 times) in FIG.

Example 11
In the same manner as in Example 1, while twisting from the fine carbon fiber from the substrate 5 on which the fine carbon fiber is growing, the fine carbon fiber twisted yarn was spun and wound around the take-up bobbin 3. At this time, a CCD camera was installed between the substrate 5 and the winding bobbin, and the fine carbon fiber twisted yarn was magnified at a magnification of 5000 and displayed on the screen. The spinning image was taken into a personal computer every 15 seconds, and the area ratio was determined by counting the number of pixels constituting the background and the twisted yarn. The ratio of the area of the twisted yarn in the screen when spinning was smoothly performed was 17.5 to 20.1%. The yarn breakage occurred 1.8 hours after the start of spinning. At this time, the ratio of the twisted yarn in the screen rapidly decreased and became 0% after 45 seconds.

Example 12
In Example 8, the fine carbon fiber manufacturing apparatus 1D (FIGS. 17 to 20) of the fourth embodiment is assembled in a vertical arrangement so that the substrate holding part is on the upper side and the rotation tip is moved to the lower side. It was. A twisted yarn was produced in the same manner as in Example 8 except that the twisted yarn was pulled downward by about 1 m and then moved upward to wind up the twisted yarn. The length of the wound twisted yarn was 16 m. SEM observation of the produced wound body was performed and the twist angle was measured (however, including the twisted yarn of the portion where the unit operations 1 and 2 were switched). The average value of the twist angle was 28 °, and the tensile strength was 253 MPa.

Comparative Example 4
A part of the carbon nanotubes is attached to the tapered end portion 31 of the apparatus for producing fine carbon fibers of the fourth embodiment from the substrate on which the aggregate of carbon nanotubes is formed in the same manner as in Example 1, and the rotation of the tapered end portion 31 is performed. With the axis A directed in the direction of movement of the substrate 5, the substrate was moved by hand in the direction away from the tapered end while rotating the motor as the first drive unit 34 at 10000 rpm. Although a 1 m twisted yarn could be pulled out, the twisted yarn was cut by the swinging of the pulled twisted yarn, and a 1 m or longer twisted yarn could not be produced.

Example 13
The carbon nanotube substrate 5 manufactured in the same manner as in the first example was held and fixed on the substrate holding unit 6 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 6 and 7). A tungsten carbide micro drill having a drill blade having a diameter (blade diameter) of 0.06 mm and a length (blade length) of 1 mm (the portion of the drill blade excluding the shank corresponds to the ultrathin shaft portion 21a). Used as the drawing tool 21, without rotating the drawing tool, the ultrathin shaft portion 21a was pierced into the side surface of the carbon nanotube aggregate C on the substrate 5, and stopped by entering 1 mm. In this place, the extraction tool was rotated at 20 rpm for 10 seconds, and then the extraction tool 21 was moved backward at 0.1 mm / second to be separated from the substrate. When the drawing tool was 1 mm away from the substrate, the substrate 5 was rotated at 10,000 rpm to stop the rotation of the drawing tool 21, and this was moved onto the take-up bobbin 3 at 0.1 m / min. After the carbon nanotube twisted yarn was wound and fixed on the bobbin 3, the carbon nanotube twisted yarn was released from the drawing tool. Winding was performed at a winding speed of 0.1 m / min, and a continuous twisted wound body having a twist number of 100,000 T / m over 1 m or more could be produced.

  When this spinning operation was repeated 10 times, it was possible to shift to the winding process of the carbon nanotube twisted yarn around the winding bobbin 3 about 7 times.

Example 14
A micro drill having a drill blade having a length (blade length) of 5 mm and a diameter (blade diameter) of 0.03 mm is used as an extraction tool, and the ultra-thin shaft portion 21a of the extraction tool 21 is an assembly of carbon nanotubes on the substrate 5. Carbon nanotubes were drawn from the carbon nanotube aggregate C on the substrate 5 in the same manner as in Example 13 except that the depth of entry into the body C was 2 mm. It was possible to pull out the carbon nanotubes 8 times after trying 10 times, and to shift to the winding process of the carbon nanotube twisted yarn on the winding bobbin 3.

Example 15
A micro drill having a length of 1 mm and a diameter of 0.03 mm and provided with a drill blade having a spiral groove of two cycles is used as an extraction tool, and the ultrathin shaft portion 21 a of the extraction tool 21 is formed on the substrate 5. The carbon nanotubes were drawn from the aggregate of carbon nanotubes on the substrate 5 in the same manner as in Example 13 except that the depth of penetration of the carbon nanotubes into the aggregate C was 2 mm. The carbon nanotubes could be pulled out 9 times after trying 10 times, and the process could be shifted to the process of winding the twisted carbon nanotubes on the winding bobbin 3.

Example 16
A drawing tool having a length of 1 mm and a diameter of 0.03 mm and having a very thin shaft portion having a large number of minute protrusions is used. Carbon nanotubes were drawn from the aggregate of carbon nanotubes on the substrate 5 in the same manner as in Example 13 except that the depth of entering the body C was 2 mm. The carbon nanotubes could be pulled out 9 times after trying 10 times, and the process could be shifted to the process of winding the twisted carbon nanotubes on the winding bobbin 3.

Example 17
A micro drill having a drill blade having a length of 5 mm and a diameter of 0.03 mm is used as an extraction tool, and the depth at which the ultrathin shaft portion 21a of the extraction tool 21 enters the aggregate C of carbon nanotubes on the substrate 5 is set. Carbon nanotubes were drawn from the aggregate of carbon nanotubes on the substrate 5 in the same manner as in Example 13 except that the thickness was 0.2 mm. It was possible to pull out the carbon nanotube 6 times after trying 10 times, and to move to the winding process of the carbon nanotube twisted yarn on the winding bobbin 3.

Example 18
A drawing tool having a length of 3 mm and a diameter of 0.03 mm and having a spiral groove blade from the tip portion toward the root is used. The ultrathin shaft portion 21 a of the drawing tool 21 is used as a carbon nanotube on the substrate 5. Carbon nanotubes were drawn from the aggregate of carbon nanotubes on the substrate 5 in the same manner as in Example 13 except that the depth of entering the aggregate C was 2 mm. The carbon nanotubes could be pulled out 9 times after trying 10 times, and the process could be shifted to the process of winding the twisted carbon nanotubes on the winding bobbin 3.

Comparative Example 5
The carbon nanotubes were extracted from the carbon nanotube aggregate C on the substrate 5 in the same manner as in Example 13 except that the extraction tool 21 having the ultrathin shaft portion 21a having a diameter of 0.08 mm was used. The carbon nanotubes could be pulled out only once after five attempts, but could not be pulled out four times.

Comparative Example 6
Carbon nanotubes were extracted from the carbon nanotube aggregate C on the substrate 5 in the same manner as in Example 13 except that the extraction tool 21 having an ultrathin shaft portion 21a having a diameter of 0.1 mm was used. The carbon nanotube could not be pulled out after 5 attempts.

Comparative Example 7
The drawing tool 21 having a length of 1 mm and a diameter of 0.03 mm and having a mirror-finished ultra-thin shaft portion 21 a has an entry depth of 2 mm into the aggregate C of carbon nanotubes on the substrate 5. Except for the above, carbon nanotubes were drawn from the aggregate of carbon nanotubes on the substrate 5 in the same manner as in Example 13. The carbon nanotube could be pulled out only once after 5 attempts.

Example 19
The carbon nanotube substrate manufactured in the same manner as in the first example was held and fixed on the substrate holding unit 6 of the fine carbon fiber twisted yarn manufacturing apparatus shown in FIGS. Without rotating the drawing tool 21 (commercially available micro-drill) having an ultrathin shaft portion 21a having a diameter of 0.03 mm and a length of 1 mm, it is pulled on the side surface of the carbon nanotube aggregate on the substrate 5. The ultra-thin shaft portion 21a of the exit tool 21 was pierced and stopped by entering 1 mm. In this state, the extraction tool was rotated around its axis at 20 rpm for 10 seconds, and then the extraction tool 21 was retracted at 0.1 mm / second to separate from the substrate. When the drawing tool 21 was 1 mm away from the substrate, the substrate was rotated at 10000 rpm to stop the rotation of the drawing tool 21, and this was moved onto the take-up bobbin 3 at 0.1 m / min. After the carbon nanotube twisted yarn was wound and fixed on the bobbin 3, the carbon nanotube twisted yarn was released from the drawing tool 21. Winding was performed at a winding speed of 0.1 m / min, and breakage occurred when a continuous twisted wound body having a twist number of 100,000 T / m over 3.1 m was produced. The rotation of the substrate was stopped.

  As shown in FIG. 8 (a), the fine shaft-like portion 21a of the extraction tool is made to enter the aggregate C of fine carbon fibers grown on the substrate 5 again, and again the fine carbon is retreated as described above. The fiber T1 was pulled out, and the twisted yarn of the fine carbon fiber was taken up to the upper part of the bobbin 3 while rotating the drawing tool 21 around its axis. Here, the rotation of the drawer was stopped. Next, as shown in FIG. 8 (b), the broken ends of the fine carbon fiber twisted yarn T2 remaining on the take-up bobbin 3 are gently pulled out, and the drawn tool-side twisted yarn T1 and the bobbin-side twisted yarn T2 Was placed on a tightly stretched fine carbon fiber twisted yarn. The tension at the time of pulling out was 0.2 to 0.4 mN. As shown in FIG. 8 (c), the drawing tool was rotated around its rotation axis at 10 rpm, the broken end of the bobbin side twisted yarn was wound around the drawing tool side twisted yarn, and both twisted yarns were twisted and connected. Thereafter, as shown in FIG. 8 (c), the rotation of the drawing tool is stopped, the substrate 5 is rotated at 10,000 rpm, and at the same time, the carbon nanotube twisted yarn connected to the drawing tool is cut, as shown in FIG. 8 (d). Then, the winding bobbin 3 was rotated to resume spinning at a winding speed of 0.1 m / min. Thus, a long fine carbon fiber twisted yarn could be manufactured. A total of two connection operations were performed to obtain a carbon nanotube twisted yarn having an average diameter of 3 μm and a length of 10 m.

Example 20
Two wound bodies of twisted carbon nanotubes having a length of 1 m manufactured by the method shown in Example 19 were set in an apparatus as shown in FIG. One end of the carbon nanotube twisted yarn Ta is pulled out from the take-up bobbin 3a, a paper weight 11a of 5 mm × 5 mm (1.9 × 10 ⁻³ mg) is connected to the drawn end, and the carbon nanotube twisted yarn is also taken from the take-up bobbin 3b. One end of Tb was pulled out, and a similar weight 11b was connected to the tip of the Tb, and it was tightened through the guides 10a and 10b. Thereafter, the take-up bobbin 3a was rotated in the direction with the stretched twisted yarn Ta as the central axis to twist the overlapping portion. The winding bobbin 3a was rotated at 10 rpm for 10 minutes to connect the two carbon nanotube twisted yarns Ta and Tb. The winding bobbins 3a and 3b were rotated at a speed of 0.1 m / min, and the twisted yarn was fed from the bobbin 3a to the bobbin 3b and wound around the bobbin 3b to produce a carbon nanotube twisted yarn having a length of 2 m. By this method, the two carbon nanotube twisted yarns were connected 10 times, and 6 times, the first connection operation was successful without any problems. The remaining 4 times tried to connect several times and succeeded.

Example 21
In the connection operation shown in Example 20, 0.5 ml of ethanol was added to the “overlap” of the overlapping portion. After air drying, the overlap portion was twisted in the same manner as in Example 20, and then the carbon nanotube twisted yarn was wound around the winding bobbin 3b. The two carbon nanotube twisted yarns were connected 10 times by this method, and 8 times, the first connection work could be connected without any problems.

Example 22
A carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 21 except that methanol was used instead of ethanol.

Example 23
A carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 21 except that isopropanol was used instead of ethanol.

Example 24
A carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 21 except that pentanol was used instead of ethanol.

Example 25
The carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 21 except that acetone was used instead of ethanol.

Example 26
A carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 21 except that methanol was used instead of ethanol.

Example 27
The carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 21 except that tetrahydrofuran was used instead of ethanol.

Example 28
The carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 21 except that dimethylformaldehyde was applied instead of ethanol, and warm air at 100 ° C. was sent for 1 hour and dried.

Example 29
The carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 21 except that dimethylacetamide was added instead of ethanol, and warm air at 100 ° C. was sent for 1 hour and dried.

Example 30
The carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 21 except that water was applied instead of ethanol and hot air at 100 ° C. was sent for 5 minutes to dry.

Example 31
As shown in FIG. 10, the carbon nanotubes were pulled out by about 1 cm with a width of 2 mm using a drawing tool 21 having a wide-width portion coated with an adhesive at the tip. I scooped this up with tweezers. The scooped 2 mm × 8 mm carbon nanotube sheet was gently placed on the “overlap” of the overlapping portion in the connection operation shown in Example 20 to cover the overlapping portion. Thereafter, in the same manner as in Example 20, the overlapping portions were twisted and connected, and then the carbon nanotube twisted yarn was wound around the winding bobbin 3b. The two carbon nanotube twisted yarns were connected 10 times by this method, and 8 times, the first connection work could be connected without any problems.

Example 32
The carbon nanotube substrate obtained in the same manner as in Example 1 was held and fixed on the substrate holder 6 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 6 and 7). Without rotating the drawing tool 21 having an ultrathin shaft portion having a diameter of 0.03 mm and a length of 1 mm, the ultrathin shaft portion 21a is pierced into the side surface of the carbon nanotube aggregate C on the substrate and stopped by entering 1 mm. I let you. In this state, the extraction tool 21 was rotated at 20 rpm for 10 seconds, and then the extraction tool 21 was moved backward at 0.1 mm / second to be separated from the substrate. When the drawing tool 21 was separated from the substrate 5 by 1 mm, the substrate was rotated at 10000 rpm to stop the rotation of the drawing tool 21, and this was moved onto the take-up bobbin 3 at 0.1 m / min. After the carbon nanotube twisted yarn was wound and fixed on the bobbin 3, the carbon nanotube twisted yarn was released from the drawing tool 21. Winding was performed at a winding speed of 0.1 m / min. When a continuous twisted wound body having a twist number of 100,000 T / m over 2.3 m was produced, yarn breakage occurred. The rotation of the substrate was stopped. The ultrafine shaft-like portion of the drawing tool 21 is again entered into the aggregate of fine carbon fibers growing on the substrate, and the fine carbon fiber is drawn again in the manner described above, and at the same time the rotation of the drawing tool is stopped. The substrate was rotated at 500 rpm to wind up the carbon nanotube twisted yarn and brought it to the top of the bobbin 3. Next, the piece of fine carbon fiber twisted yarn remaining on the take-up bobbin was gently handed out to take 1 cm of “overlap” and placed gently on the tight carbon fiber twisted yarn. The drawing tool was rotated around its rotation axis at 10 rpm, and the bobbin-side twisted yarn was wound around the drawing-tool-side twisted yarn. Thereafter, the rotation of the drawing tool is stopped, the substrate is rotated at 10000 rpm, and at the same time, the carbon nanotube twisted yarn connected to the drawing tool is cut, and the winding bobbin 3 is rotated to perform spinning at a winding speed of 0.1 m / min. Resumed. Thus, a long fine carbon fiber twisted yarn could be manufactured. A total of two connection operations were performed to obtain a carbon nanotube twisted yarn having an average diameter of 3 μm and a length of 10 m.

Example 33
The carbon nanotube substrate obtained in the same manner as in Example 1 was held and fixed on the substrate holding part 6 of the fine carbon fiber twisted yarn manufacturing apparatus (FIGS. 6 and 7). Without rotating the drawing tool 21 having the ultrathin shaft portion 21a having a diameter of 0.03 mm and a length of 1 mm, the ultrathin shaft portion is stabbed into the side surface of the carbon nanotube aggregate C on the substrate and stopped by entering 1 mm. did. In this state, the extraction tool 21 was rotated at 20 rpm for 10 seconds, and then the extraction tool 21 was moved backward at 0.1 mm / second to be separated from the substrate. When the drawing tool 21 was 1 mm away from the substrate, the substrate was rotated at 10000 rpm to stop the rotation of the drawing tool 21, and this was moved onto the take-up bobbin 3 at 0.1 m / min. After the carbon nanotube twisted yarn was wound and fixed on the bobbin 3, the carbon nanotube twisted yarn was released from the drawing tool 21. Winding was performed at a winding speed of 0.1 m / min, and thread breakage occurred when a continuous twisted wound body having a twist number of 100000 T / m over 1 m over 1.5 m was produced. The rotation of the substrate was stopped. When the ultra-thin shaft portion 21a of the drawing tool 21 is again entered into the aggregate of fine carbon fibers growing on the substrate, the fine carbon fiber is drawn again as described above, and rotation of the drawing tool is stopped. At the same time, the substrate was rotated at 500 rpm to wind up the carbon nanotube twisted yarn and brought it to the top of the bobbin 3. Next, the piece of fine carbon fiber twisted yarn remaining on the take-up bobbin was gently handed out to take 1 cm of “overlap” and placed gently on the tight carbon fiber twisted yarn. The drawing tool was rotated at 10 rpm, and the piece of the twisted yarn on the bobbin 3 side was wound on the twisted yarn on the drawing tool side. Thereafter, the rotation of the drawing tool is stopped, the substrate is rotated at 10000 rpm, and at the same time, the carbon nanotube twisted yarn connected to the drawing tool is cut, and the winding bobbin 3 is rotated to perform spinning at a winding speed of 0.1 m / min. Resumed. Thus, a long fine carbon fiber twisted yarn could be manufactured. A total of two connection operations were performed to obtain a carbon nanotube twisted yarn having an average diameter of 3 μm and a length of 10 m.

Example 34
In the same manner as in Example 31, when connecting the fine carbon material fiber drawn from the carbon nanotube on the substrate and the fine carbon material twisted yarn on the take-up bobbin, as shown in FIG. A carbon nanotube sheet of 2 mm × 8 mm, which was pulled out about 1 cm in width by 2 mm using a drawing tool provided at the tip and scooped with tweezers, was gently placed on the “overlapping” portion, and the overlapped portion was covered. 0.5 ml of ethyl acetate was given to the part covered with this sheet. Thereafter, the carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 31. The two carbon nanotube twisted yarns were connected 10 times by this method, and 9 times, the connection was possible without any problems in the first connection work.

Example 35
A carbon nanotube twisted yarn was wound around the winding bobbin 3b in the same manner as in Example 34 except that acetonitrile was applied instead of ethyl acetate and air-dried.

  According to the present invention, it becomes possible to produce a fine carbon fiber twisted yarn continuously and homogeneously. The resulting fine carbon fiber twisted yarn is a protective material, bulletproof / protective clothing, industrial use that requires high strength. It can be used for fiber materials for materials, various textile products for sports, electric wires that require electrical conductivity, wiring / members of various electrical products, and the like.

Claims (14)

A method for continuously producing twisted yarns of fine carbon fibers,
A growth step of chemical vapor deposition of an aggregate of fine carbon fibers on a substrate;
A winding step of continuously drawing out fine carbon fibers from the aggregate on the substrate and winding them on a bobbin;
By rotating at least one of the substrate and the bobbin, the fine carbon fiber continuously drawn from the aggregate of fine carbon fibers on the substrate and wound on the bobbin is twisted to form a fine carbon fiber twisted yarn. And a twisting process to
The twisting step and the winding step are performed simultaneously,
In the growth step, the fine carbon fibers are grown so that the average length (L) is 0.02 mm or more,
The twisting step is capable of moving between the substrate and the hobbin, while rotating an extraction tool having an ultra-thin shaft portion whose diameter (D) is set to D <(L / π), or Without rotating the extraction tool, the fine shaft-like portion is stabbed into the side surface of the aggregate of fine carbon fibers grown on the substrate to enter a predetermined distance, and the extraction tool is rotated while rotating at a predetermined rotation speed. A method for producing fine carbon fiber twisted yarn, comprising a step of drawing out carbon fiber. A method for continuously producing twisted yarns of fine carbon fibers,
A growth step of chemical vapor deposition of an aggregate of fine carbon fibers on a substrate;
A drawing and twisting step of forming a fine carbon fiber twisted yarn by twisting the fine carbon fiber by rotating the bobbin while continuously drawing out the fine carbon fiber from the aggregate of fine carbon fibers on the substrate,
A winding step of winding the drawn and twisted fine carbon fiber twisted yarn on a bobbin,
In the pulling and twisting step, a first arrangement in which the winding rotation axis extends in a direction in which the fine carbon fiber is drawn out, and a second arrangement in which the winding carbon rotation axis intersects with the direction in which the fine carbon fiber is drawn out. Using a repositionable bobbin, while rotating the bobbin around a winding axis while the fine carbon fiber is connected to one end of the bobbin in the first arrangement, at least one of the substrate and the bobbin is mutually connected By moving in a direction away from the substrate, twisting while pulling out the fine carbon fibers from the aggregate of fine carbon fibers on the substrate,
In the winding step, after the bobbin is stopped rotating, the bobbin is relocated to the second arrangement, and then the bobbin is rotated around the winding rotation axis and in synchronization with the bobbin rotation. By winding at least one of the substrate and the bobbin so that the distance between the substrate and the bobbin is reduced, the fine carbon fiber twisted yarn drawn and twisted in the second step is wound around the bobbin,
The method for producing a fine carbon fiber twisted yarn, wherein the draw-twisting step and the winding step are alternately performed. The method of twisting the fine carbon fiber in the twisting step is by rotating the substrate,
The twisting step prepares a plurality of substrates having the aggregate of the fine carbon fibers, and twists the fine carbon fibers drawn from the aggregate by rotating each substrate around a rotation axis passing through each substrate. 2. The fine carbon fiber twisted yarn according to claim 1, wherein the fine carbon fiber twisted yarn is further twisted by further rotating the plurality of substrates around a common rotation axis while forming the fine carbon fiber twisted yarn. Manufacturing method. It further has a recovery process for recovering the breakage of the fine carbon fiber twisted yarn,
In the recovery step, the fine carbon fiber is attached to the ultrafine shaft-shaped portion after piercing the ultrafine shaft-shaped portion of the drawing tool having the ultrafine shaft-shaped portion on the side surface of the aggregate of the fine carbon fibers, and from the substrate. Pull out the fine carbon fiber without twisting, or rotate the substrate or drawing tool to draw out the fine carbon fiber twisted yarn, and pull the end of the drawn twisted yarn on one end of the fine carbon fiber twisted yarn already wound on the bobbin After the overlapping, the twisted portion is twisted to connect both twisted yarns, and the fine carbon fiber twisted yarn connected to the ultra-thin shaft-like portion of the drawing tool is separated from the drawing tool, so that two twisted yarns The method for producing fine carbon fiber twisted yarn according to claim 1, wherein: And further comprising a connecting step of connecting the fine carbon fiber twisted yarns wound around the pair of bobbins,
In the connecting step, the other end of the first twisted yarn, one end of which is wound around the first bobbin, is pulled out, and the other end of the second twisted yarn, whose one end is wound around the second bobbin, 2. The fine carbon according to claim 1, wherein two twisted yarns of fine carbon fibers are connected by overlapping the other ends of the twisted yarns, twisting the overlapped portions and connecting the two twisted yarns. A manufacturing method of material fiber twisted yarn.   The overlap portion of the two twisted yarns to be connected is covered with a wide sheet-like fine carbon fiber drawn from a substrate subjected to chemical vapor deposition, and then twisted on the overlap portion. 6. The method for producing fine carbon fiber twisted yarn according to claim 4, wherein connection is made by applying   After applying a liquid selected from alcohol having 1 to 5 carbon atoms, acetone, tetrahydrofuran, dimethylformamide, dimethylacetamide, ethyl acetate, acetonitrile, or water to the overlapped portion, the overlapped portion is twisted. The method for producing a fine carbon fiber twisted yarn according to any one of claims 4 to 6, wherein An apparatus for continuously producing twisted yarns of fine carbon fibers from an aggregate of fine carbon fibers grown by chemical vapor deposition on a substrate,
A substrate holder for holding the substrate;
A bobbin for winding and driving the fine carbon fiber twisted yarn;
Interlocking with the bobbin winding drive so as to twist the fine carbon fiber drawn from the aggregate on the substrate held by the substrate holding unit and wound on the bobbin, the substrate holding unit and the bobbin A twisting mechanism that rotationally drives at least one ;
An extraction tool that is movable between the substrate and the hobbin, and has an ultra-thin shaft-like portion for piercing a side surface of a collection of fine carbon fibers grown on the substrate and pulling out the fine carbon fibers;
A rotation drive device that rotates the drawing tool about an axis, and
The diameter (D) of the ultrathin shaft portion of the drawing tool is set to D <(L / π) with respect to the average length (L) of the fine carbon fibers grown on the substrate. Said device characterized . An apparatus for continuously producing twisted yarns of fine carbon fibers from an aggregate of fine carbon fibers grown by chemical vapor deposition on a substrate,
A substrate holder for holding the substrate;
A bobbin for winding and driving the fine carbon fiber twisted yarn,
In the bobbin, a tapered end portion for connecting the fine carbon fibers is formed at one end in the winding rotation axis direction, and the tapered end portion faces the substrate holding portion and the fine carbon fibers are drawn out. The first arrangement along the winding rotation axis and the second arrangement in which the direction in which the fine carbon fiber is drawn out and the winding rotation axis intersect can be changed.
The apparatus according to claim 1, wherein at least one of the bobbin and the substrate holding part is provided so as to reciprocate so as to approach or separate from each other. The substrate holding portion has a rotation axis of the holding portion directed toward a peripheral edge of the bobbin so as to avoid interference between the fine carbon fibers drawn from the aggregate on the substrate and the substrate, and the substrate The apparatus according to claim 8 , wherein the apparatus is configured to hold the non-parallel to the rotation axis of the holding unit. Each of the plurality of substrate holders is twisted to twist a fine carbon fiber drawn from each of the aggregates on the substrate held on each substrate holder and the substrate that supports the plurality of substrate holders. The apparatus according to claim 8 , further comprising: a plurality of first driving units that are rotationally driven, and a second driving unit that rotationally drives the support to further twist the fine carbon fiber twisted yarns. . The apparatus according to claim 8 , further comprising a windshield near a position where the fine carbon fiber is drawn from the substrate. Further comprising a monitoring device for monitoring whether the fine carbon fibers are cut on the substrate or the fine carbon fibers are pulled out of the substrate,
The monitoring device is obtained by an imaging device that photographs the fine carbon fiber twisted yarn pulled out from the substrate while applying a twist existing between a bobbin and a substrate obtained by chemical vapor deposition of fine carbon fibers, and the imaging device. A display that displays the enlarged image data on the screen, and a determination unit that scans the image data of the image displayed on the display and determines that the yarn is broken when the number of pixels constituting the twisted yarn decreases. The apparatus for producing fine carbon fiber twisted yarn according to claim 8 , The apparatus according to claim 8 , wherein the drawing tool has at least one of a circumferential groove, a spiral groove, and a protrusion on an outer peripheral surface of the ultrathin shaft-like portion.

Images