Apparatus for manufacturing carbon nanotube wire material and method for manufacturing carbon nanotube wire material

Abstract

An apparatus for manufacturing a carbon nanotube wire material is provided with a first tube, a second tube, a first supply unit, and a second supply unit. The first tube has a first inner peripheral surface and an outer peripheral surface. The outer peripheral surface surrounds the first inner peripheral surface. The second tube has a second inner peripheral surface. The second inner peripheral surface surrounds the outer peripheral surface. The second inner peripheral surface extends along the outer peripheral surface. The first supply unit supplies a carbon nanotube raw material and chlorosulfonic acid into the first tube. The second supply unit supplies a solidification liquid to the inside of the second tube. The first tube has a first end. The first end portion is disposed inside the second tube.

Description

Technical Field

[0001] The present invention relates to an apparatus for manufacturing a carbon nanotube wire and a method for manufacturing a carbon nanotube wire. This application claims priority based on Japanese Patent Application No. 2022-196278, filed on December 8, 2022. All of the descriptions contained in the Japanese patent application are incorporated herein by reference. Background Art

[0002] Japanese Patent Application Publication No. 2011-502925 (Patent Document 1) describes a method for manufacturing a carbon nanotube article by removing chlorosulfonic acid from a carbon nanotube solution in chlorosulfonic acid.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2011-502925 Summary of the Invention

[0006] The apparatus for manufacturing a carbon nanotube wire according to the present invention includes a first tube, a second tube, a first supply unit, and a second supply unit. The first tube includes a first inner peripheral surface and an outer peripheral surface. The outer peripheral surface surrounds the first inner peripheral surface. The second tube includes a second inner peripheral surface. The second inner peripheral surface surrounds the outer peripheral surface. The second inner peripheral surface extends along the outer peripheral surface. The first supply unit supplies a carbon nanotube raw material and chlorosulfonic acid into the first tube. The second supply unit supplies a coagulating liquid into the second tube. The first tube includes a first end portion. The first end portion is disposed inside the second tube. Brief Description of the Drawings

[0007] Figure 1 is a front view showing the structure of the apparatus for manufacturing a carbon nanotube wire according to the first embodiment.

[0008] Figure 2 is showing Figure 1 an enlarged cross-sectional view of Region II.

[0009] Figure 3 is a cross-sectional view taken along line III-III Figure 2 shown.

[0010] Figure 4 is a cross-sectional view showing the region surrounded by the second inner peripheral surface.

[0011] Figure 5 is a flowchart schematically showing the method for manufacturing a carbon nanotube wire according to the first embodiment.

[0012] Figure 6 is a front view showing the process of forming a carbon nanotube wire.

[0013] Figure 7 is a schematic enlarged cross-sectional view of region VII which represents Figure 6 .

[0014] Figure 8 is a schematic view showing the configuration of a manufacturing apparatus for a carbon nanotube wire related to a second embodiment.

[0015] Figure 9 is a three-dimensional schematic view showing an evaluation method for the degree of orientation using polarized Raman analysis.

[0016] Figure 10 is a schematic view showing a Raman spectrum.

[0017] Figure 11 is a graph showing the relationship between the flow rate of the slurry in the examples and the degree of orientation of the carbon nanotube wire.

[0018] Figure 12 is a scanning electron microscope image of the carbon nanotube wire related to Sample 1.

[0019] Figure 13 is a scanning electron microscope image obtained by magnifying the surface of the carbon nanotube wire related to Sample 1.

[0020] Figure 14 is a scanning electron microscope image of the carbon nanotube wire related to Sample 4.

[0021] Figure 15 is a scanning electron microscope image obtained by magnifying the surface of the carbon nanotube wire related to Sample 4. DETAILED DESCRIPTION OF THE INVENTION

[0022] [Problems to be Solved by the Present Invention]

[0023] According to the manufacturing method described in Patent Document 1, the structure of the portion where the carbon nanotube solution and the coagulant converge is not clearly disclosed. Carbon nanotube blockages sometimes occur in the portion where the carbon nanotube solution and the coagulant converge. An object of the present invention is to provide a manufacturing apparatus for a carbon nanotube wire and a manufacturing method for a carbon nanotube wire that can suppress carbon nanotube blockages.

[0024] [Effects of the Present Invention]

[0025] According to the present invention, it is possible to provide a manufacturing apparatus for a carbon nanotube wire and a manufacturing method for a carbon nanotube wire that can suppress carbon nanotube blockages.

[0026] [Description of Embodiments of the Present Invention]

[0027] First, embodiments of the present invention will be listed and described.

[0028] (1) The manufacturing apparatus 100 for carbon nanotube wire according to the present invention includes a first tube 10, a second tube 20, a first supply unit 1, and a second supply unit 2. The first tube 10 includes a first inner peripheral surface 12 and an outer peripheral surface 11. The outer peripheral surface 11 surrounds the first inner peripheral surface 12. The second tube 20 includes a second inner peripheral surface 22. The second inner peripheral surface 22 surrounds the outer peripheral surface 11. The second inner peripheral surface 22 extends along the outer peripheral surface 11. The first supply unit 1 supplies a carbon nanotube raw material and chlorosulfonic acid into the inside of the first tube 10. The second supply unit 2 supplies a coagulating liquid 92 into the inside of the second tube 20. The first tube 10 includes a first end portion 13. The first end portion 13 is disposed inside the second tube 20.

[0029] Thus, before the slurry 94 and the coagulating liquid 92 converge, the flows of the slurry 94 and the coagulating liquid 92 are rectified along the direction in which the second inner peripheral surface 22 extends. Therefore, the carbon nanotube wire 200 is formed along the direction in which the second inner peripheral surface 22 extends, and the formed carbon nanotube wire 200 flows along the direction in which the second inner peripheral surface 22 extends. Thereby, winding of the carbon nanotube wire 200 can be suppressed. As a result, clogging of carbon nanotubes in the manufacturing apparatus 100 for carbon nanotube wire can be suppressed.

[0030] (2) Alternatively, in the manufacturing apparatus 100 for carbon nanotube wire according to (1) above, the coagulating liquid 92 contains acetone. The solubility of chlorosulfonic acid in acetone is high. Therefore, when the carbon nanotube raw material, chlorosulfonic acid, and the coagulating liquid 92 are mixed, coagulation of the carbon nanotube raw material can be promoted. As a result, the flow rate of the slurry can be increased. Therefore, the degree of orientation of the carbon nanotube wire 200 can be improved.

[0031] (3) Alternatively, the manufacturing apparatus 100 for carbon nanotube wire according to (1) or (2) above further includes a part that stirs while heating the carbon nanotube raw material and chlorosulfonic acid. Thereby, in the slurry 94, the carbon nanotube raw material can be more uniformly dispersed. Therefore, the degree of orientation of the carbon nanotube wire 200 can be improved.

[0032] (4) Alternatively, in the manufacturing apparatus 100 for carbon nanotube wire according to any one of (1) to (3) above, in a cross section perpendicular to the direction in which the second inner peripheral surface 22 extends and intersecting the first tube 10 and the second tube 20 respectively, when the area surrounded by the first inner peripheral surface 12 is defined as a first area and the area of the region surrounded by the second inner peripheral surface 22 is defined as a second area, the value obtained by dividing the first area by the second area is 0.0001 or more and 0.2 or less.

[0033] (5) Alternatively, in the manufacturing apparatus 100 for carbon nanotube wire according to any one of (1) to (4) above, the length of the portion of the first tube 10 disposed inside the second tube 20 is 0 mm or more and 300 mm or less. Thus, when the slurry 94 and the coagulating liquid 92 converge, the flows of the slurry 94 and the coagulating liquid 92 are further rectified along the direction in which the second inner peripheral surface 22 extends. As a result, clogging of carbon nanotubes can be further suppressed.

[0034] (6) In the manufacturing apparatus 100 for carbon nanotube wire according to any one of (1) to (5) above, the second tube 20 includes a second end portion 23. The second end portion 23 is disposed to face the second supply portion 2. The length between the first end portion 13 and the second end portion 23 in the direction in which the second inner peripheral surface 22 extends may also be 10 mm or more and 2000 mm or less.

[0035] (7) The method for manufacturing a carbon nanotube wire according to the present invention includes the following steps. Prepare the manufacturing apparatus 100 for carbon nanotube wire according to any one of (1) to (6) above. Mix the carbon nanotube raw material, chlorosulfonic acid, and the coagulating liquid 92 by supplying the carbon nanotube raw material and chlorosulfonic acid into the inside of the first tube 10 and supplying the coagulating liquid 92 into the inside of the second tube 20.

[0036] (8) Alternatively, in the method for manufacturing a carbon nanotube wire according to (7) above, in the step of mixing, the flow rate of the liquid flowing inside the first tube 10 is 0.001 cm 3 / min or more and 5 cm 3 / min or less.

[0037] (9) Alternatively, in the method for manufacturing a carbon nanotube wire according to (7) or (8) above, in the step of mixing, the flow rate of the liquid flowing inside the second tube 20 is 0.02 cm 3 / min or more and 100 cm 3 / min or less.

[0038] (10) Alternatively, in the method for manufacturing a carbon nanotube wire according to any one of (7) to (9) above, the carbon nanotube wire 200 formed in the step of mixing can be wound using a spool 7. The rotation speed of the spool 7 is 1 rpm or more and 1000 rpm or less.

[0039] (11) Alternatively, in the method for manufacturing a carbon nanotube wire according to any one of (7) to (10) above, before the step of mixing, prepare the slurry 94 by heating and stirring the carbon nanotube raw material and chlorosulfonic acid. The concentration of the carbon nanotube raw material in the slurry 94 is 0.01 wt% or more and 3 wt% or less.

[0040] [Details of the Embodiments of the Present Invention]

[0041] Next, the details of the embodiments of the present invention will be described based on the drawings. In addition, in the following drawings, the same or corresponding parts are denoted by the same reference numerals, and their descriptions will not be repeated.

[0042] (First Embodiment)

[0043] First, the configuration of the manufacturing apparatus 100 for carbon nanotube wire of the first embodiment will be described. Figure 1 It is a front view schematic diagram showing the configuration of the manufacturing apparatus 100 for carbon nanotube wire of the first embodiment.

[0044] As Figure 1 shown, the manufacturing apparatus 100 for carbon nanotube wire mainly includes a first supply unit 1, a first tube 10, a second supply unit 2, a second tube 20, a first connection unit 30, a second connection unit 40, a hot air gun 5, a first spool 7, a waste liquid container 6, a third tube 43, and a fourth tube 44. The manufacturing apparatus 100 for carbon nanotube wire is configured to form a carbon nanotube wire 200 by mixing a slurry 94 and a coagulating liquid 92. The slurry 94 contains a carbon nanotube raw material and chlorosulfonic acid. The coagulating liquid 92 contains, for example, acetone. The concentration of acetone in the coagulating liquid 92 is, for example, 99.5% by weight or more.

[0045] The first supply unit 1 is configured to supply the slurry 94 to the inside of the first tube 10. The first tube 10 forms a flow path for the slurry 94. A part of the first tube 10 is disposed inside the second tube 20. The inside of the second tube 20 includes a space surrounded by the end of the second tube 20. From another perspective, in the extending direction of the first tube 10, the ends of the first tube 10 and the second tube 20 may also be located at substantially the same position. The second supply unit 2 is configured to supply the coagulating liquid 92 to the inside of the second tube 20.

[0046] The first connection unit 30 connects the first tube 10 and the second tube 20. The second connection unit 40 connects the second tube 20, the third tube 43, and the fourth tube 44. The third tube 43 guides the formed carbon nanotube wire 200 to the first spool 7. The first spool 7 winds the formed carbon nanotube wire 200. The diameter of the first spool 7 is, for example, 20 mm or more and 200 mm or less. The diameter of the first spool 7 refers to the diameter of the part of the first spool 7 around which the carbon nanotube wire 200 is wound.

[0047] The hot air gun 5 dries the formed carbon nanotube wire 200. Specifically, as Figure 1As shown, the hot air gun 5 conveys hot air in the direction of the first arrow A1 between the third tube 43 and the first spool 7. The direction of the first arrow A1 may be perpendicular to the moving direction of the carbon nanotube wire 200. The fourth tube 44 forms a flow path connected to the inside of the waste liquid container 6. The waste liquid container 6 recovers the mixture of chlorosulfonic acid and the solidifying liquid 92.

[0048] The first supply unit 1 has a first container 61 and a first tube pump 51. The first container 61 is connected to the first tube 10. The first container 61 contains the slurry 94. The slurry 94 is a liquid in which carbon nanotube raw materials are dispersed in chlorosulfonic acid. The shape of the carbon nanotube raw materials is, for example, fibrous. The first container 61 may also be configured to be able to mix the carbon nanotube raw materials and chlorosulfonic acid to produce the slurry 94. Specifically, the first container 61 may be configured to stir while heating the carbon nanotube raw materials and chlorosulfonic acid. The first container 61 may also have a heating unit (not shown) and a stirring unit (not shown).

[0049] As Figure 1 shown, the first tube pump 51 is installed on the first tube 10. From another perspective, a part of the first tube 10 is disposed inside the first tube pump 51. The first tube pump 51 is configured to send out the liquid located inside the first tube 10 in the direction of the second arrow A2. The second arrow A2 is the direction from the first supply unit 1 towards the second tube 20. The first tube 10 is, for example, linear. The direction of the second arrow A2 is substantially parallel to the extending direction of the first tube 10.

[0050] The second supply unit 2 has a second container 62, a fifth tube 45, and a second tube pump 52. The second container 62 contains the solidifying liquid 92. The fifth tube 45 connects the inside of the second container 62 to the inside of the first connection part 30. The second tube pump 52 is installed on the fifth tube 45. From another perspective, a part of the fifth tube 45 is disposed inside the second tube pump 52. The second tube pump 52 is configured to send out the liquid located inside the fifth tube 45 in the direction of the third arrow A3. The third arrow A3 is the direction from the second supply unit 2 towards the second tube 20.

[0051] The first tube 10 includes a first outer peripheral surface 11, a first inner peripheral surface 12, a first end 13, and a third end 14. The first inner peripheral surface 12 faces the first outer peripheral surface 11. The first end 13 is disposed inside the second tube 20. The third end 14 faces the first end 13. The third end 14 is installed on the first container 61.

[0052] In the first tube 10, the point located at the outlet of the first tube pump 51 is the middle point 15. From another point of view, in the portion of the first tube 10 disposed between the first tube pump 51 and the second tube 20, the point closest to the first tube pump 51 is the middle point 15. In the direction in which the first inner peripheral surface 12 extends, the length between the middle point 15 and the first end 13 is the first length D1. The first length D1 is, for example, 500 mm or more and 10000 mm or less. The direction in which the first inner peripheral surface 12 extends refers to the direction from the third end 14 toward the first end 13 along the first inner peripheral surface 12.

[0053] The second tube 20 is, for example, linear. The second tube 20 includes a second outer peripheral surface 21, a second inner peripheral surface 22, a second end 23, and a fourth end 24. The second inner peripheral surface 22 is opposite to the second outer peripheral surface 21. The second inner peripheral surface 22 extends along the first outer peripheral surface 11. The fourth end 24 is mounted on the first connecting portion 30. In the direction in which the first inner peripheral surface 12 extends, the fourth end 24 is, for example, located between the first end 13 and the third end 14. In the direction in which the first inner peripheral surface 12 extends, the fourth end 24 may also be located at substantially the same position as the first end 13. The second end 23 is opposite to the fourth end 24. The second end 23 is opposite to the second supply portion 2. From another point of view, the liquid supplied from the second supply portion 2 reaches the second end 23 through the fourth end 24. The second end 23 is mounted on the second connecting portion 40.

[0054] The length between the first end 13 and the second end 23 in the direction in which the second inner circumferential surface 22 extends is the second length D2. The second length D2 is, for example, greater than 10 mm and less than 2000 mm. The lower limit of the second length D2 is not particularly limited, and for example, it may be greater than 50 mm, or greater than 100 mm. The upper limit of the second length D2 is not particularly limited, and for example, it may be less than 1500 mm, or less than 1000 mm. The direction in which the second inner circumferential surface 22 extends is the direction from the fourth end 24 toward the second end 23 along the second inner circumferential surface 22. The second length D2 may also be longer than the first length D1.

[0055] Figure 2 Yes means Figure 1 Schematic diagram of an enlarged cross section of region II. Figure 2 The cross section shown is a cross section parallel to the direction in which the first inner peripheral surface 12 extends and intersecting the first tube 10 and the second tube 20. Figure 2 As shown, the first connection portion 30 has a first portion 31 and a second portion 32. The first portion 31 surrounds the first tube 10. The first portion 31 is in contact with the first tube 10. The first portion 31 extends in a direction (radial direction) perpendicular to the direction in which the first inner peripheral surface 12 extends.

[0056] The second part 32 is connected to the first part 31. The second part 32 extends along the direction in which the first inner peripheral surface 12 extends. The second part 32 surrounds the first tube 10. The second part 32 is separated from the first tube 10. The second part 32 may also surround the fourth end portion 24 of the second tube 20. In the second outer peripheral surface 21, the second part 32 may also be in contact with the second tube 20. A through hole (not shown) is provided in the second part 32. The through hole extends in the radial direction. A fifth tube 45 is installed in the through hole. In other words, the inside of the fifth tube 45 is connected to the inside of the second part 32 via the through hole. On the other hand, no through hole extending in the radial direction is provided in the first tube 10 and the second tube 20 respectively.

[0057] The length of the portion of the first tube 10 disposed inside the second tube 20 is the third length D3. From another perspective, the third length D3 is the length between the fourth end portion 24 of the second tube 20 and the first end portion 13 of the first tube 10 in the direction in which the first inner peripheral surface 12 extends. The third length D3 is, for example, 0 mm or more and 300 mm or less. The lower limit of the third length D3 is not particularly limited. For example, it may be 5 mm or more or 10 mm or more. The upper limit of the third length D3 is not particularly limited. For example, it may be 200 mm or less or 150 mm or less.

[0058] Figure 3 is a schematic cross-sectional view along the Figure 2 III-III line. Figure 3 The cross-section shown is a cross-section perpendicular to the direction in which the first inner peripheral surface 12 extends and intersecting the first tube 10 and the second tube 20 respectively. As Figure 3 shown, the shape of the first tube 10 is annular. When observed from the direction in which the first inner peripheral surface 12 extends, the first inner peripheral surface 12 is, for example, circular. The first outer peripheral surface 11 surrounds the first inner peripheral surface 12. The shape of the second tube 20 is annular. When observed from the direction in which the first inner peripheral surface 12 extends, the second inner peripheral surface 22 is, for example, circular. The second inner peripheral surface 22 surrounds the first outer peripheral surface 11. The second inner peripheral surface 22 is separated from the first outer peripheral surface 11. The second outer peripheral surface 21 surrounds the second inner peripheral surface 22.

[0059] In Figure 3 the area represented by a plurality of dots indicates the area surrounded by the first inner peripheral surface 12. In a cross-section perpendicular to the direction in which the second inner peripheral surface 22 extends and intersecting the first tube 10 and the second tube 20 respectively, the area of the region surrounded by the first inner peripheral surface 12 is the first area. In other words, the first area is the area of the region represented by a plurality of dots in Figure 3 The first area is, for example, 0.008 mm 2 or more and 16 mm 2 or less.

[0060] Figure 4It is a schematic cross-sectional view showing the region surrounded by the second inner peripheral surface 22. Figure 4 The cross-section shown corresponds to Figure 3 the cross-section shown. In Figure 4 the region indicated by a plurality of dots represents the region surrounded by the second inner peripheral surface 22. In a cross-section perpendicular to the extending direction of the second inner peripheral surface 22 and intersecting the first tube 10 and the second tube 20 respectively, the area of the region surrounded by the second inner peripheral surface 22 is the second area. In other words, the second area is the area of the region indicated by a plurality of dots in Figure 4 The second area is, for example, 1 mm 2 or more and 80 mm 2 or less.

[0061] The value obtained by dividing the first area by the second area is, for example, 0.0001 or more and 0.2 or less. The lower limit of the value obtained by dividing the first area by the second area is not particularly limited. For example, it may be 0.001 or more, or may be 0.01 or more. The upper limit of the value obtained by dividing the first area by the second area is not particularly limited. For example, it may be 0.1 or less, or may be 0.05 or less.

[0062] (Manufacturing method of carbon nanotube wire)

[0063] Next, the manufacturing method of the carbon nanotube wire according to the first embodiment will be described. Figure 5 It is a flowchart schematically showing the manufacturing method of the carbon nanotube wire according to the first embodiment. As Figure 5 shown, the manufacturing method of the carbon nanotube wire mainly includes: a step (S10) of preparing a manufacturing apparatus 100 for the carbon nanotube wire; a step (S20) of preparing a slurry 94 by heating and stirring a carbon nanotube raw material and chlorosulfonic acid; and a step (S30) of forming a carbon nanotube wire 200 by mixing the carbon nanotube raw material, chlorosulfonic acid, and a coagulant 92.

[0064] First, the step (S10) of preparing the manufacturing apparatus 100 for the carbon nanotube wire is implemented. Prepare Figure 1 the manufacturing apparatus 100 for the carbon nanotube wire shown.

[0065] Next, the step (S20) of preparing the slurry 94 by heating and stirring the carbon nanotube raw material and chlorosulfonic acid is implemented. The carbon nanotube raw material and chlorosulfonic acid are put into the inside of the first container 61.

[0066] The first container 61 stirs while heating the carbon nanotube raw material and chlorosulfonic acid. In the step (S20) of preparing the slurry 94, the heating temperature of the carbon nanotube raw material and chlorosulfonic acid is, for example, 120 °C. The heating temperature can be, for example, 100 °C or higher and 150 °C or lower. When the heating temperature is too high, thermal decomposition of chlorosulfonic acid sometimes occurs, so the heating temperature is preferably within the above range.

[0067] The concentration of the carbon nanotube raw material in the slurry 94 is 0.01 wt% or more and 3 wt% or less. The concentration of the carbon nanotube raw material in the slurry 94 is a value obtained by dividing the weight of the carbon nanotube raw material by the sum of the weight of chlorosulfonic acid and the weight of the carbon nanotube raw material. The lower limit of the concentration of the carbon nanotube raw material in the slurry 94 is not particularly limited. For example, it can be 0.05 wt% or more, or 0.1 wt% or more. The upper limit of the concentration of the carbon nanotube raw material in the slurry 94 is not particularly limited. For example, it can be 1 wt% or less, or 0.5 wt% or less. Through the above, the slurry 94 is prepared.

[0068] Next, a step (S30) of forming the carbon nanotube wire 200 by mixing the carbon nanotube raw material, chlorosulfonic acid, and the coagulating liquid 92 is performed. Figure 6 is a front view schematic diagram showing the step (S30) of forming the carbon nanotube wire 200. In Figure 6 the area represented by a plurality of dots represents a liquid.

[0069] As Figure 6 shown, the slurry 94 is supplied from the first container 61 to the inside of the first tube 10 using the first tube pump 51. The slurry 94 flows in the direction of the second arrow A2. Thus, the carbon nanotube raw material contained in the slurry 94 is subjected to a shear force caused by the flow of the slurry 94. Therefore, the carbon nanotube raw material is oriented in such a way that the longitudinal direction of the carbon nanotube raw material is along the extending direction of the first inner peripheral surface 12.

[0070] In the step (S30) of forming the carbon nanotube wire 200, the flow rate of the slurry 94 flowing inside the first tube 10 is set as the first flow rate. The first flow rate is, for example, 0.001 cm 3 / min or more and 5 cm 3 / min or less. The lower limit of the first flow rate is not particularly limited. For example, it can be 0.005 cm 3 / min or more, or 0.009 cm 3 / min or more. The upper limit of the first flow rate is not particularly limited. For example, it can be 1 cm 3 / min or less, or 0.6 cm 3 / min or less.

[0071] Using the second tube pump 52, a solidifying liquid 92 is supplied from the second container 62 to the inside of the fifth tube 45. The solidifying liquid 92 flows along the third arrow A3. The solidifying liquid 92 flows into the inside of the second tube 20 through the fifth tube 45 and the first connection part 30.

[0072] The slurry 94 and the solidifying liquid 92 are mixed by converging inside the second tube 20. The chlorosulfonic acid contained in the slurry 94 dissolves into the solidifying liquid 92. Thereby, a mixed liquid 95 is generated. The mixed liquid 95 flows into the waste liquid container 6 through the second tube 20, the second connection part 40, and the fifth tube 45 respectively.

[0073] In the process (S30) of forming the carbon nanotube wire 200, the flow rate of the mixed liquid 95 flowing inside the second tube 20 is set as the second flow rate. The second flow rate is, for example, 0.02 cm 3 / min or more and 100 cm 3 / min or less. The lower limit of the second flow rate is not particularly limited. For example, it may be 0.1 cm 3 / min or more, or may be 0.5 cm 3 / min or more. The upper limit of the second flow rate is not particularly limited. For example, it may be 10 cm 3 / min or less, or may be 1 cm 3 / min or less. The first flow rate is less than the second flow rate. The value obtained by dividing the first flow rate by the second flow rate is, for example, 0.00001 or more and 0.05 or less.

[0074] The carbon nanotube raw material contained in the slurry 94 solidifies into a linear shape. Thereby, the carbon nanotube wire 200 is formed. The carbon nanotube wire 200 is wound around the first spool 7 through the second tube 20, the second connection part 40, and the third tube 43 respectively. Between the third tube 43 and the first spool 7, a hot air gun 5 is used to dry the carbon nanotube wire 200.

[0075] The first spool 7 winds the formed carbon nanotube wire 200 by rotating. From another perspective, a tension is applied to the carbon nanotube wire 200 by the first spool 7. In the process (S30) of forming the carbon nanotube wire 200, the rotation speed of the first spool 7 is 1 rpm or more and 1000 rpm or less. The lower limit of the rotation speed of the first spool 7 is not particularly limited. For example, it may be 5 rpm or more, or may be 10 rpm or more. The upper limit of the rotation speed of the first spool 7 is not particularly limited. For example, it may be 500 rpm or less, or may be 100 rpm or less.

[0076] Figure 7 is a schematic enlarged cross-sectional view of region VII showing Figure 6 . Figure 7 The cross-section shown corresponds to the cross-section shown in Figure 2 . As shown in Figure 6 andFigure 7 As shown, the slurry 94 flows along the second arrow A2. The slurry 94 flows into the interior of the second tube 20 through the first end portion 13. The solidifying liquid 92 surrounds the first tube 10 inside the first connection portion 30. The solidifying liquid 92 flows into the second tube 20 from the first connection portion 30 through the fourth end portion 24. The solidifying liquid 92 flows along the fourth arrow A4. The direction of the fourth arrow A4 is the direction in which the second inner peripheral surface 22 extends. The flow direction of the solidifying liquid 92 may also be substantially parallel to the flow direction of the slurry 94.

[0077] As Figure 7 shown, between the fourth end portion 24 and the first end portion 13, the slurry 94 and the solidifying liquid 92 are separated by the first tube 10. Between the first end portion 13 and the second end portion 23 (refer to Figure 6 ), the slurry 94 and the solidifying liquid 92 converge with each other. The slurry 94 flowing out from the first end portion 13 mixes with the solidifying liquid 92 near the first end portion 13. In the downstream region of the first end portion 13, the carbon nanotube raw material is further oriented to form the carbon nanotube wire 200.

[0078] Thus, the carbon nanotube wire 200 is manufactured. The length of one carbon nanotube wire 200 is, for example, 100 m or more and 100,000 m or less. The length of one carbon nanotube wire 200 can be, for example, 1000 m or more. The diameter of the carbon nanotube wire 200 is, for example, 10 μm or more and 100 μm or less.

[0079] (Second Embodiment)

[0080] Next, the configuration of the manufacturing apparatus 100 for the carbon nanotube wire according to the second embodiment will be described. The manufacturing apparatus 100 for the carbon nanotube wire according to the second embodiment is mainly different from the manufacturing apparatus 100 for the carbon nanotube wire according to the first embodiment in that it has a second spool 8 for supplying the linear carbon nanotube raw material 91, and the other aspects are substantially the same as those of the manufacturing apparatus 100 for the carbon nanotube wire according to the first embodiment. Hereinafter, the description will be centered on the points different from the configuration of the manufacturing apparatus 100 for the carbon nanotube wire according to the first embodiment.

[0081] Figure 8 is a schematic diagram showing the configuration of the manufacturing apparatus 100 for the carbon nanotube wire according to the second embodiment. As Figure 8 shown, the first supply unit 1 may also include a second spool 8, a third container 63, a third tube pump 53, and a sixth tube 46.

[0082] The carbon nanotube raw material 91 is wound around the second spool 8. The shape of the carbon nanotube raw material 91 is linear. The carbon nanotube raw material 91 is synthesized by, for example, the honeycomb method. The first tube pump 51 is configured to supply the carbon nanotube raw material 91 from the second spool 8 into the interior of the first tube 10.

[0083] The third container 63 contains chlorosulfonic acid 93. The sixth tube 46 forms a flow path for the chlorosulfonic acid 93. The sixth tube 46 connects the interior of the third container 63 to the interior of the first tube 10. The sixth tube 46 is connected to the first tube 10 at a portion of the first tube 10 between the first end 13 and the midpoint 15.

[0084] The third tube pump 53 is installed in the sixth tube 46. The third tube pump 53 is configured to supply the chlorosulfonic acid 93 along the fifth arrow A5 to the first tube 10. The fifth arrow A5 is the direction from the third container 63 toward the first tube 10.

[0085] As Figure 8 shown, the manufacturing apparatus 100 for carbon nanotube wire may have a fourth tube pump 54. The fourth tube pump 54 is installed in the second tube 20. In the direction in which the second inner peripheral surface 22 extends, the fourth tube pump 54 is disposed between the first end 13 and the second end 23. The fourth tube pump 54 is configured to send out the carbon nanotube wire 200 and the mixed liquid 95 (refer to Figure 6 ). The sixth arrow A6 is the direction from the fourth end 24 toward the second end 23. The direction of the sixth arrow A6 is substantially parallel to the direction in which the second tube 20 extends. The direction of the sixth arrow A6 may also be substantially parallel to the fourth arrow A4 (refer to Figure 7 ).

[0086] Inside the first tube 10, the carbon nanotube raw material 91 is immersed in the chlorosulfonic acid 93. Thereby, the carbon nanotube raw material 91 is unraveled. The loose carbon nanotube raw material 91 is subjected to a shear force caused by the flow of the chlorosulfonic acid 93. Thereby, the carbon nanotube raw material 91 is oriented.

[0087] The slurry formed by mixing the chlorosulfonic acid 93 and the carbon nanotube raw material 91 is transported to the second tube 20. The slurry converges with the coagulating liquid 92 inside the second tube 20. Thereby, the carbon nanotube raw material 91 solidifies. As a result, the carbon nanotube wire 200 is formed.

[0088] Next, the operation and effects of the manufacturing apparatus 100 for carbon nanotube wire and the manufacturing method for carbon nanotube wire according to the present embodiment will be described.

[0089] When the flow direction of the slurry 94 is orthogonal to the flow direction of the coagulating liquid 92 at the time of the confluence of the slurry 94 and the coagulating liquid 92, the carbon nanotube wire 200 formed by the coagulation of the carbon nanotubes flows in a direction perpendicular to the extending direction of the carbon nanotube wire 200 by the flow of the coagulating liquid 92. Therefore, the shape of the carbon nanotube wire 200 is deformed and the carbon nanotube wire 200 is wound. As a result, clogging of the carbon nanotubes occurs inside the tube.

[0090] The manufacturing apparatus 100 for carbon nanotube wires according to the present embodiment includes a first tube 10 and a second tube 20. The second inner peripheral surface 22 of the second tube 20 extends along the first outer peripheral surface 11 of the first tube 10. The first end portion 13 of the first tube 10 is disposed inside the second tube 20. Therefore, before the slurry 94 and the coagulating liquid 92 converge, the flows of the slurry 94 and the coagulating liquid 92 are rectified along the direction in which the second inner peripheral surface 22 extends. Therefore, the carbon nanotube wire 200 is formed in the direction in which the second inner peripheral surface 22 extends, and the formed carbon nanotube wire 200 flows in the direction in which the second inner peripheral surface 22 extends. As a result, winding of the carbon nanotube wire 200 can be suppressed. As a result, clogging of the carbon nanotubes in the manufacturing apparatus 100 for carbon nanotube wires can be suppressed.

[0091] In the manufacturing apparatus 100 for carbon nanotube wires according to the present embodiment, the coagulating liquid 92 contains acetone. The solubility of chlorosulfonic acid in acetone is high. Therefore, when the carbon nanotube raw material, chlorosulfonic acid, and the coagulating liquid 92 are mixed, coagulation of the carbon nanotube raw material can be promoted. As a result, the flow rate of the slurry can be increased. Therefore, the degree of orientation of the carbon nanotube wire 200 can be increased.

[0092] The manufacturing apparatus 100 for carbon nanotube wires according to the present invention includes a part that stirs while heating the carbon nanotube raw material and chlorosulfonic acid. Therefore, in the slurry 94, the carbon nanotube raw material can be more uniformly dispersed. As a result, the degree of orientation of the carbon nanotube wire 200 can be increased.

[0093] In the manufacturing apparatus 100 for carbon nanotube wires according to the present invention, the length (third length D3) of the part of the first tube 10 disposed inside the second tube 20 is 0 mm or more. Therefore, when the slurry 94 and the coagulating liquid 92 converge, the flows of the slurry 94 and the coagulating liquid 92 are further rectified along the direction in which the second inner peripheral surface 22 extends. As a result, clogging of the carbon nanotubes can be further suppressed.

[0094] Example 1

[0095] (Sample preparation)

[0096] First, carbon nanotube wires 200 related to Samples 1 to 4 are prepared. The carbon nanotube wires 200 related to Samples 1 to 4 are examples.

[0097] The carbon nanotube wire materials 200 related to Samples 1 to 4 are fabricated using the above-described manufacturing method of carbon nanotube wire materials. In the fabrication of the carbon nanotube wire material 200 related to Sample 1, the length (second length D2) between the first end portion 13 and the second end portion 23 in the extending direction of the second inner peripheral surface 22 is set to 1000 mm. The length (third length D3) of the portion of the first tube 10 disposed inside the second tube 20 is set to 150 mm. The concentration of the carbon nanotube raw material in the slurry 94 is set to 1 wt%. The coagulating liquid 92 is set to acetone. The flow rate of the coagulating liquid 92 is set to 10 cm 3 / min.

[0098] In the fabrication of the carbon nanotube wire material 200 related to Sample 1, the flow rate of the slurry 94 is set to 0.01 cm 3 / min. In the fabrication of the carbon nanotube wire material 200 related to Sample 2, the flow rate of the slurry 94 is set to 0.08 cm 3 / min. In the fabrication of the carbon nanotube wire material 200 related to Sample 3, the flow rate of the slurry 94 is set to 0.15 cm 3 / min. In the fabrication of the carbon nanotube wire material 200 related to Sample 4, the flow rate of the slurry 94 is set to 0.5 cm 3 / min.

[0099] (Evaluation Method 1)

[0100] Next, using polarized Raman analysis, the degree of orientation of the carbon nanotube wire materials 200 related to Samples 1 to 4 is evaluated. Figure 9 is a three-dimensional schematic diagram showing the evaluation method of the degree of orientation using polarized Raman analysis. As Figure 9 shown, the carbon nanotube wire material 200 is disposed on the specimen stage 98. The extending direction of the carbon nanotube wire material 200 is set as the first direction 101. The direction perpendicular to the first direction 101 and along the specimen stage 98 is set as the second direction 102.

[0101] The carbon nanotube wire material 200 is irradiated with polarized laser 99, and the intensity of the Raman scattered light from the carbon nanotube wire material 200 is measured to obtain a Raman spectrum. The laser 99 is irradiated along a direction perpendicular to the first direction 101 and the second direction 102, respectively. The excitation wavelength of the laser 99 is set to 532 nm.

[0102] Figure 10 is a schematic diagram showing the Raman spectrum. In Figure 10 it, the horizontal axis represents the Raman shift. The Raman shift is a value obtained by subtracting the vibration number of the incident laser 99 from the vibration number of the measured Raman scattered light. The vertical axis represents the intensity of the Raman scattered light. In Figure 10In this case, the first spectrum G1 represents the Raman spectrum when the polarization direction of the laser 99 is set to the first direction 101. The second spectrum G2 represents the Raman spectrum when the polarization direction of the laser 99 is set to the second direction 102.

[0103] The peak value of the intensity is calculated from the obtained Raman spectrum. The peak value in the first spectrum G1 is set as the first value IP. The peak value in the second spectrum G2 is set as the second value IV. The more the carbon nanotube wire 200 is oriented in the first direction 101, the larger the first value IP is, and the smaller the second value IV is. The value obtained by dividing the first value IP by the second value IV (IP / IV) is used as an evaluation index for the degree of orientation of the carbon nanotube wire 200.

[0104] (Evaluation result 1)

[0105] Figure 11 is a graph showing the relationship between the flow rate of the slurry 94 in the examples and the degree of orientation of the carbon nanotube wire 200. In Figure 11 the horizontal axis represents the flow rate of the slurry 94. The vertical axis represents IP / IV. Figure 11 The first plotted point P1 shown represents the measurement result of the carbon nanotube wire 200 related to sample 1. The second plotted point P2 represents the measurement result of the carbon nanotube wire 200 related to sample 2. The third plotted point P3 represents the measurement result of the carbon nanotube wire 200 related to sample 3. The fourth plotted point P4 represents the measurement result of the carbon nanotube wire 200 related to sample 4.

[0106] As Figure 11 shown, the IP / IV of the carbon nanotube wire 200 related to sample 1 is 3 or more and 4 or less. The IP / IV of the carbon nanotube wire 200 related to sample 2 is 4 or more and 5 or less. The IP / IV of the carbon nanotube wire 200 related to sample 3 is 5 or more and 6 or less. The IP / IV of the carbon nanotube wire 200 related to sample 4 is 9 or more and 11 or less.

[0107] Based on the above results, as Figure 11 shown, it can be confirmed that as the flow rate of the slurry 94 increases, IP / IV increases. It can be confirmed that in the range where the flow rate of the slurry 94 is 0.01 cm 3 / min or more and 0.5 cm 3 / min or less, the relationship between the flow rate of the slurry 94 and IP / IV can be approximated as linear.

[0108] (Evaluation method 2)

[0109] The carbon nanotube wires 200 related to samples 1 and 4 are observed using a scanning electron microscope (SEM: Scanning Electron Microscope).

[0110] (Evaluation result 2)

[0111] Figure 12 It is a scanning electron microscope image of the carbon nanotube wire 200 related to Sample 1. Figure 13 It is a scanning electron microscope image of the surface of the carbon nanotube wire 200 related to Sample 1 magnified. Figure 14 It is a scanning electron microscope image of the carbon nanotube wire 200 related to Sample 4. Figure 15 It is a scanning electron microscope image of the surface of the carbon nanotube wire 200 related to Sample 4 magnified.

[0112] As Figure 12 and Figure 13 shown, the direction in which the fibers constituting the carbon nanotube wire 200 related to Sample 1 extend is inclined with respect to the direction (the first direction 101) in which the carbon nanotube wire 200 extends. On the other hand, as Figure 14 and Figure 15 shown, the direction in which the fibers constituting the carbon nanotube wire 200 related to Sample 4 extend is along the first direction 101.

[0113] As Figure 12 and Figure 14 shown, compared with the shape of the surface of the carbon nanotube wire 200 related to Sample 1, the unevenness of the shape of the surface of the carbon nanotube wire 200 related to Sample 4 is small.

[0114] From the above results, it can be confirmed that by increasing the flow rate of the slurry 94, the unevenness of the shape of the surface of the carbon nanotube wire 200 becomes smaller, and the degree of orientation of the carbon nanotube wire 200 is improved.

[0115] Example 2

[0116] (Sample preparation)

[0117] First, carbon nanotube wires 200 of Samples 5 to 7 are prepared. The carbon nanotube wires 200 related to Samples 5 and 6 are comparative examples. The carbon nanotube wire 200 related to Sample 7 is an example. The carbon nanotube wires 200 related to Samples 5 to 7 are produced using the above manufacturing method of the carbon nanotube wire 200.

[0118] In the production of the carbon nanotube wire 200 related to Sample 5, the coagulating liquid 92 is chloroform. In the production of the carbon nanotube wire 200 related to Sample 6, the coagulating liquid 92 is water. In the production of the carbon nanotube wire 200 related to Sample 7, the coagulating liquid 92 is acetone.

[0119] (Evaluation method)

[0120] In the production of the carbon nanotube wire 200 related to Samples 5 to 7, the solubility of chlorosulfonic acid in the coagulating liquid 92 was confirmed. Specifically, when increasing the flow rate of the slurry 94, it was confirmed whether the carbon nanotube raw material could solidify into a linear shape. As the solubility of chlorosulfonic acid in the coagulating liquid 92 increased, the flow rate of the slurry 94 in which the carbon nanotube raw material could solidify into a linear shape increased. The solubility of the carbon nanotube raw material in the coagulating liquid 92 was confirmed. Between the coagulating liquid 92 and the slurry 94, it was visually confirmed whether there was a chemical reaction that affected the production of the carbon nanotube wire 200.

[0121] (Evaluation results)

[0122] [Table 1]

[0123]

[0124] Table 1 shows the solubility of chlorosulfonic acid (CSA) and the carbon nanotube raw material (CNT) in the coagulating liquid 92 respectively, and the presence or absence of a chemical reaction that affects the production of the carbon nanotube wire 200 in the production of the carbon nanotube wire 200 related to Samples 5 to 7.

[0125] In the column of the solubility of CSA in Table 1, A indicates that chlorosulfonic acid dissolves quickly in the coagulating liquid. B indicates that chlorosulfonic acid dissolves slowly in the coagulating liquid. In the column of the solubility of CNT in Table 1, A indicates that no dissolution of the carbon nanotube raw material in the coagulating liquid was confirmed. In the column of the chemical reaction in Table 1, A indicates that no chemical reaction that affects the production of the carbon nanotube wire 200 was confirmed. B indicates that a chemical reaction that affects the production of the carbon nanotube wire 200 was confirmed.

[0126] As shown in Table 1, in Sample 6, a chemical reaction between chlorosulfonic acid and the coagulating liquid was confirmed. Specifically, chlorosulfonic acid reacted violently with water and generated heat. In Sample 7, a chemical reaction in which the mixed liquid 95 changed color when chlorosulfonic acid was mixed with the coagulating liquid was confirmed, but no effect on the production of the carbon nanotube wire 200 was confirmed.

[0127] From the above results, it can be confirmed that in the manufacturing method of the carbon nanotube wire 200, it is preferable to use acetone as the coagulating liquid 92.

[0128] The embodiments and examples of the present invention should be considered illustrative in all respects and not restrictive. The scope of the present invention is not represented by the above embodiments, but by the claims, including meanings equivalent to the claims and all modifications within the scope.

[0129] Explanation of reference numerals

[0130] 1: First supply unit; 2: Second supply unit; 5: Hot air gun; 6: Waste liquid container; 7: First spool; 8: Second spool; 10: First tube; 11: First outer peripheral surface; 12: First inner peripheral surface; 13: First end; 14: Third end; 15: Intermediate point; 20: Second tube; 21: Second outer peripheral surface; 22: Second inner peripheral surface; 23: Second end; 24: Fourth end; 30: First connection part; 31: First part; 32: Second part; 40: Second connection part; 43: Third tube; 44: Fourth tube; 45: Fifth tube; 46: Sixth tube; 51: First tube pump; 52: Second tube pump; 53: Third tube pump; 54: Fourth tube pump; 61: First container; 62: Second container; 63: Third container; 91: Carbon nanotube raw material; 92: Solidifying liquid; 93: Chlorosulfonic acid; 94: Slurry; 95: Mixed liquid; 98: Specimen stage; 99: Laser; 100: Manufacturing device; 101: First direction; 102: Second direction; 200: Carbon nanotube wire; A1: First arrow;

[0131] A2: Second arrow; A3: Third arrow; A4: Fourth arrow; A5: Fifth arrow; A6: Sixth arrow; D1: First length; D2: Second length; D3: Third length; G1: First spectrum; G2: Second spectrum; IP: First value; IV: Second value; P1: First plotting point; P2: Second plotting point; P3: Third plotting point; P4: Fourth plotting point.

Claims

1. A manufacturing apparatus for carbon nanotube wire, wherein, the manufacturing apparatus for carbon nanotube wire comprises: a first tube, including a first inner peripheral surface and an outer peripheral surface surrounding the first inner peripheral surface; a second tube, including a second inner peripheral surface surrounding the outer peripheral surface and extending along the outer peripheral surface; a first supply part for supplying carbon nanotube raw material and chlorosulfonic acid into the interior of the first tube; and a second supply part for supplying a coagulating liquid into the interior of the second tube, wherein the first tube includes a first end portion disposed inside the second tube.

2. The manufacturing apparatus of the carbon nanotube wire according to claim 1, wherein, The coagulating liquid contains acetone.

3. The manufacturing apparatus for carbon nanotube wire according to claim 1 or 2, wherein, The manufacturing apparatus for carbon nanotube wire further comprises a part for heating and stirring the carbon nanotube raw material and the chlorosulfonic acid.

4. The manufacturing apparatus for carbon nanotube wire according to any one of claims 1 to 3, wherein, in a cross-section perpendicular to the direction in which the second inner peripheral surface extends and intersecting the first tube and the second tube respectively, when the area of the region surrounded by the first inner peripheral surface is set as a first area and the area of the region surrounded by the second inner peripheral surface is set as a second area, the value obtained by dividing the first area by the second area is 0.0001 or more and 0.2 or less.

5. The manufacturing apparatus of the carbon nanotube wire according to any one of claims 1 to 4, wherein, The length of the portion of the first tube disposed inside the second tube is 0 mm or more and 300 mm or less.

6. The manufacturing apparatus for carbon nanotube wire according to any one of claims 1 to 5, wherein, the second tube includes a second end portion arranged to face the second supply part, and the length between the first end portion and the second end portion in the direction in which the second inner peripheral surface extends is 10 mm or more and 2000 mm or less.

7. A manufacturing method for carbon nanotube wire, wherein, the manufacturing method for carbon nanotube wire comprises: a step of preparing the manufacturing apparatus for carbon nanotube wire according to any one of claims 1 to 6; and a step of mixing the carbon nanotube raw material, the chlorosulfonic acid and the coagulating liquid by supplying the carbon nanotube raw material and the chlorosulfonic acid into the interior of the first tube and supplying the coagulating liquid into the interior of the second tube.

8. The manufacturing method of the carbon nanotube wire according to claim 7, wherein, In the process of performing the mixing, the flow rate of the liquid flowing inside the first tube is 0.001 cm 3 / min or more and 5 cm 3 / min or less.

9. The manufacturing method of the carbon nanotube wire according to claim 7 or 8, wherein, In the process of performing the mixing, the flow rate of the liquid flowing inside the second pipe is 0.02 cm 3 / min or more and 100 cm 3 / min or less.

10. The manufacturing method for carbon nanotube wire according to any one of claims 7 to 9, wherein, the carbon nanotube wire formed in the step of performing the mixing is wound using a spool, and the rotational speed of the spool is 1 rpm or more and 1000 rpm or less.

11. The manufacturing method for carbon nanotube wire according to any one of claims 7 to 10, wherein, before the step of performing the mixing, there is a step of preparing a slurry by heating and stirring the carbon nanotube raw material and the chlorosulfonic acid, and the concentration of the carbon nanotube raw material in the slurry is 0.01 wt% or more and 3 wt% or less.

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