JP6675610B2 - Open substrate - Google Patents

Description

  The present invention relates to an aperture substrate having at least a part of its inner surface as a growth surface of a CNT forest.

  In the present specification, a CNT forest is a composite structure of a plurality of carbon nanotubes (also referred to as “CNT” in the present specification) (hereinafter, the individual shape of CNT that gives such a composite structure is referred to as a “primary structure”, The composite structure is also a kind of “secondary structure”, in which a plurality of CNTs are fixed in at least a part of the major axis direction in a certain direction (as a specific example, one method of the surface provided on the substrate). A direction substantially parallel to the line). The length (height) of the CNT forest grown from the growth base surface in the direction parallel to the normal line of the growth base surface in a state of being attached to the growth base surface is referred to as “growth height”. When the secondary structure of the CNT forest is formed on a substrate consisting of only one plane, a plurality of CNTs are arranged in a certain direction at least in part in the major axis direction. On the other hand, when formed on a substrate having a plurality of planes or curved surfaces, since the normals of the surfaces constituting the substrate are non-parallel, the straight lines extending the long axis of the CNT intersect. They are arranged in a non-parallel, not fixed direction.

  In this specification, a part of CNTs in the CNT forest is pulled away from the CNT forest, and a plurality of CNTs are continuously extracted from the CNT forest. A structure having a structure in which a plurality of CNTs are entangled with each other is formed as a "CNT entangled body". In the present specification, “capable of spinning” means that the spinning length (length in the spinning direction) can be 1 cm or more.

  Since CNT has a specific structure of having an outer surface made of graphene, application in various fields as a functional material and a structural material is expected. Specifically, CNTs have high mechanical strength, are light, have good electric conduction properties, have good thermal properties such as heat resistance and thermal conductivity, have high chemical corrosion resistance, and have good field electron emission properties. It has such excellent characteristics. Therefore, applications of CNTs include lightweight high-strength wires, scanning probe microscope (SPM) probes, field emission display (FED) cold cathodes, conductive resins, high-strength resins, corrosion-resistant resins, abrasion-resistant resins, Highly lubricating resins, electrodes for secondary batteries and fuel cells, interlayer wiring materials for LSIs, biosensors, and the like have been considered.

  As one of the methods for producing CNTs, Patent Document 1 discloses that a solid metal catalyst layer is previously formed on a surface of a substrate by means of sputtering or the like by depositing a thin film of a metal-based material, and the like. A method of disposing a substrate having a metal catalyst layer in a reaction furnace, forming catalyst particles serving as growth nuclei on the substrate from the metal catalyst layer, and supplying a hydrocarbon gas to the reaction furnace to form a CNT forest on the substrate. Is disclosed. Hereinafter, a solid phase catalyst particle as a growth nucleus is formed on a substrate as described above, and a hydrocarbon-based material is supplied to a reactor provided with a substrate having the solid phase catalyst particle to prepare a CNT forest. Is referred to as a solid phase catalytic method.

  As a method for producing a CNT forest with high efficiency by a solid phase catalytic method, Patent Document 2 discloses a method in which a raw material gas containing carbon and no oxygen, a catalyst activator containing oxygen, and an atmosphere gas are mixed with a predetermined gas. There is disclosed a method in which the catalyst is supplied while satisfying the conditions and is brought into contact with a solid catalyst layer.

  A method for producing a CNT forest by a method different from the above solid phase catalysis method is also disclosed. That is, Patent Literature 3 discloses a method in which iron chloride is sublimated, a catalyst serving as a growth nucleus is formed on a substrate using this as a precursor, and a CNT forest is formed using the catalyst. This method is essentially different from the techniques disclosed in Patent Documents 1 and 2 in that a substance containing a halogen and in a gaseous state is used as a catalyst precursor and a catalyst is formed using this substance. ing. In this specification, the method for producing a CNT forest disclosed in Patent Document 3 is also referred to as a gas phase catalytic method.

JP 2004-107196 A Patent No. 4803687 JP 2009-196873 A

  In any of the solid-phase catalysis method and the gas-phase catalysis method, CNT entangled bodies having various shapes are manufactured by spinning a spinning source member provided with the obtained CNT forest. It is desired to improve the ease of production of the CNT entangled body, that is, the spinnability. However, because the CNT forest is a relatively new material and the CNT entangled body can take various shapes, etc. It is not yet clear what kind of CNT forest has excellent spinnability.

As a result of investigations by the present inventors to solve the above-described problems, the present inventors have found that a configuration including a spinning-possible portion at an end of a CNT forest formed with the inner surface of an open substrate having an internal space as a growth base surface, New knowledge has been obtained that the spinnability of CNT Forest may be improved. However, there is a problem that it is difficult to clean the open substrate having the CNT forest formed on the inner surface thereof after spinning the CNT forest.
An object of the present invention is to provide an open substrate that can be easily cleaned after use.

The present invention provided to solve the above problems is as follows.
[1] An open substrate that has an internal space that communicates with the outside through an open portion, has at least a part of the inner surface as a growth base surface of a CNT forest, and is used for spinning for continuously drawing a plurality of CNTs from the CNT forest. there are, assembly der where several components assembled divisible is, by dividing a plurality of said component, open board wherein at least a portion of said inner surface is exposed.

[2] The aperture substrate according to the above [1], wherein the growth base surface includes a region surrounding the opening on the inner surface.

[3] The apertured substrate according to the above [1] or [2], wherein the apertured substrate has at least two of the open portions.

[4] The aperture substrate according to the above [3], wherein the aperture substrate is cylindrical.

[5] The apertured substrate according to the above [4], wherein the open portions are formed at both ends of the internal space.

[6] The aperture substrate according to the above [5], wherein the aperture substrate has a cylindrical shape.

[7] The aperture substrate according to any one of [1] to [6] , wherein at least one of the open portions is formed by assembling two or more of the plurality of components.

[8] The apertured substrate according to the above [7] , wherein the plurality of components have the same shape.

[9] The apertured substrate according to the above [7] , wherein the plurality of parts include those having different shapes.

[10] The aperture substrate according to any one of [1] to [9] , further including a fixing component for fixing an assembled state of the plurality of components.

[11] The open substrate according to [10], wherein the fixed component is a cylindrical open substrate, and the fixed component restrains a plurality of the components from an outer surface side of the open substrate to form the assembly.

[12] The aperture substrate according to any one of [1] to [11] , wherein positions of the plurality of components in the assembly are determined by a fitting structure of the adjacent components.

[13] The aperture substrate according to [12] , wherein the fitting structure comprises a fitting structure of a convex portion and a concave portion of the adjacent component.

  ADVANTAGE OF THE INVENTION Since the opening board | substrate which concerns on this invention is set as the assembly which assembled | attached the several part so that division | segmentation was possible, washing | cleaning of an inner surface after use becomes easy and it can be set as the thing excellent in handleability.

It is a schematic diagram which shows roughly the structure of the cylindrical opening board | substrate which the CNT forest which concerns on embodiment of this invention was formed in the inner surface, (a) is the perspective view which looked at the opening board from diagonal lateral direction, (B) is a front view as viewed from the open portion side, and (c) is a cross-sectional view as viewed from the side of the apertured substrate in the cross section taken along the line AA ′ of (a). It is an image which shows an example of CNT which constitutes a CNT forest manufactured by a manufacturing method concerning one embodiment of the present invention. It is a graph which shows an example of the outside diameter distribution of CNT which comprises the CNT forest manufactured by the manufacturing method concerning one embodiment of the present invention. FIGS. 2A and 2B are schematic diagrams schematically illustrating a structure of an opening substrate different from that of FIG. 1, wherein FIG. 1A is a perspective view of a spindle hemispherical opening substrate viewed from an oblique lateral direction, and FIG. It is the perspective view which looked at the opening board | substrate from diagonal horizontal direction, (c) is the perspective view which looked at the cylindrical substrate different from FIG. 1 from diagonal horizontal direction. FIG. 3 is a perspective view of a disassembled cylindrical open substrate formed by combining two semi-cylinders having the same shape according to the embodiment of the present invention, as viewed obliquely from above. It is the perspective view which looked at the state where the dividable opening board concerning other embodiments was disassembled from diagonally upward. FIG. 6 is a perspective view of a state in which the open board of FIG. 5 is assembled and fixed by fixing components when viewed obliquely from above. It is the perspective view which looked at the state where the dividable opening board concerning other embodiments was disassembled from diagonally upward. It is the perspective view which looked at the state where the dividable opening board concerning other embodiments was disassembled from diagonally upward. It is the perspective view which looked at the state where the dividable opening board concerning other embodiments was disassembled from diagonally upward. It is a figure showing roughly composition of a manufacturing device used for a manufacturing method of a CNT forest concerning one embodiment of the present invention. 5 is a flowchart illustrating a method for manufacturing a CNT forest according to an embodiment of the present invention. It is an image which shows the state which spins the CNT forest manufactured by the manufacturing method which concerns on one Embodiment of this invention, and manufactures a CNT entangled body. It is the image which expanded a part of CNT entangled body obtained from the CNT forest manufactured by the manufacturing method concerning one embodiment of the present invention. FIG. 1C schematically shows a mode in which CNTs are spun from a CNT forest formed on a cylindrical opening substrate shown in FIG. 1C, FIG. 1A is a cross-sectional view showing an initial stage, and FIG. FIG. 4 is a cross-sectional view showing a stage where spinning has progressed. 5 is a flowchart illustrating a method for manufacturing a linear structure according to an embodiment of the present invention. FIG. 1C schematically shows a mode in which CNTs are spun from a CNT forest formed on a cylindrical opening substrate shown in FIG. 1C and focused, and FIG. 1A is a cross-sectional view showing an initial stage. (B) is a cross-sectional view showing a stage in which spinning has proceeded. 1 (a) to 1 (c) schematically show a mode in which CNTs are spun from a CNT forest formed on a cylindrical opening substrate, (a) is a perspective view, and (b) is a perspective view. It is a front view, and (c) is a sectional view which looked at a section of an AA 'arrow direction of (a) from the side of an opening board. 1 is a flowchart illustrating a method for manufacturing a composite according to an embodiment of the present invention. 3 is a photograph as a drawing substitute of a CNT forest and a spun structure manufactured by the manufacturing method according to Example 1. It is a mimetic diagram showing typically the conventional method of converging CNT drawn out from the flat board in which CNT was formed by twisting.

Hereinafter, embodiments of the present invention will be described.
1. CNT Forest FIG. 1 is a schematic view schematically showing a structure of a cylindrical open substrate in which a CNT forest according to one embodiment of the present invention is formed, and FIG. It is the perspective view seen, (b) is the front view seen from the open part side, (c) is the sectional view which looked at the section of the direction of AA 'of (a) from the side of the opening board. is there.

  As shown in FIGS. 1A to 1C, an example of the CNT forest according to the present embodiment is configured such that an inner surface 43 of an open substrate 40 having an inner space 42 communicating with the outside through an opening 41 is formed on a growth base surface 44. The CNT forest 45 has a spinning-possible portion 47 at an end 46 on the open portion 41 side.

  As shown in FIG. 2, one example of the CNT forest includes a portion having a structure in which a plurality of CNTs are arranged so as to be oriented in a certain direction. When the diameters of a plurality of CNTs in this portion are measured and their distributions are obtained, the diameters of the CNTs are mostly in the range of 20 to 50 nm as shown in FIG.

  In this specification, the “spinnable portion” refers to a portion of the CNT forest having a spinnable configuration. By forming CNTs grown at a density within the range of 1012 / m2 or more and 1012 / m2 or less from the growth base surface, the CNT forest can be spun out of the CNTs, so that the CNT forest can be spun. it can.

  As shown in FIG. 1B, the CNT forest 45 according to the present embodiment has a configuration formed on the entire end on the opening 41 side. In this manner, by forming the entire end 46 on the side of the open portion 41 as the spinning-possible portion 47, a spinning line that is a virtual line constituted by the spinning position of the CNT forest from which CNT is being spun. , Can be a closed line. When the spinning line is a closed line, a tubular structure, a linear structure, a coaxial laminated structure, a rope, and the like can be easily formed by the CNT entangled body.

  Since the CNT forest 45 of the present embodiment is formed by using the inner surface 43 of the apertured substrate 40 having the internal space 42 as the growth base surface 44, compared with the case where one plane is used as the growth base surface, A large area can be formed by effectively utilizing the space.

  The method for producing the CNT forest is not limited, and may be formed by any of the solid-phase catalysis method and the gas-phase catalysis method, but the catalyst is efficiently placed on the inner surface 43 of the open substrate 40 having the inner space 42. In order to apply, it is preferable to use a gas phase catalytic method.

2. Opening substrate of CNT forest An opening substrate of a CNT forest according to one embodiment of the present invention will be described with reference to the drawings.
FIGS. 4A and 4B are schematic views schematically showing another example different from the cylindrical opening substrate shown in FIG. 1, wherein FIG. 4A is a perspective view of a spindle hemispherical opening substrate, and FIG. It is a perspective view of a cylindrical opening board, and (c) is a perspective view of a cylindrical opening board different from FIG.

  The opening substrate for forming the CNT forest has a continuously changing inner diameter of the internal space 52 and the sizes of the open portions 51A and 51B at both ends, like the spindle hemispherical opening substrate 50 shown in FIG. May be different. Further, the internal space 62 may be configured by a plurality of planes, as in the case of the square-pillar opening substrate 60 shown in FIG. 4B.

  Examples of the material forming the apertured substrate include, but are not limited to, silicon, quartz, glass, and metal. Further, the aperture substrate is not limited to one having the property of not being easily deformed, and may be formed using a flexible sheet that can be elastically deformed or a deformable sheet such as a metal foil.

  The open substrates 40, 50 and 60 shown in FIGS. 1 and 4 (a) and 4 (b) each have open portions 41, 51A, 51B and 61 formed at both ends thereof. However, as in the case of the opening substrate 70 shown in FIG. 4C, a configuration may also be provided that includes not only the open portions 71A at both ends of the cylinder but also open portions 71B on the side surfaces.

  In this specification, the “open portion” refers to a portion that can introduce and / or discharge gas into the internal space of the open substrate. The number of open portions provided in the open substrate may be one or two or more. In the case of an open part of an open substrate having only one open part, gas is introduced and discharged from the same open part. On the other hand, if an open substrate having two or more open portions is used, the open portion used for supplying gas and the open portion used for discharging gas can be different. For this reason, it is possible to form a smooth flow of gas serving as a carbon source in the CNT forest. The smooth flow of gas has a positive effect on the growth of the CNT forest. Therefore, it is preferable to use an open board having at least two open portions.

  By making the shape of the open substrate provided with at least two open portions cylindrical, the flow of gas serving as a carbon source can be made smoother. By making the gas flow uniform in the entire inner space of the open substrate, the growth of the CNT forest on the inner growth base surface can be made uniform.

  In the present specification, the term “tubular” refers to an elongated and hollow inside, a variable inner diameter shown in FIG. 4 (a), and a polygonal cylindrical shape shown in FIG. 4 (b). 4 (c) also includes those provided with an opening on the side surfaces other than both ends.

  In the case where the shape of the open substrate is a polygonal cylindrical shape, a rectangular cylindrical shape shown in FIG. 4B is preferable from the viewpoint of productivity. In the case of a quadrangular cylindrical shape, the growth base surface on the inner surface is composed of four planes, and corners are formed by adjacent planes. The CNT forest formed at this corner may have different properties from the CNT forest formed on a plane. For this reason, when spinning CNTs, it is good also as spinning CNTs separately for every plane which comprises an inner surface.

  When the shape of the open substrate is cylindrical, a CNT forest is formed with a smooth inner surface having no corner unlike a polygonal cylindrical shape as a growth base surface. For this reason, by making the open substrate cylindrical, the uniformity of conditions when the CNT forest formed on the inner surface grows is improved. Therefore, in order to supply a gas serving as a carbon source and to increase the uniformity of the shape of the growth base surface on which the CNT forest grows, the shape is preferably cylindrical.

  The open substrate having two or more open portions has open portions formed at both ends of the cylinder as in the open substrates 40, 50, 60, and 70 shown in FIGS. 1 and 4A to 4C. It is preferable to use a dual-aperture substrate. By using a double-aperture substrate, the gas serving as the carbon source of the CNT flows along the cylinder, and the supply and discharge of the gas become smoother, so that the growth of the CNT forest is improved. The “dual-opening substrate” only needs to have open portions formed at both ends of the cylinder, and open portions are formed at side surfaces other than both ends as in the open substrate shown in FIG. Including things.

2-1. Opening substrate that can be divided The opening substrate has a CNT forest formed on its inner surface. For this reason, by being configured to be separable, washing after the CNT forest is spun out becomes easy. That is, by dividing the components of the open board, at least a part of the inner face of the open board is exposed, so that the inner face can be easily cleaned. Hereinafter, an example of an opening substrate configured to be dividable will be described.

  5 to 10 are perspective views of a state in which the dividable opening substrate according to the embodiment of the present invention is disassembled, as viewed obliquely from above. In these drawings, an example in which the cylindrical opening substrate shown in FIGS. 1A to 1C is configured to be divisible will be described. However, the opening substrate shown in FIGS. Similarly, a structure that can be divided can be used.

  FIG. 5 shows a dividable cylindrical opening substrate formed by combining two half cylinders having the same shape. When the components 80A and 80B having the same shape are combined as in the case of the opening substrate 80 shown in FIG. 7, only the components 80A and 80B having a single shape can be manufactured as the components of the opening substrate that can be divided. . For this reason, it can be manufactured at a lower cost as compared with an apertured board in which different parts are combined.

  The openable substrate that can be divided may be configured by combining two half-cylindrical components 81A and 81B having different shapes, like the cylindrical open substrate 81 shown in FIG. Each of the open substrates 80 and 81 shown in FIGS. 5 and 6 has an open portion formed by assembling two parts.

  FIG. 7 is a perspective view of the assembled state of the open board of FIG. 5 fixed by a fixing component as viewed from obliquely above. The opening substrate 82 shown in the figure fixes the components 80A and 80B constituting the opening substrate 80 by using a fixing component 83 that restrains from the outer surface side of the opening substrate 80 to form the opening substrate 82 as an assembly. . According to the configuration shown in FIG. 7, a state in which the dividable opening substrate 82 is assembled, that is, an assembly can be easily formed and held.

  8 to 10 show an example of an embodiment in which the positions of a plurality of parts in an assembled state are determined by a fitting structure of adjacent parts. The open substrates shown in these figures are obtained by combining two semi-cylindrical parts to form an assembly.

  In the open board 84 shown in FIG. 8, a concave portion 85A and a convex portion 85B are formed on each joint surface of the component 84A and the component 84B. By fitting the concave portion 85A and the convex portion 85B, the relative positional relationship between the component 84A and the component 84B is fixed, and the opening substrate 84 as an assembly is obtained. As described above, the relative positional relationship between the component 84A and the component 84B is fixed by the fitting structure of the concave portion 85A of the component 84A and the convex portion 85B of the component 84B adjacent to the component 84A. The opening substrate 84 as an assembly is obtained.

  In the open board 86 shown in FIG. 9, each of the joining surfaces of the component 86A and the component 86B is a concave portion 86A1 and a convex portion 86B1. That is, the concave portion 86A1 and the convex portion 86B1 constitute a part of the inner surface of the opening substrate 86. For this reason, the fitting substrate 86 of each of the component 86A and the component 86B is fitted together to form an open board 86 as an assembly. By adopting a structure in which the joining surfaces themselves are fitted as in the case of the opening substrate 86, positioning can be performed easily and accurately.

  The opening substrate 87 shown in FIG. 10 is an assembly obtained by combining two half-cylindrical parts 87A and 87B. Each joining surface itself of the component 87A and the component 87B is formed as a valley-shaped portion 87A1 having a low center and a mountain-shaped portion 87B1 having a high center. With the fitting structure of the valley shape and the mountain shape in this way, even if the components are slightly displaced during fitting, the components can be easily and smoothly moved to a predetermined position, so that assembly is easy. Although FIG. 10 shows an example in which each joint surface has one valley-shaped portion or one crest-shaped portion, a configuration having a plurality of valley-shaped portions and crest-shaped portions may be employed.

3. CNT Forest Manufacturing Apparatus A CNT forest manufacturing apparatus according to one embodiment of the present invention will be described with reference to the drawings.
FIG. 11 is a diagram schematically showing a configuration of a manufacturing apparatus used in the method for manufacturing a CNT forest according to one embodiment of the present invention.

  As shown in FIG. 11, the manufacturing apparatus 10 includes an electric furnace 12. The electric furnace 12 has a substantially cylindrical shape extending along a predetermined direction A (the direction in which the raw material gas flows). Inside the electric furnace 12, a reaction vessel tube 14 as a growth chamber for carbon nanotubes is passed. The reaction vessel tube 14 is a substantially cylindrical member made of a heat-resistant material such as quartz, has an outer diameter smaller than that of the electric furnace 12, and extends along a predetermined direction A. In FIG. 11, an open substrate 28 is installed in the reaction vessel tube 14.

  The electric furnace 12 includes a heater 16 and a thermocouple 18. The heater 16 is provided in a certain area of the reaction vessel tube 14 in the predetermined direction A (in other words, a certain area in the axial direction of the substantially cylindrical reaction vessel pipe 14, also referred to as a “heating area”). It is disposed so as to surround it and generates heat for raising the temperature of the atmosphere in the heating vessel of the reaction vessel tube 14. The thermocouple 18 is disposed inside the electric furnace 12 near the heating region of the reaction vessel tube 14 and can output an electric signal indicating a temperature related to the temperature of the atmosphere in the heating vessel of the reaction vessel tube 14. The heater 16 and the thermocouple 18 are electrically connected to the control device 20.

  A gas supply device 22 is connected to one end of the reaction vessel tube 14 in the predetermined direction A. The gas supply device 22 includes a source gas supply unit 30, a gas phase catalyst supply unit 31, a gas phase co-catalyst supply unit 32, and an auxiliary gas supply unit 33. The gas supply device 22 is electrically connected to the control device 20, and is also electrically connected to each supply unit included in the gas supply device 22.

  The source gas supply unit 30 can supply a source gas (for example, a hydrocarbon gas such as acetylene) containing a carbon compound as a source of CNT constituting the CNT forest to the inside of the reaction vessel tube 14. The supply flow rate of the source gas from the source gas supply unit 30 can be adjusted using a known flow rate adjusting device such as a mass flow.

  The gas-phase catalyst supply unit 31 can supply the gas-phase catalyst to the inside of the reaction vessel tube 14. The gas phase catalyst will be described later. The supply flow rate of the gas phase catalyst from the gas phase catalyst supply unit 31 can be adjusted using a known flow rate adjusting device such as a mass flow.

  The gas-phase co-catalyst supply unit 32 can supply the gas-phase co-catalyst to the inside of the reaction vessel tube 14. The gas phase promoter will be described later. The supply flow rate of the gas-phase co-catalyst from the gas-phase co-catalyst supply section 32 can be adjusted using a known flow control device such as a mass flow.

  The auxiliary gas supply unit 33 supplies the raw material gas, the gaseous catalyst and a gas other than the gaseous cocatalyst, for example, an inert gas such as argon (this gas is generally referred to as “auxiliary gas” in the present specification) to the reaction vessel. It can be supplied inside the tube 14. The supply flow rate of the auxiliary gas from the auxiliary gas supply unit 33 can be adjusted using a known flow rate adjusting device such as a mass flow.

  A pressure regulating valve 23 and an exhaust device 24 are connected to the other end of the reaction vessel tube 14 in the predetermined direction A. The pressure adjusting valve 23 can adjust the pressure of the gas in the reaction vessel tube 14 by changing the degree of opening and closing of the valve. The exhaust device 24 evacuates the inside of the reaction vessel tube 14. The specific type of the exhaust device 24 is not particularly limited, and a rotary pump, an oil diffusion pump, a mechanical booster, a turbo molecular pump, a cryopump, or the like can be used alone or in combination. The pressure adjustment valve 23 and the exhaust device 24 are electrically connected to the control device 20. A pressure gauge 13 for measuring the internal pressure is provided inside the reaction vessel tube 14. The pressure gauge 13 is electrically connected to the control device 20, and can output an electric signal indicating the pressure inside the reaction vessel tube 14 to the control device 20.

  As described above, the control device 20 is electrically connected to the heater 16, the thermocouple 18, the gas supply device 22, the pressure gauge 13, the pressure regulating valve 23, and the exhaust device 24, and the electric signals output from these devices and the like. And controls the operation of these devices and the like based on the input electric signal. Hereinafter, a specific operation of the control device 20 will be exemplified.

  The control device 20 inputs an electric signal related to the internal temperature of the reaction vessel tube 14 output from the thermocouple 18 and outputs a control signal related to the operation of the heater 16 determined based on the electric signal to the heater 16. can do. The heater 16 that has received the control signal from the control device performs an operation of increasing or decreasing the amount of generated heat based on the control signal, and changes the internal temperature of the heating region of the reaction vessel tube 14.

  The control device 20 receives an electric signal related to the internal pressure of the heating region of the reaction vessel tube 14 output from the pressure gauge 13 and operates the pressure regulating valve 23 and the exhaust device 24 determined based on the electric signal. A control signal can be output to the pressure regulating valve 23 and the exhaust device 24. The pressure adjusting valve 23 and the exhaust device 24 to which the control signal is input from the control device change the opening degree of the pressure adjusting valve 23 or change the exhaust capability of the exhaust device 24 based on the control signal. The operation is performed.

  The control device 20 can output a control signal for controlling the operation of each device or the like to each device according to a preset time table. For example, start and stop of gas supply from each of the source gas supply unit 30, the gas-phase catalyst supply unit 31, the gas-phase co-catalyst supply unit 32, and the auxiliary gas supply unit 33 included in the gas supply device 22, and the supply flow rate are determined. A control signal can be output to the gas supply device 22. The gas supply device 22 that has received the control signal operates each supply unit according to the control signal to start or stop supplying each gas such as a raw material gas into the reaction vessel tube 14.

4. Method for Manufacturing CNT Forest A method for manufacturing a CNT forest according to an embodiment of the present invention will be described with reference to the drawings.
The method for manufacturing a CNT forest according to the present invention includes a growth step of forming a CNT forest on the growth base surface of the above-described apertured substrate. In one embodiment, as shown in FIG. 12, the growth step includes first and second two steps.

(1) First Step The first step is a step in which an open substrate is present in an atmosphere containing a gas phase catalyst. As one embodiment, for example, a step of allowing an open substrate provided with a growth base surface, which is a surface made of a material containing a silicon oxide, as at least a part of the surface, to be present in an atmosphere containing a gas-phase catalyst is included. .

  The specific configuration of the aperture substrate is not limited. The shape may be any as long as it has an internal space communicating with the outside through the open portion, and may be a simple shape such as a sphere, an ellipsoid, a square tube or a cylinder, or provided with complicated irregularities. It may have a three-dimensional shape. Further, the entire surface of the opening substrate may be a growth base surface, or only a part of the surface of the opening substrate may be a growth base surface and the other portion may not be a growth base surface, that is, in a so-called patterned state. Is also good.

  The growth base surface is, for example, a surface made of a material containing a silicon oxide, and a CNT forest is formed on the growth base surface in the second step. The details of the material constituting the growth base surface are not limited as long as the material contains silicon oxide. A specific example of a material forming the growth base surface is quartz (SiO 2). Another example of a material constituting the growth base surface is SiOx (x ≦ 2), which can be obtained by sputtering silicon in an atmosphere containing oxygen. Yet another example is a composite oxide containing silicon. Examples of elements other than silicon and oxygen that constitute the composite oxide include Fe, Ni, and Al. Still another example is a compound in which a nonmetallic element such as nitrogen or boron is added to silicon oxide.

  The material forming the growth base surface may be the same as or different from the material forming the apertured substrate. As a specific example, the material forming the opening substrate is made of quartz and the material forming the growth base surface is also made of quartz, or the material forming the opening substrate is made of a silicon substrate mainly composed of silicon and the growth base surface is made of quartz. The case where the constituent material is made of the oxide film is exemplified.

  In the first step, an open substrate having the above growth base surface is present in an atmosphere containing a gas phase catalyst. As an example of the gas phase catalyst according to the present embodiment, a halide of an iron group element (that is, at least one of iron, cobalt, and nickel) (also referred to as “iron group element halide” in the present specification) can be given. More specific examples of such iron group element halides include iron fluoride, cobalt fluoride, nickel fluoride, iron chloride, cobalt chloride, nickel chloride, iron bromide, cobalt bromide, nickel bromide, and iodide. Iron, cobalt iodide, nickel iodide and the like. The iron-group element halide may include different compounds depending on the valency of iron-group element ions, such as iron (II) chloride and iron (III) chloride. , Or a plurality of types of substances.

  The method of supplying the gas phase catalyst to the inside of the reaction vessel tube is not limited. As in the above-described manufacturing apparatus 10, the gas may be supplied from the gas-phase catalyst supply unit 31 or a physical state (typically, a solid state other than the gas phase) that provides the gas-phase catalyst inside the heating region of the reaction vessel tube 14. Phase material) (herein, also referred to as a “catalyst source”), and the inside of the heating region of the reaction vessel tube 14 is heated and / or a negative pressure is applied to convert the gas phase catalyst from the catalyst source. After being generated, the gas phase catalyst may be present inside the heating region of the reaction vessel tube 14. If a specific example of generating a gaseous phase catalyst using a catalyst source is shown, an anhydride of iron (II) chloride is disposed as a catalyst source inside the heating region of the reaction vessel tube 14, and the heating of the reaction vessel tube 14 is performed. When the inside of the region is heated and negative pressure is applied to sublime the anhydride of iron (II) chloride, a gas phase catalyst composed of vapor of iron (II) chloride can be present in the reaction vessel tube 14.

The pressure of the atmosphere in the reaction vessel tube 14 in the first step, specifically, the portion where the open substrate is installed is not particularly limited. Atmospheric pressure (about 1.0 × 10 ⁵ Pa), negative pressure, or positive pressure may be used. When the inside of the reaction vessel tube 14 is set to a negative pressure atmosphere in the second step, it is preferable that the atmosphere is set to the negative pressure also in the first step to shorten the transition time between steps. When the inside of the reaction vessel tube 14 is set to a negative pressure atmosphere in the first step, the specific total pressure of the atmosphere is not particularly limited. As an example, it is set to 10 ⁻² Pa or more and 10 ⁴ Pa or less.

The temperature of the atmosphere in the reaction vessel tube 14 in the first step is not particularly limited. It may be at room temperature (about 25 ° C.), may be heated, or may be cooled. As described later, since the atmosphere inside the heating region of the reaction vessel tube 14 is preferably heated in the second step, the atmosphere in that region is also heated in the first step, and the transition between the steps is performed. It is preferable to reduce the time. When heating the atmosphere inside the heating region of the reaction vessel tube 14 in the first step, the temperature of the heating region is not particularly limited. One example is 8 × 10 ² K to 1.3 × 10 ³ K, and a preferable example is 9 × 10 ² K to 1.2 × 10 ³ K.

In the case where an anhydride of iron (II) chloride is used as the catalyst source, as described above, the conditions under which the catalyst source sublimates by heating the atmosphere inside the heating region of the reaction vessel tube 14 also in the first step. Preferably, it is satisfied. The sublimation temperature of iron (II) chloride is 950 K at atmospheric pressure (about 1.0 × 10 ⁵ Pa), but the sublimation temperature is reduced by setting the atmosphere inside the heating area of the reaction vessel tube 14 to a negative pressure. Can be reduced.

  Iron (II) chloride anhydride may be used as a catalyst source, and vapor of iron (II) chloride may be supplied from the gas phase catalyst supply unit 31 as a part of the gas phase catalyst. In this case, the iron (II) chloride anhydride disposed in the gas phase catalyst supply unit 31 is heated to sublime the iron (II) chloride, and the generated iron (II) vapor is transferred to the open substrate 28. Is guided into the reaction vessel tube 14 in which is installed, the first step can be completed.

(Second step)
In the second step, a plurality of carbon nanotubes are grown on the growth base surface of the open substrate by allowing the raw material gas and the gas phase co-catalyst to exist in the atmosphere containing the gas phase catalyst realized in the first step. A step of obtaining a CNT forest comprising the plurality of carbon nanotubes on a surface.

The type of the source gas is not particularly limited, but usually, a hydrocarbon-based material is used, and acetylene is a specific example. The method for causing the source gas to be present in the atmosphere inside the reaction vessel tube 14 is not particularly limited. As in the above-described manufacturing apparatus 10, the source gas may be provided by supplying the source gas from the source gas supply unit 30, or a material capable of generating the source gas may be provided in the reaction vessel tube 14 in advance. Alternatively, the second step may be started by generating a source gas from the material and diffusing it into the reaction vessel tube 14. When the source gas is supplied from the source gas supply unit 30, it is preferable to control the supply flow rate of the source gas into the reaction vessel tube 14 using a flow rate adjusting device. Usually, the supply flow rate is expressed in units of sccm, and 1 sccm means a flow rate of 1 ml per minute for gas converted into an environment of 273 K and 1.01 × 10 ⁵ Pa. In the case of a manufacturing apparatus having a configuration as shown in FIG. Is set. In the case where the pressure of the pressure gauge 13 is 1 × 10 ² Pa or more and 1 × 10 ³ Pa or less, a preferable supply flow rate of the acetylene-containing source gas is 10 sccm or more and 1000 sccm or less, and in this case, 20 sccm or more and 500 sccm or less. More preferably, it is more preferably not less than 50 sccm and not more than 300 sccm.

  In the present specification, the “gas-phase co-catalyst” has a function of increasing the growth rate of the CNT forest produced by the above-described gas-phase catalytic method (hereinafter, also referred to as “growth promoting function”), and is a preferable embodiment. In addition, it means a component having a function of improving the spinnability of the manufactured CNT forest (hereinafter, also referred to as “spinnability improving function”). The details of the growth promoting function are not particularly limited. One example is to lower the activation energy of the reaction related to the growth of the CNT forest. Further, details of the spinnability improving function are not particularly limited. One example is to increase the spinning length of a CNT entangled body obtained from a CNT forest.

  The specific components of the gas-phase cocatalyst are not particularly limited as long as they fulfill the above-mentioned growth promoting function and preferably also the function of improving spinnability, and a specific example is acetone. Acetone as a gas-phase co-catalyst can reduce the activation energy of the reaction when the CNT forest grows by the gas-phase catalysis method, and among the properties related to the spinnability of the obtained CNT forest, Can have a good effect on the spinning length. Details of these functions will be described in embodiments.

  In the second step, there is no particular limitation on the method for causing the gas-phase co-catalyst to exist in the atmosphere inside the reaction vessel tube 14. As in the above-described production apparatus 10, the gas phase co-catalyst may be present by supplying the gas phase co-catalyst from the gas phase co-catalyst supply section 32, or a material capable of generating the gas phase co-catalyst may be previously placed in the reaction vessel tube 14. The gas phase co-catalyst may be generated from the material by heating, depressurizing, or the like, and the gas phase co-catalyst may be diffused into the reaction vessel tube 14.

When supplying the gas-phase co-catalyst from the gas-phase co-catalyst supply section 32, it is preferable to control the supply flow rate of the gas-phase co-catalyst to the inside of the reaction vessel tube 14 using a flow rate adjusting device. When the pressure of the pressure gauge 13 is 1 × 10 ² Pa or more and 1 × 10 ³ Pa or less, a preferable supply flow rate of acetone which is an example of a gas phase removal catalyst is 10 sccm or more and 1000 sccm or less, and in this case, 20 sccm or more It is more preferably at most 500 sccm, particularly preferably at least 50 sccm and at most 300 sccm. When the source gas (acetylene as a specific example) and the gas-phase co-catalyst (acetone as a specific example) are supplied from the source gas supply unit 30 and the gas-phase co-catalyst supply unit 32, respectively, the supply flow rate (unit: sccm) of the source gas is The ratio of the gas-phase co-catalyst supply flow rate (unit: sccm) (gas-phase co-catalyst / source gas) is preferably 150% or less, more preferably 5% or more and 120% or less, and more preferably 10% or more and 100%. It is particularly preferable to set the following. With such a ratio, the growth rate of the CNT forest can be more stably increased.

  As described above, the degree of the growth promoting function of acetone as a gas-phase co-catalyst varies depending on the quantitative relationship with the raw material gas, and the effect of containing acetone as a gas-phase co-catalyst depends on the initial reaction. Is more remarkably confirmed, and acetone as a gas-phase co-catalyst is strongly involved in a relatively early stage in a process in which a raw material gas interacts with a catalyst to grow a CNT forest. there is a possibility.

  In the second step, the timing at which the raw material gas is present in the atmosphere inside the reaction vessel tube 14 and the timing at which the gas-phase cocatalyst is present are not particularly limited. Either one may be first or the same. However, when the gas phase co-catalyst is first or simultaneously present, unlike the conventional method of producing a CNT forest by the gas phase catalyst method, the growth of the CNT forest based on the interaction between the raw material gas and the gas phase catalyst is carried out. Since it is possible to prevent starting before the introduction, it is possible to fully obtain the benefit of including the gas phase promoter. Therefore, it is preferable to set the gas-phase co-catalyst so as to exist in the atmosphere in the reaction vessel tube 14 before or at the same time as the raw material gas.

  An auxiliary gas may be present in the atmosphere in the reaction vessel tube 14 in the second step, for example, for the purpose of adjusting the total pressure to a predetermined range. As the auxiliary gas, a gas having a relatively low influence on the generation of the CNT forest, specifically, an inert gas such as an argon gas or a nitrogen gas is exemplified. The method for causing the auxiliary gas to exist in the atmosphere in the reaction vessel tube 14 is not particularly limited. As in the above-described manufacturing apparatus 10, the supply device includes the auxiliary gas supply unit 33, and it is simple to supply the auxiliary gas from the auxiliary gas supply unit 33 into the atmosphere in the reaction vessel tube 14, and the controllability is excellent. ,preferable.

The total pressure of the atmosphere in the reaction vessel tube 14 in the second step is not particularly limited. Atmospheric pressure (about 1.0 × 10 ⁵ Pa), negative pressure, or positive pressure may be used. What is necessary is just to set suitably considering the composition (partial pressure ratio) of the substance which exists in the atmosphere in the reaction vessel tube 14, etc. If a specific example of the pressure range when the atmosphere inside the heating region in the reaction vessel tube 14 is set to a negative pressure is 1 × 10 ¹ Pa or more and 1 × 10 ⁴ Pa or less, and 2 × 10 ¹ Pa or more 5 It is preferably set to × 10 ³ Pa or less, more preferably 5 × 10 ¹ Pa to 2 × 10 ³ Pa, particularly preferably 1 × 10 ² Pa to 1 × 10 ³ Pa.

  The temperature of the atmosphere inside the heating region of the reaction vessel tube 14 in the second step is not particularly limited as long as the CNT forest can be formed using the raw material gas in the atmosphere where the gas phase catalyst and the gas phase cocatalyst are present. When a gaseous catalyst is obtained by heating a catalyst source such as the above-mentioned iron (II) chloride, the temperature of the atmosphere inside the heating region of the reaction vessel tube 14 is set to be equal to or higher than the temperature at which the gaseous catalyst is formed. Is done.

The temperature of the growth base surface during the second step is preferably heated to 8 × 10 ² K or more. When the temperature of the growth base is 8 × 10 ² K or more, the interaction between the gaseous catalyst and the gas-phase co-catalyst and the source gas tends to occur on the growth base, and the CNT forest grows on the growth base. It's easy to do. From the viewpoint of making this interaction more likely to occur, the temperature of the growth base surface during the second step is preferably heated to 9 × 10 ² K or more. The upper limit of the temperature of the growth base during the second step is not particularly limited, but if it is excessively high, the material forming the growth base or the material forming the apertured substrate (these may be the same). May lack the stability as a solid, so it is preferable to set the upper limit in consideration of the melting points and sublimation temperatures of these materials. In consideration of the load on the reaction vessel tube, the upper limit temperature is preferably up to about 1.5 × 10 ³ K.

5. Spinning source member The CNT forest manufactured by the manufacturing method according to the present embodiment has excellent spinnability. Specifically, a structure (CNT entanglement) including a plurality of CNTs entangled with each other by pinching the spinnable portion of the end of the CNT forest and pulling it out in a direction away from the CNT forest (spinning). Body) can be obtained. FIG. 13 is an image showing a state in which a CNT entangled body is formed from a CNT forest, and FIG. 14 is an image in which a part of the CNT entangled body is enlarged. As shown in FIG. 13, CNTs constituting the CNT forest are continuously pulled out to form a CNT entangled body. As shown in FIG. 14, the CNTs constituting the CNT entangled body are entangled with each other to form a connected body while being oriented in a direction (spinning direction) drawn from the CNT forest. In the present specification, a member including a CNT forest and capable of forming a CNT entangled body is also referred to as a “spinning source member”.

  The CNT forest that can be a spinning source member may be any CNT forest that can form a CNT entangled body. (The height in the state of being performed) is high. That is, when the growth height of the CNT forest is sufficiently high, the degree of entanglement of the CNTs becomes high, and it becomes easy to continuously spun. The ease of forming a CNT entangled body from the CNT forest (spinnability) can be evaluated by the spinning direction length of the CNT entangled body formed from the CNT forest (the length in the direction in which CNTs are drawn from the CNT forest). it can. A CNT forest that has a long length in the spinning direction and can be formed without interruption is preferable. (It is most preferable that all the CNT forest is spun out and consumed without interruption.)

  The CNT forest produced by the production method using the gas-phase co-catalyst according to the present embodiment has a higher spinning speed than the production method according to the related art, that is, the CNT forest produced by the gas-phase catalyst method without using the gas-phase co-catalyst. Good CNT forest growth range is wide. That is, according to the production method using the gas-phase cocatalyst, the spinnability of a CNT forest made of CNT longer than before and a CNT forest made of CNT shorter than before becomes better. In other words, by using the CNT forest manufactured by the manufacturing method according to the present embodiment as a spinning source member, the CNT made of CNTs having a length that could not be manufactured using the CNT forest according to the conventional method. The entangled body can be manufactured more stably.

  The fact that the CNT forest manufactured by the manufacturing method according to the present embodiment has excellent spinnability will be specifically described below. When a CNT entangled body is formed by using a CNT forest produced by a gas phase catalytic method using acetone as a raw material gas and an anhydride of iron (II) chloride as a catalyst source, good spinnability (as a specific example, spinning) The growth height of the CNT forest from which the length is 1 cm or more, that is, the range of the CNT length is limited to a predetermined range. Although the upper and lower limits vary depending on the manufacturing conditions, the range of the growth height (upper limit height-lower limit height) is generally about 0.5 mm. On the other hand, in the case of a CNT forest produced by a method using acetone as a gas phase co-catalyst in the above-mentioned gas phase catalytic method, the range of the growth height of the CNT forest at which the above-mentioned spinning property is good is determined by the gas phase co-catalyst Compared to the case without a catalyst, both the lower limit and the upper limit are widened and can be twice or more, that is, 1 mm or more, and in a preferred embodiment, about three times or more, that is, about 1.5 mm or more. To reach.

  To explain from another viewpoint that the CNT forest manufactured by the manufacturing method according to the present embodiment is excellent in spinnability, the CNT forest manufactured by the manufacturing method according to the present embodiment is, in a preferred embodiment, a CNT forest. Even if the growth height is 2 mm or more, spinning with a spinning length of 1 cm or more can be stably performed.

  Such a CNT forest having excellent spinnability can be more easily produced by using a gas phase co-catalyst in a gas phase catalytic method. In the case of the solid phase catalytic method, the production process of the CNT forest is different from the case of the gas phase catalytic method, and the basic structure of the obtained CNT forest may be different from that of the gas phase catalytic method. There is no circumstance which hinders the application of the manufacturing method.

  It is preferable that the upper limit of the range of the growth height of the CNT forest in which the spinnability is good is increased from the viewpoint of improving the properties of the CNT entangled body obtained from the CNT forest. That is, the CNT entangled body obtained from the CNT forest having a large value of the growth height has a relatively large value of the length of the CNTs constituting the CNT entangled body in the long axis direction. Easy to grow. Therefore, when the CNT entangled body has a thread-like shape or a web-like shape, mechanical properties (for example, tensile strength), electrical properties (for example, volume conductivity), heat Characteristic (for example, thermal conductivity) is easily improved.

  It is not clear why the spinning source member including the CNT forest manufactured by the manufacturing method according to the present embodiment has excellent spinnability as described above. When the drawing (spinning) of CNTs is continuously progressing from the CNT forest, the drawn CNTs are appropriately entangled with each other, and the drawn CNTs are drawn in the drawing direction in the drawing direction of the CNTs. By appropriately interacting with the nearest nearest CNT (hereinafter, also referred to as “nearest CNT”) on the opposite side, the nearest CNT is extracted. Accordingly, in order to increase the spinning length of the CNT entangled body spun from the CNT forest, the balance between the interaction between the extracted CNT and the already extracted CNT and the interaction between the extracted CNT and the nearest CNT are considered. It needs to be appropriate. It is possible that the spinning co-catalyst is involved in forming a CNT forest in which the balance of these interactions is appropriate.

6. Structure The CNT entangled body obtained from the spinning source member can have various shapes. A specific example is a linear shape, and another example is a web shape. The linear CNT entangled body can be handled as well as a fiber, and can be used as an electric wiring. Further, the web-shaped CNT entangled body can be handled as it is in the same manner as a nonwoven fabric.

  The length of the CNT entangled body in the spinning direction is not particularly limited, and may be appropriately set according to the application. Generally, if the spinning length is 2 mm or more, the CNT entangled body can be applied to a part level such as a contact portion and an electrode. The degree of orientation of the CNTs constituting the web-shaped CNT entangled body can be arbitrarily controlled by changing the spinning method from the spinning source member. Therefore, by changing the spinning method from the spinning source member, it is possible to manufacture CNT entangled bodies having different mechanical properties and electrical properties.

  If the degree of entanglement is reduced, the CNT entangled body becomes thinner in the case of a linear shape and thinner in the case of a web shape. If the degree increases, it becomes difficult to visually confirm the CNT entangled body, and at this time, the CNT entangled body can be used as a transparent fiber, a transparent wiring, or a transparent web (a transparent sheet-like member).

  Since the spinning source member of the present embodiment has good spinnability as described above, a web-like structure can be obtained. In the present specification, the term "web-like" refers to a spider's web-like, woven or non-woven fabric formed intricately by entanglement of fibers.

  For example, when a tubular structure is used as the opening substrate 28, a tubular structure having an inner surface and an outer surface is obtained as a web-like structure. When this tubular web-like structure is cut out, a sheet-like structure is obtained.

  If the CNTs are bundled by twisting, a twisted yarn as a linear structure is obtained, and if the CNTs are bundled without twisting, a non-twisted yarn as a linear structure is obtained. A rope can also be produced using these twisted or untwisted yarns as a part thereof. When the CNTs are bundled by twisting, the side of the open substrate may be rotated, or the side of the yarn that has bundled the linear structure may be rotated.

7. Method for Manufacturing Structure A method for manufacturing a structure according to an embodiment of the present invention will be described. Hereinafter, among the structures, a method of manufacturing a web-like structure and a linear structure having an inner surface and an outer surface will be described.

7-1. Method of Manufacturing Web-Shaped Structure The web-shaped structure having the inner surface and the outer surface according to the present embodiment is formed on the entire open-side end of the CNT forest formed on the inner surface of the cylindrical opening substrate. It can be manufactured by spinning out a spinnable part.

  FIG. 15 schematically illustrates a mode in which CNTs are spun from a CNT forest formed on the cylindrical apertured substrate illustrated in FIG. 1C and focused, and FIG. 15A illustrates an initial stage. It is sectional drawing, (b) is sectional drawing which shows the stage which spinning advanced.

  As shown in FIG. 15A, a web-like structure 90 having an inner surface 90A and an outer surface 90B is obtained by pulling out the spinnable portion 47 of the entire end 46 of the CNT forest 45. By pulling out the spinnable portion 47 in a direction parallel to the central axis C of the cylindrical opening substrate 40, a cylindrical structure having the inner surface 90A and the outer surface 90B can be easily manufactured.

  As illustrated in FIG. 15B, the CNT forest 45 is consumed as the spinning proceeds, and the end 46 moves inward from the open portion 41 of the open substrate 40. Therefore, when the spinning is restarted after being interrupted, the end 46 is located inside the open substrate 40.

7-2. Method for Manufacturing Linear Structure A method for manufacturing a linear structure according to the present embodiment includes a spinning step and a converging and focusing step, as shown in FIG.
FIGS. 17 (a) and 17 (b) and FIGS. 18 (a) and 18 (c) show a mode in which CNTs are spun from the CNT forest formed on the cylindrical opening substrate shown in FIGS. 1 (a) to 1 (c). It is the figure which showed typically.

  FIG. 17A is a cross-sectional view showing an initial stage, and FIG. 17B is a cross-sectional view showing a stage in which spinning has proceeded. FIGS. 18A to 18C schematically show a mode in which CNTs are spun from a CNT forest formed on a cylindrical opening substrate, wherein FIG. 18A is a perspective view, FIG. 18B is a front view, and FIG. It is sectional drawing. 18 (a) to 18 (c), for convenience, the CNT entangled body spun from the spunable portion 47 at the end 46 in the CNT forest 45 is schematically illustrated using a plurality of lines. The CNT entangled body is spun from the entire end 46 as a tube. FIG. 18A shows only the spinning-out possible portion 47 at the end 46 of the CNT forest 45 formed on the inner surface 43 of the opening substrate 40.

(Spinning process)
In the manufacturing method of the linear structure, the CNT entangled body spun from the spunable part 47 of the CNT forest 45 is drawn out in the direction of the central axis C of the open substrate 40 in FIG. The light is converged at the convergence point P to form a linear structure. When a highly symmetric open substrate such as the open substrate 40 is used, the CNT forest 45 can be spun from any part of the end 46 of the end 46 of the CNT forest 45 under uniform conditions. It will be. The consumption amount of the CNT forest can be evaluated, for example, using the length of the CNT forest 45 consumed. In the case of a cylindrical opening substrate like the opening substrate 40, if the convergence point P is set on the central axis C, spinning can be performed under uniform conditions. By setting the convergence point P on the central axis C of the apertured substrate 40, the consumption of the portion where the CNT forest 45 is least consumed is in the range of 80 to 100% of the consumption of the portion where the CNT forest 45 is most consumed. The spinning process can be performed under “equal conditions”. However, the convergence point P does not necessarily have to be on the center axis C in order to spin out under uniform conditions. Alternatively, the convergence point P may be set as an arbitrary location, and a linear structure may be manufactured without uniform conditions for spinning. By pulling the structure so as to have a spindle shape, a good linear structure can be obtained.

(Bundling process, twisting process)
The bundling step is a step of bundling the CNTs spun in the spinning step to form a linear structure. When forming a linear structure in the bundling step, a twisted yarn can be obtained by twisting the CNT, and a non-twisted yarn can be obtained by twisting the CNT.
Hereinafter, a case where the bunching step is a twisting step of twisting CNTs to form a twisted yarn will be described.

  FIG. 21 is a schematic view schematically showing a conventional method for converging CNTs drawn from a flat substrate on which CNTs are formed by twisting. As shown in the drawing, when the CNTs pulled out from the flat substrate on which the CNT forest 105 is formed are converged by twisting, both sides of the CNT forest 105 are consumed earlier than the center. This is because when the twisted yarn 110, which is a linear structure, is twisted at the convergence point P, the outer yarns 107A and 107C (shown by dotted lines) spun from both sides 106A and 106C of the end 106 near the center 106B. This is due to the structure surrounding the middle thread 107B (shown by the solid line) spun from the yarn, and is consumed more than the middle thread 107B. In other words, the length used per unit length of the twisted yarn 110 is longer in the outer yarns 107A and 107C surrounding the middle yarn than in the straight middle yarn 107B, and therefore, as shown in FIG. The CNT forest near the center is consumed on both sides of the 105 first and remains on the substrate.

  On the other hand, in the structure manufacturing method of the present embodiment, in the twisting step, CNT spun from a CNT forest formed on the inner surface of the cylindrical opening substrate 40 is twisted. For this reason, by adjusting the direction in which the CNTs are pulled out, it is possible to prevent the structure drawn out from a specific region on the substrate from becoming a middle thread or an outer thread and to uniformly consume the CNT forest.

  For example, if the convergence point P where the twisting step is performed is on or near the central axis C of the apertured substrate 40, the relative positional relationship between the twisted position and the position where the CNTs are spun out is equalized. be able to. Therefore, it is possible to prevent the CNT entangled body drawn out from a specific region on the apertured substrate from becoming exclusively a middle thread or an outer thread, and to uniformly consume the CNT forest. Here, “the position where the CNT forest is consumed the least” means a position where the consumption of the portion where the CNT forest is consumed least is in the range of 80 to 100% of the consumption of the portion where the consumption is the largest.

8. Composite Structure The CNT entangled body may be composed of only CNTs, or may be a composite structure with another material. As described above, since the CNT entangled body has a structure in which a plurality of CNTs are intertwined with each other, voids exist between the intertwined CNTs, similarly to the plurality of fibers constituting the nonwoven fabric. Powder (inorganic particles such as metal fine particles and silica, and organic particles such as an ethylene polymer) is introduced into the void portion, or the liquid is impregnated with the powder so that the powder can be easily impregnated. A composite structure can be formed.

  Further, the surface of CNT constituting the CNT entangled body may be modified. Since the outer surface of CNT is composed of graphene, the CNT entangled body is hydrophobic as it is, but the CNT entangled body is made hydrophilic by performing a hydrophilic treatment on the surface of the CNT constituting the CNT entangled body. can do. An example of such a means for making hydrophilic is a plating treatment. In this case, the obtained CNT entangled body becomes a composite structure of CNT and plated metal.

  The composite structure can have a laminated structure including at least a part of a structure layer composed of the structure. For example, if a linear member serving as a core is arranged on the inner surface of a cylindrical structure and CNTs are focused, a composite structure having a coaxial laminated structure can be obtained. In addition, a rope having a composite structure as a part thereof can impart properties of the composite to the rope.

  The composite structure may have a structure having a CNT entangled body as a skeletal structure. In this specification, “providing a structure as a skeletal structure” refers to a structure having a structure as a center that forms a composite structure formed by combining a plurality of materials. For example, among the plurality of materials constituting the composite structure, the one in which the structure occupies the maximum volume or the maximum mass corresponds to “providing the structure as a skeletal structure”.

9. Method for Manufacturing Composite Structure A method for manufacturing a composite structure according to an embodiment of the present invention will be described.
The method for manufacturing a composite structure according to the present embodiment includes a spinning step and a compounding step, as shown in FIG.

(Spinning process)
The spinning process is the same as the above-described spinning process in the structure manufacturing method. As shown in FIG. 15, when a cylindrical structure is to be formed, it is drawn out in a direction parallel to the central axis C of the open substrate and spun. When a linear structure is to be formed, as shown in FIGS. Then, it is drawn out in the direction of the central axis C of the open substrate and spun.

(Composite process)
The compounding step is a step of combining the web-like structure obtained in the spinning step with another material. The web-like structure obtained in the spinning process has an inner surface and an outer surface. Introducing powder (inorganic particles such as metal fine particles and silica, and organic particles such as ethylene polymer) into the inner surface of the web-like structure, or impregnating with a liquid. Thereby, a composite structure can be easily formed. By adding a composite material to the inner surface, a larger amount of composite material can be compounded than before. Further, a stable composite structure is formed by surrounding the added composite material with the web-like structure.

  Hereinafter, the present invention will be described more specifically with reference to Examples and the like, but the scope of the present invention is not limited to these Examples and the like.

(Example 1)
Using a manufacturing apparatus having the structure shown in FIG. 11, a CNT forest was manufactured by the manufacturing method shown in FIG.
Specifically, first, the first step was performed as follows.
In a reaction vessel tube of the manufacturing apparatus having the structure shown in FIG. 11, cylindrical quartz (18 mm in outer diameter, 15 mm in inner diameter, 20 mm in length) was placed on a quartz boat. Therefore, in this embodiment, the material constituting the growth base surface and the material constituting the apertured substrate were both quartz. Further, 130 mg of anhydrous iron (II) chloride as a catalyst source was placed on a portion other than the boat in the reaction vessel tube.

After the inside of the reaction vessel tube was evacuated to 1 × 10 ⁻¹ Pa or less using an exhaust device, the inside of the reaction vessel tube (including the open substrate) was heated to 1.1 × 10 ³ K using a heater. As a result, the anhydride of iron (II) chloride sublimates in the reaction vessel tube, and the inside of the heating region of the reaction vessel tube contains a gas-phase catalyst formed from anhydride of iron (II) chloride as a catalyst source. It became the atmosphere including.

After performing the first step in this manner, the atmospheric pressure is maintained at 4.5 × 10 ² Pa using the pressure adjusting valve, and the temperature inside the reaction vessel tube (including the open substrate) is set to 1.1 using the heater. While maintaining the temperature at × 10 ³ K, 200 (sccm) of acetylene as a source gas from the source gas supply unit and 10 (sccm) of acetone as a gas phase cocatalyst from the gas phase co-catalyst supply unit were respectively introduced into the reaction vessel tube. The second step was performed by feeding.

  By starting the second step, ie, starting the supply of acetylene and acetone, the CNT forest grew on the growth substrate. The CNT forest was grown by growing the CNT forest for 7 minutes from the start of the second step.

After finishing the heating by the heater and confirming that the temperature in the reaction vessel tube has reached room temperature, the exhaust in the reaction vessel tube by the exhaust device is terminated, and the atmosphere pressure is increased by introducing air into the reaction vessel tube. Atmospheric pressure (1 × 10 ⁵ Pa) was set. Thereafter, the reaction vessel tube was opened, and the CNT forest was taken out together with the open substrate.

  Some CNTs, including the CNTs located on the side of the edge of the CNT forest, were pulled away from the CNT forest. As a result, as shown in FIG. 20, a web-like structure having an inner surface and an outer surface including a plurality of carbon nanotubes entangled with each other was obtained.

  By using the CNT forest obtained as described above, a portion of the CNTs including the CNTs located on the side surfaces at the ends of the CNT forest are pulled away from the CNT forest, thereby forming a cylindrical structure having a continuous side surface. The body is obtained. The reason why a CNT forest having good spinnability was obtained is considered to be that spinnability was improved by using acetone as a gas-phase co-catalyst in addition to the raw material gas.

  Since the CNT forest formed on the inner surface of the open substrate having the internal space as the growth base surface and the CNT forest formed on the flat substrate have different physical conditions (environment) during production, the spinning property is high. Factors that affect properties such as these may also be different. For example, it is well known that the air flow and temperature distribution in a reaction vessel tube are affected by the shape of an object installed in the reaction vessel tube. Therefore, it is not clear what effect the obtained CNT forest has due to the fact that the substrate installed in the reaction vessel becomes a three-dimensional open substrate from a planar substrate.

  In particular, in the case of the gas phase catalytic method, the shape of the substrate greatly affects the state of the sublimated catalyst in the reaction vessel tube. For this reason, conditions for obtaining a CNT forest having good spinnability are greatly affected by the shape of the substrate used. Therefore, the conditions that contributed to the improvement of spinnability when using a flat substrate cannot be said to be similarly effective for a CNT forest formed on the inner surface of a more three-dimensional open substrate.

  The CNT entangled body obtained from the CNT forest manufactured by the method for manufacturing a CNT forest according to the present invention is suitably used as, for example, an electric wiring, a heating element, a stretchable sheet-shaped strain sensor, a transparent electrode sheet, and the like.

DESCRIPTION OF SYMBOLS 10 ... Manufacturing apparatus 12 ... Electric furnace 13 ... Pressure gauge 14 ... Reaction vessel tube 16 ... Heater 18 ... Thermocouple 20 ... Control apparatus 22 ... Gas supply apparatus 23 ... Pressure adjustment valve 24 ... Exhaust apparatus 28 ... Open substrate 30 ... Raw material gas Supply unit 31 ... gas phase catalyst supply unit 32 ... gas phase co-catalyst supply unit 33 ... auxiliary gas supply units 40, 50, 60, 70 ... open substrates 41, 51A, 51B, 61, 71A, 71B ... open units 42, 52, 62, 72 ... internal space 43 ... inner surface 44 ... growth base surface 45 ... CNT forest 46 ... end 47 ... spunable parts 80, 81, 82, 84, 86, 87 ... open substrates 80A, 80B, 81A, 81B, 84A. , 84B, 86A, 86B, 87A, 87B ... part 83 ... fixed part 85A ... concave part 85B ... convex part 86A1 ... concave part 86B1 ... convex part 87A1 ... valley part 87B1 ... crest part 90,9 ... structure 90A ... the inner surface 90B ... the outer surface

Claims (13)

An open substrate used for spinning that has an internal space communicating with the outside through an open part, at least a part of the inner surface is a growth base surface of a CNT forest, and a plurality of CNTs are continuously drawn from the CNT forest,
An apertured substrate, wherein a plurality of parts are assembled so as to be dividable, and at least a part of the inner surface is exposed by dividing the plurality of parts.   The aperture substrate according to claim 1, wherein the growth base surface includes a region surrounding the opening on the inner surface.   The aperture substrate according to claim 1, wherein the aperture substrate has at least two openings.   The aperture substrate according to claim 3, which is cylindrical.   The aperture substrate according to claim 4, wherein the open portions are formed at both ends of the internal space.   The aperture substrate according to claim 5, which has a cylindrical shape.   The aperture substrate according to any one of claims 1 to 6, wherein at least one of the open portions is formed by assembling two or more of the plurality of components.   The aperture substrate according to claim 7, wherein all of the plurality of components have the same shape.   The aperture substrate according to claim 7, wherein the plurality of components include those having different shapes.   The aperture substrate according to any one of claims 1 to 9, further comprising a fixing component for fixing a state in which the plurality of components are assembled. A tubular opening substrate,
The opening board according to claim 10, wherein the fixed component restrains a plurality of the components from the outer surface side of the opening board to form the assembly.   The aperture board according to any one of claims 1 to 11, wherein the positions of the plurality of components in the assembly are determined by a fitting structure of the adjacent components. 13. The aperture board according to claim 12 , wherein the fitting structure comprises a fitting structure of a convex part and a concave part of the adjacent components.