Apparatus for manufacturing long carbon nanotube sheets, method for manufacturing long carbon nanotube sheets, long carbon nanotube sheets, and laminates

Abstract

This invention provides a CNT (carbon nanotube) long sheet manufacturing apparatus for efficiently producing highly useful CNT long sheets. [Solution] The lamination drum for laminating CNT films has a cylindrical shape and a slit-shaped discontinuous portion extending parallel to the axial direction on its outer circumference; a first inner roll disposed in the hollow space of the lamination drum and winding a release film that is wrapped around the outer circumference of the lamination drum via the discontinuous portion; a second inner roll disposed in the hollow space and recovering and winding the release film wound around the outer circumference of the lamination drum via the discontinuous portion; and a substrate to which a CNT forest is attached for adhering a CNT web to the release film wound around the outer circumference of the lamination drum. The lamination drum is rotatably positioned so that the CNT film with the CNT web laminated on it can be laminated on the release film, and the second inner roll winds the CNT film together with the release film.

Description

[Technical Field]

[0001] The present invention relates to an apparatus for manufacturing long sheets made of carbon nanotubes, a method for manufacturing long sheets made of carbon nanotubes, long sheets made of carbon nanotubes, and laminates. [Background technology]

[0002] Carbon nanotubes (CNTs) have been known for some time as tubular nanomaterials composed solely of carbon atoms (see, for example, Patent Document 1). Due to their thinness, lightness, and flexibility, carbon nanotubes (hereinafter abbreviated as CNTs) are attracting attention as a next-generation carbon material. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-128466 [Overview of the project] [Problems that the invention aims to solve]

[0004] If it becomes possible to manufacture long sheets of carbon nanotubes (hereinafter referred to as CNT long sheets) by utilizing the properties of CNTs, it will be possible to obtain long sheets that are highly strong, lightweight, and flexible, making them suitable for a wide range of applications, and their usefulness is immeasurable.

[0005] In this disclosure, a CNT long sheet refers to a long sheet that is substantially made of CNTs only, without the addition of additives, adhesives, resins, etc. A long sheet substantially made of CNTs only means a long sheet in which no materials other than CNTs, such as additives, adhesives, or resins, are intentionally used in the manufacturing process. For example, it means a long sheet in which 97% to 100% by mass, preferably 98% to 100% by mass, is composed of CNTs. Furthermore, a long sheet means a sheet with a length of at least 50m, preferably 100m or more, more preferably 105m or more, and particularly preferably 110m or more. There is no particular upper limit on the length, but for example, it is 1000m or less.

[0006] To manufacture long sheets made of carbon nanotubes (CNTs), it is necessary to prepare a CNT web (definition described below). A CNT web can be obtained, for example, from a CNT forest. A CNT forest refers to an aggregate of multiple CNTs arranged on a substrate and oriented perpendicular to the surface of the substrate. In a CNT forest, multiple CNTs stand upright on the substrate. A CNT web can be obtained by extracting multiple CNTs from the CNT forest into a sheet-like form using van der Waals forces. The web state (single layer) extracted from a CNT forest is called a CNT web, and a stack of two or more CNT webs is called a CNT film.

[0007] However, obtaining long sheets made solely from carbon nanotubes (CNTs) was difficult. While non-long sheets made solely from CNTs were known, a method for manufacturing long sheets made solely from CNTs had not been established.

[0008] One possible method for processing CNTs into long sheets is to wind and laminate the CNT web onto the circumferential surface of a cylindrical or cylindrical roll. However, this method presents the problem that long sheets exceeding the circumferential length of the roll cannot be manufactured.

[0009] In this case, for example, manufacturing a 100m long sheet of CNT would require a roll with a diameter of approximately 32m, which is impractical. On the other hand, if it were manufactured in a factory without being rolled, a production line equal to the length of the CNT sheet would be required, which is also impractical.

[0010] The object of the present invention is to provide a highly useful long sheet made of carbon nanotubes (CNT), a laminate containing the long sheet made of CNT, a CNT long sheet manufacturing apparatus for efficiently producing the long sheet made of CNT, and a method for manufacturing a long sheet made of CNT. [Means for solving the problem]

[0011] In other words, the present invention provides, for example, the following means to solve the above problems. [1] A lamination drum for laminating carbon nanotube films, having a cylindrical shape and having slit-shaped discontinuous portions extending parallel to the axial direction on its outer circumference, A first inner roll is positioned in the hollow space of the laminated drum and winds a release film around the outer circumference of the laminated drum via the discontinuous portion, A second inner roll is positioned in the hollow space and recovers and winds the release film, which is wound around the outer circumference of the laminated drum, through the discontinuous portion. A substrate to which a carbon nanotube forest for adhering a carbon nanotube web is attached to the release film wrapped around the outer circumference of the laminated drum, Equipped with, The lamination drum is rotatably arranged so that a carbon nanotube film, on which the carbon nanotube webs are laminated, can be laminated onto the release film. The apparatus for manufacturing long sheets made of carbon nanotubes is characterized in that the second inner roll winds the carbon nanotube film together with the release film. [2] The carbon nanotube long sheet manufacturing apparatus according to [1], characterized in that the first inner roll and the second inner roll are arranged such that the central axis of the first inner roll and the central axis of the second inner roll are located between the central axis of the laminated drum and the outer circumference of the laminated drum, respectively. [3] The apparatus for manufacturing long carbon nanotube sheets according to [1], characterized in that the length of the outer circumference of the laminated drum is 1.5 m or more and 10 m or less. A method for manufacturing carbon nanotube long sheets using the carbon nanotube long sheet manufacturing apparatus of [4] [1], wherein the method is as follows: Setting steps include: wrapping the release film, which is set on the first inner roll, around the outer circumference of the laminated drum and then fixing it to the second inner roll; A layer formation step comprising: drawing the carbon nanotube web from the carbon nanotube forest, rotating the lamination drum multiple times while bringing it into contact with the release film, thereby forming the carbon nanotube film on the release film by laminating the carbon nanotube web; A cutting step of cutting the carbon nanotube film at the location of the discontinuous portion, A coating step is to fix one side of an additional release film, which has a length equal to 1 / n of the circumference of the outer edge of the separately prepared laminated drum, to the position of the edge of the discontinuous portion, and to cover the carbon nanotube film with the additional release film. A winding process in which the sandwich-like layer formed in the coating process, in which the carbon nanotube film is sandwiched between the release film and the additional release film, is wound onto the second inner roll. A method for producing a long sheet made of carbon nanotubes, characterized by including the layering step, the cutting step, the coating step, and the winding step being repeated multiple times. [5] Immediately before the winding step of the nth cycle, the release film wound around the outer circumference of the laminated drum is formed on the release film, in order from the first inner roll side end of the discontinuous portion toward the second inner roll side end, a carbon nanotube laminated film in which n layers of the carbon nanotube film are laminated, a carbon nanotube laminated film in which n-1 layers of the carbon nanotube film are laminated, ..., and the carbon nanotube laminated film consisting of one layer of the carbon nanotube film is formed. A method for manufacturing a long sheet of carbon nanotubes according to [4], wherein the carbon nanotube laminated film is formed by laminating multiple layers of the carbon nanotube film, and the carbon nanotube film formed in newer cycles is laminated towards the upper layers. [6] Immediately before the winding step of the second cycle of the carbon nanotube long sheet manufacturing method, the additional release film having a length equivalent to half the circumference of the laminated drum, On the half-circumference of the laminated drum on the second inner roll side, a two-layer carbon nanotube laminated film is formed, in which a carbon nanotube film newly formed in the second cycle is laminated on top of the carbon nanotube film formed in the first cycle. A method for manufacturing a long sheet made of carbon nanotubes, characterized in that a single layer of the carbon nanotube laminated film, which is newly formed in the second cycle, is formed on half of the first inner roll side of the laminated drum [5]. [7] Length 100m or more, width 1m or more, and basis weight 0.0226mg / cm 2 More than 170mg / cm 2 The following are long sheets made of carbon nanotubes. [8] A long sheet of carbon nanotubes made of 20 to 10,000 layers of carbon nanotube webs [7]. [9] [7] Long sheets made of carbon nanotubes, A release film is placed on both surfaces of the long sheet made of carbon nanotubes and A laminate including

Advantages of the Invention

[0012] According to the present invention, it is possible to provide a highly useful long CNT sheet, a laminate including the long CNT sheet, a long CNT sheet manufacturing apparatus for efficiently manufacturing the long CNT sheet, and a long CNT sheet manufacturing method.

Brief Description of the Drawings

[0013] [Figure 1] It is a perspective view showing an outline of a long CNT sheet manufacturing apparatus according to an embodiment. [Figure 2] It is a schematic view showing a state of a setting step (S1) in which a release film fed out from a first inner roll is wound around an outer periphery of a laminating drum in a long CNT sheet manufacturing method according to an embodiment. [Figure 3] It is a schematic view showing a state of a layer forming step (S2) of forming a first layer of carbon nanotubes (hereinafter referred to as a first CNT film layer) on a release film wound around an outer periphery of a laminating drum in a long CNT sheet manufacturing method according to an embodiment. [Figure 4] It is a schematic view showing a state of a CNT layer cutting step (S3) of cutting a position of a non - continuous portion and a covering step (S4) of covering a first CNT film layer with an additional release film having a length corresponding to a half circumference of a laminating drum in a long CNT sheet manufacturing method according to an embodiment. [Figure 5] It is a schematic view showing a state in which a sandwich - like layer is formed on a half circumference on the second inner roll side of an outer periphery of a laminating drum and a base layer is formed on a half circumference on the first inner roll side of an outer periphery of a laminating drum in a long CNT sheet manufacturing method according to an embodiment. [Figure 6] It is a schematic view showing a state of a winding step (S5) of winding a sandwich - like layer around a second inner roll in a long CNT sheet manufacturing method according to an embodiment. [Figure 7]This is a schematic diagram showing the layer formation process (S2) of the second cycle in the CNT long sheet manufacturing method according to the embodiment, in which a second CNT film layer is formed on top of the first CNT film layer. [Figure 8] This is a schematic diagram showing the second cycle CNT layer cutting step (S3), in which the discontinuous portion is cut, and the second cycle coating step (S4), in which a release film with a length equivalent to half the circumference of the laminated drum is placed over the second layer of CNT film, in a CNT long sheet manufacturing method according to an embodiment. [Figure 9] This is a schematic diagram showing a CNT long sheet manufacturing method according to an embodiment, in which a sandwich-like layer is formed on the second inner roll side of the outer circumference of the laminated drum, and a base layer is formed on the first inner roll side of the outer circumference of the laminated drum. [Figure 10] This is a schematic diagram showing the winding process (S5) of the second cycle in the CNT long sheet manufacturing method according to the embodiment, in which a sandwich-like layer is wound onto a second inner roll. [Figure 11] This is a schematic diagram showing the layer formation process (S2) of the third cycle in the CNT long sheet manufacturing method according to the embodiment, in which a second CNT film layer is formed on top of the first CNT film layer. [Figure 12] This is a schematic diagram showing the process of obtaining a long sheet made of CNT according to the embodiment. [Modes for carrying out the invention]

[0014] Hereinafter, an embodiment of the CNT long sheet manufacturing apparatus according to the present invention will be described with reference to the drawings. Figure 1 is a perspective view showing an overview of the CNT long sheet manufacturing apparatus.

[0015] In this disclosure, expressions describing relative or absolute arrangements such as "in a certain direction," "along a certain direction," "parallel," "orthogonal," "center," "intermediate," "concentric," or "coaxial" not only strictly describe such arrangements but also include states of relative displacement with tolerances or angles or distances sufficient to achieve the same function.

[0016] As shown in Figure 1, the CNT long sheet manufacturing apparatus 2 comprises a laminated drum 4, a first inner roll 6, a second inner roll 8, and a substrate 15 to which the CNT forest 16 is attached.

[0017] The laminated drum 4 is a cylindrical drum having a cylindrical hollow space 10 inside, and is equipped with a slit-shaped discontinuous portion 12 extending in a direction parallel to the axial direction. The length of the outer circumference of the laminated drum 4 is preferably 1.5m to 10m, more preferably 2m to 6m from the viewpoint of workability, and even more preferably 2.5m to 4m. From the viewpoint of manufacturing long sheets of CNT with a small number of cycles, it is more preferably 6m to 10m, and even more preferably 8m to 10m. The thickness of the laminated drum 4 is preferably 0.1cm to 5cm. The material used for the laminated drum 4 may be resin or metal.

[0018] A release film 13 made of paper or vinyl resin is wrapped around the outer circumference of the laminated drum 4, and a CNT web 14 is wound on top of the release film 13. The CNT web 14 is normally laminated and laminated on top of the release film 13 as a CNT film.

[0019] The laminated drum 4 is rotatably arranged such that the discontinuous portion 12 is located at a predetermined position on the outer circumference. The following description will use the case where the laminated drum 4 is rotatably arranged such that the discontinuous portion 12 is located at the top of the outer circumference as an example. In this case, as shown in Figure 2, a first inner roll 6 and a second inner roll 8 are provided in the hollow space 10 of the laminated drum 4 near the central axis X of the laminated drum 4.

[0020] The first inner roll 6 is a cylindrical roll for winding the release film 13, which is fed out toward the outer circumference of the laminated drum 4. The outer diameter of the first inner roll 6 is preferably 1 cm or more and 15 cm or less, more preferably 5 cm or more and 10 cm or less, and even more preferably 7 cm or more and 8 cm or less.

[0021] The second inner roll 8 is a cylindrical roll for recovering and winding the release film 13, on which the CNT film is laminated, from the outer circumference of the laminated drum 4. The outer diameter of the second inner roll 8 is preferably 1 cm to 15 cm, more preferably 5 cm to 10 cm, and even more preferably 7 cm to 8 cm.

[0022] Here, the axial lengths of the first inner roll 6 and the second inner roll 8 are equal to those of the stacked drum 4. Furthermore, the first inner roll 6 and the second inner roll 8 are positioned such that their respective central axes, 6x and 8x, are located between the central axis X of the stacked drum 4 and the outer circumference of the stacked drum 4.

[0023] Furthermore, it is preferable that the central axis 6x of the first inner roll 6 and the central axis 8x of the second inner roll 8 are located midway between the central axis X of the laminated drum 4 and the outer circumference of the laminated drum 4. This allows for maximizing the winding capacity of each inner roll.

[0024] In this embodiment, the first inner roll 6 and the second inner roll 8 are positioned symmetrically across a straight line Y connecting the central axis X and the midpoint of the discontinuous portion 12. Furthermore, the ends of both the first inner roll 6 and the second inner roll 8 on the axial depth side are fixed to the stacking drum 4 (not shown).

[0025] The CNT forest 16 is an aggregate of multiple CNTs arranged on a substrate 15 and oriented perpendicular to the surface of the substrate 15. In the CNT forest 16, multiple CNTs stand upright on the substrate 15. By drawing out multiple CNTs 11 from the CNT forest 16 in a sheet-like manner using van der Waals forces, a CNT web 14 (a web consisting of one layer) can be obtained. A stack of multiple CNT webs 14 is referred to as a CNT film.

[0026] Next, a method for manufacturing a long sheet made of CNT according to an embodiment of the present invention will be described with reference to the drawings. In this embodiment, an example is given in which an additional release film 20 (details to be described later) with a length equivalent to half the circumference of the lamination drum 4 is used to wind the CNT film in half-circle increments, thereby obtaining a long sheet made of CNT by laminating two layers of CNT film.

[0027] First, the operator sets the wound release film 13 onto the first inner roll 6, as shown in Figure 2. Next, the release film 13 is unwound from the first inner roll 6, passed through the discontinuous section 12, and made to circle the outer circumference of the laminated drum 4 in the direction of the first inner roll 6 (counterclockwise in Figure 2). Then, the leading edge of the release film 13 is inserted from the discontinuous section 12 into the hollow space 10 and fixed onto the second inner roll 8. Furthermore, in this state, the second inner roll 8 is rotated counterclockwise in Figure 2 to wind the release film 13 onto the second inner roll 8 (S1: setting process).

[0028] Here, as shown in Figure 3, the operator rotates the lamination drum 4 counterclockwise, drawing out multiple CNTs 11 from the CNT forest 16 in a sheet-like manner using van der Waals forces, and bringing them into contact with the release film 13 wrapped around the outer circumference of the lamination drum 4. This first forms a CNT web 14 (see Figure 1) on the release film 13.

[0029] Then, with the CNT web 14 in contact with the release film 13, the lamination drum 4 is rotated multiple times. This forms a first layer of CNT film 17, in which multiple layers of CNT web 14 are laminated on top of the release film 13 wrapped around the outer circumference of the lamination drum 4.

[0030] For example, when manufacturing a long sheet of CNT with a length of 100m and a width of 1m using a lamination drum 4 with an outer diameter of 1m, first, the lamination drum 4 is rotated 25 times with the CNT web 14 in contact with the release film 13. This forms a first layer 17 of CNT film, consisting of 25 layers of CNT web 14, on the release film 13 (S2: layer formation process).

[0031] Next, the worker uses a sharp tool such as a knife to cut the first layer 17 of the CNT film laminated on the outer circumference of the laminated drum 4 at the location of the discontinuous portion 12 (S3: cutting process). This exposes the discontinuous portion 12 so that it can be seen from the outside again. Here, the discontinuous portion 12 defines a groove sandwiching two ridges that extend in the axial direction of the laminated drum 4. In the direction of rotation of the laminated drum 4, the ridge located in the leading direction of rotation is defined as the leading ridge 22a, and the ridge located in the trailing direction of rotation is defined as the trailing ridge 22b (see Figure 3).

[0032] Next, the worker prepares an additional release film 20 that is the length of half the circumference of the laminated drum 4. The width of the additional release film 20 is the same as that of the release film 13 that was wrapped around the laminated drum 4 in the setup step (S1). As shown in Figure 4, the worker attaches and fixes the short side of the additional release film 20 to the position of the trailing edge 22b of the release film 13, and covers the first layer of CNT film 17 with the additional release film 20 (S4: covering step).

[0033] As a result, as shown in Figure 5, on the outer circumference of the laminated drum 4, a sandwich-like layer 24 is formed on the second inner roll 8 side (right side in Figure 5) of the laminated drum 4, where the first layer of CNT film 17 is sandwiched between a release film 13 and an additional release film 20, and on the first inner roll 6 side (left side in Figure 5) half of the circumference, a base layer 19 is formed where the first layer of CNT film 17 is laminated on the release film 13.

[0034] Next, the operator rotates the second inner roll 8 counterclockwise, as shown in Figure 6, to wind up the release film 13. By continuing to wind up the release film 13, the sandwich-like layer 24 is wound onto the second inner roll 8 (S5: winding process). That is, the first layer 17 of the CNT film (for example, 25 layers of CNT web 14) with a length equivalent to half the circumference of the laminated drum 4 is wound onto the second inner roll 8.

[0035] In this state, a single layer of CNT laminated film consisting only of the first layer of CNT film 17 is formed on the release film 13 wrapped around the outer circumference of the laminated drum 4, on the half-circumference on the side of the second inner roll 8.

[0036] The following steps are repeated multiple times: layer formation (S2), cutting (S3), coating (S4), and winding (S5). Specifically, when producing a 100m long sheet of CNT, the layer formation (S2), cutting (S3), coating (S4), and winding (S5) steps are repeated 66 times.

[0037] Note that the second cycle and beyond differ from the first cycle in that the second layer of carbon nanotube film (hereinafter referred to as the second CNT film layer), described later, is laminated on top of the first CNT film layer 17. Also, the first CNT film layer 17 and the second CNT film layer are collectively referred to as the CNT layer. The process from the second cycle onward will be explained below.

[0038] In the winding process (S5), when the rear end of the sandwich-like layer 24 in the winding direction reaches the discontinuous portion 12 (see Figure 6), the operator, as shown in Figure 7, pulls out the CNT 11 again from the CNT forest 16 and rotates the lamination drum 4 the same number of times as in the first cycle's layer formation process (S2) while bringing it into contact with the first layer 17 of the CNT film formed on the release film 13 (S2: layer formation process). For example, if the lamination drum 4 was rotated 25 times in the first cycle's layer formation process (S2), the lamination drum 4 is rotated 25 times in the same manner.

[0039] As a result, on the release film 13 wrapped around the outer circumference of the laminated drum 4, a second CNT film layer 26 is newly formed on the half-circumference on the second inner roll 8 side (right side in Figure 7), by laminating the same number of CNT webs 14 (25 layers in this embodiment) on top of the first CNT film layer 17 formed in the first cycle, and a first CNT film layer 17 is newly formed on the half-circumference on the first inner roll 6 side (left side in Figure 7).

[0040] In other words, the CNT film newly wound in the second cycle forms a second layer of CNT film 26 on top of the first layer of CNT film 17 generated in the second cycle on the half-circumference on the second inner roll 8 side, and becomes a new first layer of CNT film 17 on the half-circumference on the first inner roll 6 side. On the half-circumference on the second inner roll 8 side, a two-layer CNT laminated film 28 is formed, consisting of the first layer of CNT film 17 and the second layer of CNT film 26.

[0041] Here, no release film 13 is placed between the first CNT film layer 17 and the second CNT film layer 26, and the first CNT film layer 17 and the second CNT film layer 26 are in direct contact. Therefore, when the lamination drum 4 is rotated 25 times in the layer formation process (S2), a CNT laminated film 28 is formed on the release film 13, consisting of 50 layers of CNT web 14.

[0042] Next, as shown in Figure 8, the worker cuts the first layer 17 of the CNT film newly laminated on the lamination drum 4 at the location of the discontinuous portion 12 (S3: cutting process).

[0043] Then, the worker attaches and fixes the short side of the additional release film 20 to the position of the trailing edge 22b of the release film 13, and covers the second layer of CNT film 26 with the additional release film 20 (S4: covering process). As a result, as shown in Figure 9, on the outer circumference of the laminated drum 4, a sandwich-like layer 29 is formed on the second inner roll 8 side (right side in Figure 9) where the CNT laminated film 28, which consists of the first layer of CNT film 17 and the second layer of CNT film 26, is sandwiched between the release film 13 and the additional release film 20, and on the first inner roll 6 side (left side in Figure 9) where the base layer 19 is formed on the release film 13 where the first layer of CNT film 17 is laminated, is formed on the release film 13.

[0044] Next, the operator rotates the second inner roll 8 counterclockwise, as shown in Figure 10, to wind up the release film 13. By continuing to wind up the release film 13, the sandwich-like layer 29 is wound onto the second inner roll 8 (S5: winding process).

[0045] In this state, a single layer of CNT laminated film consisting only of the first layer of CNT film 17 is formed on the release film 13 wrapped around the outer circumference of the laminated drum 4, on the half-circumference on the side of the second inner roll 8.

[0046] When the rear end of the sandwich-like layer 29 in the winding direction reaches the discontinuous portion 12, the process proceeds to the third cycle of layer formation (S2). Here, as shown in Figure 11, the operator pulls out the CNTs 11 again from the CNT forest 16 and rotates the lamination drum 4 the same number of times as in the second cycle of layer formation (S2), while bringing it into contact with the first layer 17 of the CNT film formed on the release film 13.

[0047] As a result, on the release film 13 wrapped around the outer circumference of the laminated drum 4, a second CNT film layer 26 is newly formed on the half-circumference on the second inner roll 8 side (right side in Figure 11), by laminating the same number of CNT webs 14 (25 layers in this embodiment) on top of the first CNT film layer 17 formed in the second cycle, and a first CNT film layer 17 is newly formed on the half-circumference on the first inner roll 6 side (left side in Figure 11).

[0048] In other words, the CNT film newly wound in the third cycle forms a second CNT film layer 26 on top of the first CNT film layer 17 generated in the second cycle on the half-circumference on the second inner roll 8 side, and forms a new first CNT film layer 17 on the half-circumference on the first inner roll 6 side. On the half-circumference on the second inner roll 8 side, a two-layer CNT laminated film 28 consisting of the first CNT film layer 17 and the second CNT film layer 26 is formed.

[0049] In the final cycle, after the winding process (S5), the next layer formation process (S2) is skipped and the process proceeds to the cutting process (S3). That is, the first layer 17 of CNT film laminated on the outer circumference of the laminated drum 4 is cut at the position of the discontinuous portion 12. Next, an additional release film 20 is placed over the first layer 17 of CNT film and covers the entire circumference of the laminated drum 4 (S4: covering process), and the second inner roll 8 is rotated counterclockwise to wind up the release film 13 (S5: winding process).

[0050] As a result, a sandwich-like layer 24, in which the first layer 17 of the CNT film, similar to that of the first cycle, is sandwiched between a release film 13 and an additional release film 20, is wound onto the second inner roll 8. After removing the wound material from the second inner roll 8, the worker unwinds the material to make it into a long length.

[0051] As a result, as shown in Figure 12(a), a laminate 32 can be obtained in which a long CNT laminate film 30, whose ends are made of a first CNT film layer 17, is sandwiched between a release film 13 and an additional release film 20. The laminate 32 is a structure in which a long CNT sheet 34 (see Figure 12(c)) is sandwiched between a release film 13 and an additional release film 20.

[0052] Here, the worker cuts the portions consisting of the first layer 17 of the CNT film at both ends together with the release film 13 and the additional release film 20 to obtain a laminate 32 of uniform thickness, as shown in Figure 12(b). That is, the laminate 32 obtained here is a structure in which a long sheet 34 made of CNT of uniform thickness (see Figure 12(c)) is sandwiched between the release film 13 and the additional release film 20.

[0053] The user cuts the uniformly thick laminate 32 to a predetermined length as needed each time, then peels off the release film 13 and additional release film 20 to obtain a long sheet 34 made of CNT consisting only of CNT laminate film 28, as shown in Figure 12(c).

[0054] The CNT long sheet 34 constituting the laminate 32 (see Figure 12(a)) has a length of at least 50 m, preferably 100 m, more preferably 105 m, and particularly preferably 110 m or more. There is no particular upper limit on the length, but for example, it is 1000 m or less, preferably 500 m or less. There is no particular limit on the width of the CNT long sheet 34, but for example, it is 10 cm or more and 5 m or less, preferably 50 cm or more and 4 m or less, and more preferably 1 m or more and 3 m or less. The CNT long sheet 34 has a length of 100 m or more, a width of 1 m or more, and a basis weight of 0.02260 mg / cm². 2 More than 170mg / cm 2 One preferred embodiment is as follows: The user may use the material after cutting it to the desired length and shape.

[0055] There is no particular limitation on the use of the long CNT sheet 34. For example, it can be compounded with a thermoplastic resin or a thermosetting resin to produce a prepreg, and by molding the prepreg, it can be used as an automotive member, a machine tool member, an aircraft member, a drone member, a sports and leisure member, a suitcase member, etc.

[0056] The basis weight of the long CNT sheet 34 may be set according to the purpose of the long CNT sheet, and there is no particular limitation. However, for example, from the viewpoints of productivity and adhesiveness, etc., it is preferably 0.0226 mg / cm 2 or more and 170 mg / cm 2 or less, more preferably 0.0339 mg / cm 2 or more and 85 mg / cm 2 or less, even more preferably 0.0565 mg / cm 2 or more and 17 mg / cm 2 or less. The basis weight of the long CNT sheet 34 can be determined, for example, by measuring the mass of part or all of the long CNT sheet 34 with a mass meter and dividing the mass by the area of part or all of the long CNT sheet 34.

[0057] In addition, in the above-described embodiment, the case where the CNT long sheet 34 is manufactured by repeating the layer formation step (S2), the cutting step (S3), the coating step (S4), and the winding step (S5) while collecting the sandwich-like layers 24 and 29 for half of the outer circumference of the lamination drum 4 is illustrated. However, the method for manufacturing the long CNT sheet is not necessarily limited to this cycle. For example, the layer formation step (S2), the cutting step (S3), the coating step (S4), and the winding step (S5) may be repeated while collecting the sandwich-like layer for one-third or one-fourth of the outer circumference of the lamination drum 4.

[0058] For example, when manufacturing a long sheet 34 made of CNTs by repeatedly performing the layer formation process (S2), cutting process (S3), coating process (S4), and winding process (S5) while recovering the sandwich-like layer in 1 / n turns of the outer circumference of the laminated drum 4, the operator prepares an additional release film 20 in the coating process (S4) that is equivalent in length to 1 / n turns of the outer circumference of the laminated drum 4. The operator attaches and fixes the short side of this additional release film 20 to the position of the trailing edge 22b of the release film 13, and covers the second layer 26 of the CNT film with the additional release film 20. Then, the operator rotates the second inner roll 8 counterclockwise and winds the release film 13 for 1 / n turns of the laminated drum 4 (S5: winding process).

[0059] Immediately before the winding process (S5) of the nth cycle, a CNT laminated film consisting of n layers of CNT film, a CNT laminated film consisting of n-1 layers of CNT film, ..., and a first CNT film layer 17 are formed on the release film 13 wound around the outer circumference of the laminated drum 4, in order from the end of the discontinuous portion 12 on the second inner roll 8 side toward the end on the first inner roll 6 side. At this point, an additional release film 20 is covered on top of the CNT laminated film consisting of n layers of CNT film.

[0060] For example, when n=3, on the release film 13 wrapped around the outer circumference of the laminated drum 4, a three-layer CNT laminated film 28 is formed by laminating a third CNT film, a second CNT film 26, and a first CNT film 17, in order from the end of the discontinuous portion 12 on the second inner roll 8 side toward the end on the first inner roll 6 side, a two-layer CNT laminated film 28 is formed by laminating the second CNT film 26 and the first CNT film 17, and a single layer CNT laminated film 28 is formed by laminating only the first CNT film 17.

[0061] The uppermost layer of each CNT film is formed by a CNT film newly wound during the nth cycle. The first layer 17 of the CNT film is itself formed by a CNT film newly wound during the nth cycle.

[0062] Here, let's consider the CNT laminated film, which is located at the end of the discontinuous portion 12 on the second inner roll 8 side, immediately before the winding process (S5) of the nth cycle, and in which n layers of CNT film are laminated. Then, the uppermost layer of the CNT laminated film is formed by the CNT film newly wound in the nth cycle, the second layer (if any) on top of the CNT laminated film is formed by the CNT film newly wound in the (n-1)th cycle, and the bottommost layer of the CNT laminated film is the CNT film laminated in the first cycle [the (n-(n-1))th cycle], i.e., the first CNT film layer 17, which is formed as the CNT laminated film.

[0063] Similarly, let's consider the CNT laminated film, which consists of n layers of CNT film, located at the end of the discontinuous portion 12 on the second inner roll 8 side, immediately before the winding process (S5) of the (n+1)th cycle. Then, the top layer of the CNT laminated film is formed by the CNT film newly wound in the (n+1)th cycle, the second layer (if any) above the CNT laminated film is formed by the CNT film newly wound in the nth cycle, and the bottom layer of the CNT laminated film is the CNT film laminated in the second cycle [the (n+1-(n-1))th cycle], i.e., the first CNT film layer 17, which is formed as the CNT laminated film.

[0064] Thus, on the outer circumference of the laminated drum 4, CNT films formed in a new cycle are stacked on top of CNT films formed in a previous cycle, and as you move from the end of the discontinuous portion 12 on the second inner roll 8 side to the end on the first inner roll 6 side (counterclockwise), the number of CNT laminated films increases from one layer to n layers. For this reason, in a CNT laminated film in which multiple layers of CNT films are stacked, the higher the layer, the more CNT films formed in newer cycles are stacked.

[0065] Furthermore, if we consider 1 / n of the circumference, the preferred range for n is 2 to 6. Furthermore, although the above-described embodiment illustrates the case in which the stacked drum 4, the first inner roll 6, and the second inner roll 8 are rotated counterclockwise, they may of course be rotated clockwise as well.

[0066] Furthermore, although the above-described embodiment illustrates the case where the first inner roll 6 and the second inner roll 8 are cylindrical rolls, the first inner roll 6 and the second inner roll 8 may also be cylindrical rolls.

[0067] Furthermore, in the above-described embodiment, an example was given in which the short side of the additional release film 20 is attached and fixed to the position of the trailing ridge 22b of the release film 13 during the coating process (S4). However, it is not necessarily required that the short side be fixed to the position of the trailing ridge 22b; any side will suffice. For example, if the outer circumference of the lamination drum 4 is short, or if the length of the additional release film 20 is short and the number of rotations of the lamination drum 4 is high, it may be possible that the short side is not the one fixed to the position of the trailing ridge 22b.

[0068] Furthermore, although the above-described embodiment illustrates a case where the CNT long sheet 34 is formed by laminating 50 layers of CNT web 14, the CNT long sheet 34 may be formed by laminating, for example, 20 to 10,000 layers of CNT web 14. The number of layers of CNT web 14 in the CNT long sheet can be set according to the application of the CNT long sheet and is not particularly limited, but from viewpoints such as productivity and mechanical properties, it is preferably 20 to 10,000 layers, more preferably 30 to 5,000 layers, and even more preferably 50 to 1,000 layers. [Explanation of symbols]

[0069] 2 CNT long sheet manufacturing equipment 4-layer drum 6. First Inner Roll 6x Central axis of the first inner roll 8. Second Inner Roll 8x Second Inner Roll Central Axis 10 Hollow space 11 CNT 12. Discontinuous portions 13 Release film 14 CNT Web 15 circuit boards 16 CNT Forest 17 CNT film first layer 19 Base layer 20 Additional release film 22a Leading Ridge 22b Rear ridge 24, 29 Sandwich-like layers 26 CNT film second layer 28 CNT laminated film 30 Long-length CNT laminated film 32 Laminate 34 CNT long sheet X Central axis of stacked drum 4 Y is a straight line connecting the central axis X and the midpoint of the discontinuous section 12.

Claims

1. Length of 100m or more, width of 1m or more, and basis weight of 0.0226 mg / cm² ２ More than 170mg / cm ２ The following are long sheets made of carbon nanotubes.

2. A long carbon nanotube sheet according to claim 1, comprising 20 to 10,000 layers of carbon nanotube webs laminated together.

3. A long sheet made of carbon nanotubes according to claim 1, wherein 97% by mass or more and 100% by mass or less is composed of carbon nanotubes.

4. A long sheet made of carbon nanotubes according to claim 1, A release film is placed on both surfaces of the long sheet made of carbon nanotubes and A laminate containing the above.

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