Composite, production method for composite, and use for composite

Abstract

One embodiment of a composite according to the present disclosure comprises: a first member containing a first carbonaceous material; a second member containing a second carbonaceous material; and a web-shaped body of carbon nanotubes which is positioned between the first member and the second member, and is in contact with the first member and the second member, respectively.

Description

Composite, method for manufacturing the composite, and use of the composite

[0001] The present disclosure relates to composites, methods for producing composites, and uses of composites.

[0002] One proposed application of carbon nanotubes is to mold multiple carbon nanotubes and use them in products such as heaters. For example, Patent Document 1 proposes a surface heat source that includes a rectangular heating element formed by laminating a carbon nanotube film and two electrodes connected to both ends of the heating element.

[0003] JP 2010-257971 A

[0004] Although the use of carbon nanotube films in products such as heaters has been proposed, once carbon nanotube films are produced, they usually do not adhere to each other even when they are stacked and pressure is applied to the overlapping portions. Furthermore, in order to utilize carbon nanotube films in products without damaging their electrical properties, it is desirable to bond carbon nanotube films to each other without using adhesives containing resins such as epoxy resins.

[0005] Therefore, an object of the present disclosure is to provide a composite in which members containing a carbon material are bonded together without using an adhesive containing a resin, and a method for producing the same.

[0006] One aspect of the composite of the present disclosure comprises a first member including a first carbon material, a second member including a second carbon material, and a web of carbon nanotubes located between the first member and the second member and in contact with each of the first member and the second member.

[0007] According to the present disclosure, it is possible to provide a composite in which members containing a carbon material are bonded together without using an adhesive containing a resin, and a method for producing the composite.

[0008] Fig. 1 is a schematic cross-sectional view of a composite according to one embodiment. Fig. 2 is a schematic cross-sectional view of a composite according to one embodiment. Fig. 3 is a top view of a carbon nanotube forest and a carbon nanotube web, illustrating a method for producing a carbon nanotube web. Fig. 4 is a cross-sectional view taken along line AA in Fig. 3.

[0009] An example of an embodiment of the present disclosure will be described in detail below with reference to the drawings. Note that the drawings used in the following description may show characteristic portions enlarged for convenience in order to make the features of the contents of the present disclosure easier to understand. Therefore, the dimensional ratios of each component may differ from the actual ones.

[0010] In this specification, a numerical range A to B means not less than A and not more than B. In this specification, when the units of the numerical values ​​written before and after "to" indicating a numerical range are the same, the unit of the numerical value written before "to" may be omitted.

[0011] In this specification, carbon nanotubes are also referred to as "CNTs," carbon nanotube forests are also referred to as "CNT forests," carbon nanotube fibers are also referred to as "CNT fibers," and webs of carbon nanotubes are also referred to as "CNT webs."

[0012] In this specification, "parallel" includes not only strictly parallel but also approximately parallel. Regarding parallel, the angle formed by them may be, for example, 30° or less, 20° or less, 10° or less, or 5° or less. Regarding "perpendicular" in this specification, "perpendicular" includes not only strictly perpendicular but also approximately perpendicular, and "orthogonal" includes not only strictly perpendicular but also approximately perpendicular. Regarding perpendicular and orthogonal, the angle formed by them may be, for example, 60° or more and 90° or less, 70° or more and 90° or less, 80° or more and 90° or less, or 85° or more and 90° or less.

[0013] [Composite] The composite of the present disclosure comprises a first member containing a first carbon material, a web of carbon nanotubes, and a second member containing a second carbon material. The web of carbon nanotubes is located between the first member and the second member. The web of carbon nanotubes is in contact with both the first member and the second member.

[0014] 1 and 2 comprises a first member 10, a second member 20, and a CNT web-like body 30 located between the first member 10 and the second member 20. The CNT web-like body 30 is in contact with the first member 10, and the CNT web-like body 30 is in contact with the second member 20.

[0015] <Web of Carbon Nanotubes> The composite includes a web of carbon nanotubes (CNT web). A CNT web refers to a web containing a plurality of CNT fibers. For example, when the CNT web is viewed in a plan view, the CNT web may be an aggregate in which a plurality of CNT fibers extend in one direction and are aligned in a direction perpendicular to that direction. "Viewing the CNT web in a plan view" means viewing the planar CNT web from its normal direction.

[0016] For example, when viewed from above, the CNT web may be an assembly including a first fiber group in which a plurality of CNT fibers extend along a first direction and are aligned in a direction perpendicular to the first direction, and a second fiber group in which a plurality of CNT fibers extend along a second direction and are aligned in a direction perpendicular to the second direction, where the first direction and the second direction intersect. The angle between the first direction and the second direction is not particularly limited. The first direction and the second direction may be, for example, perpendicular to each other. The CNT web may further include an nth fiber group (n is an integer of 3 or greater) in which a plurality of CNT fibers extend along an nth direction and are aligned in a direction perpendicular to the nth direction.

[0017] In the composite, the first and second components are bonded together via the CNT web, which serves to bond the components containing carbon materials together.

[0018] In conventional carbon nanotube films (CNT films), the surface energy due to the van der Waals forces of the CNTs is stabilized, resulting in low adhesive strength between CNT films. Therefore, even if two CNT films are stacked on top of each other and pressure is applied to the overlapping portions, the CNT films usually do not adhere to each other. In contrast, a CNT web is presumed to maintain a high surface energy due to the van der Waals forces of the CNTs compared to a CNT film, and therefore has a high adhesive strength. For these reasons, a CNT web can bond components containing carbon materials, such as CNT films, together.

[0019] CNT webs can be produced using CNT fibers. CNT fibers can be produced, for example, by extracting multiple CNTs from a CNT forest. CNT webs can be produced, for example, by extracting multiple CNTs from a CNT forest, specifically by extracting multiple CNTs in a sheet form. The size of the CNT web can be adjusted by adjusting the width of the CNTs extracted from the CNT forest.

[0020] A CNT forest is an aggregate of CNTs arranged on a substrate and aligned perpendicular to the surface of the substrate.

[0021] CNT forests can be obtained, for example, by chemical vapor deposition (CVD) using a catalyst substrate comprising a substrate and a catalyst layer provided on the substrate. CVD involves placing the catalyst substrate in a reaction chamber, supplying raw material gas into the chamber, and growing CNTs on the surface of the catalyst layer. Thermal CVD is preferred as the CVD method.

[0022] Examples of the substrate include a silicon substrate, an alumina substrate, a magnesium oxide substrate, a glass substrate, a sapphire substrate, and a stainless steel substrate.

[0023] The catalyst layer can be formed by depositing catalyst particles on the substrate, for example, by sputtering. Examples of catalysts include metals, specifically iron (Fe), nickel (Ni), cobalt (Co), molybdenum (Mo), gold (Au), and alloys containing at least one metal selected from the group consisting of these. Examples of alloys include iron alloys, nickel alloys, and cobalt alloys. The catalyst may also be a metal precursor, such as a metal oxide or a metal compound. Examples of metal oxides include iron oxide, nickel oxide, and cobalt oxide. Examples of metal compounds include iron chloride. When a precursor is used, it must be converted to a metal by, for example, heating the precursor before performing the CVD method.

[0024] The catalyst substrate may further include a buffer layer between the substrate and the catalyst layer. Materials used for the buffer layer include, for example, silica (SiO), alumina (AlO), silicon nitride (SiN), zinc oxide (ZnO), copper oxide (CuO), and nickel oxide (NiO). The buffer layer can be formed, for example, by sputtering.

[0025] The sputtering for forming the catalyst layer and the sputtering for forming the buffer layer can be performed using known apparatus and conditions depending on the target of sputtering. The pressure condition for sputtering is preferably about 0.01 to 10 Pa, more preferably about 0.1 to 1 Pa.

[0026] The source gas may be a carbon-containing source gas, such as a hydrocarbon, a sulfur-containing organic gas, a phosphorus-containing organic gas, carbon monoxide, or an alcohol. Examples of hydrocarbons include alkane compounds such as methane and ethane, alkene compounds such as ethylene and butadiene, alkyne compounds such as acetylene, aryl hydrocarbon compounds such as benzene, toluene, and styrene, aromatic hydrocarbons with condensed rings such as indene, naphthalene, and phenanthrene, cycloalkane compounds such as cyclopropane and cyclohexane, cycloolefin compounds such as cyclopentene, and alicyclic hydrocarbon compounds with condensed rings such as steroids. Examples of alcohols include methanol and ethanol. From the viewpoint of the purity of the resulting CNTs, the source gas is preferably a hydrocarbon.

[0027] A carrier gas, which is a gas that carries the source gas, may be supplied to the reaction chamber together with the source gas. Examples of the carrier gas include helium, neon, argon, nitrogen, and hydrogen.

[0028] The temperature in the reaction chamber in the CVD method is preferably 600 to 850°C, more preferably 650 to 800°C, from the viewpoints of the growth rate of CNTs and the purity of the resulting CNTs. The pressure in the reaction chamber in the CVD method is preferably atmospheric pressure, from the viewpoints of the growth rate and purity of CNTs. The pressure in the reaction chamber may be reduced or increased from atmospheric pressure depending on other conditions when the CVD method is carried out.

[0029] The average length of the CNTs in the CNT forest is preferably 10 to 1000 μm, more preferably 30 to 800 μm, and even more preferably 50 to 500 μm. The average length of the CNTs in the CNT forest can be adjusted, for example, by adjusting the time for which the CVD method is performed, i.e., the CNT growth time.

[0030] The average diameter of the CNTs is preferably 1 to 50 nm, more preferably 3 to 30 nm, and even more preferably 5 to 15 nm. The average diameter of the CNTs can be adjusted, for example, by adjusting the thickness of the catalyst layer and the type of catalyst.

[0031] The average length and average diameter of CNTs are measured using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Specifically, 10 images of CNTs are obtained using an SEM or TEM. Ten length measurement points are randomly selected and measured for each of the 10 images, resulting in a total of 100 length measurements. The average length of the CNTs is then determined by arithmetically averaging the 100 length measurements. Additionally, ten diameter measurement points are randomly selected and measured for each of the 10 images, resulting in a total of 100 diameter measurements. The average diameter of the CNTs is then determined by arithmetically averaging the 100 diameter measurements.

[0032] The carbon purity of the CNT is preferably 95.0 to 99.999%. The lower limit of the carbon purity of the CNT is preferably 96.0%, more preferably 97.0%, even more preferably 98.0%, still more preferably 99.0%, and particularly preferably 99.8%. The upper limit of the carbon purity of the CNT may be, for example, 99.99% or 99.9%. The carbon purity of the CNT can be determined, for example, by elemental analysis using fluorescent X-rays.

[0033] The crystallinity of CNTs can be evaluated, for example, by Raman spectroscopy. In the evaluation of crystallinity by Raman spectroscopy, the value of the D / G ratio is used as an index. The D / G ratio is the ratio of the D / G ratio at 1580 cm -1 The G band peak intensity appearing near 1360 cm -1 The D / G ratio is the ratio of the peak intensity of the D band that appears near the center of the carbon nanotube. The smaller the D / G ratio, the higher the crystallinity of the carbon nanotube. The D / G ratio of CNTs is preferably 0.5 to 1.0, and more preferably 0.6 to 0.8.

[0034] The purity and crystallinity of the CNTs can be adjusted, for example, by adjusting the thickness of the buffer layer, the type of buffer, the thickness of the catalyst layer, the type of catalyst, the type and flow rate of the raw material gas in the CVD method, and the temperature and pressure inside the reaction chamber.

[0035] The CNT may be a single-walled carbon nanotube or a multi-walled carbon nanotube having two or more walls. From the viewpoint of adhesiveness, the CNT is preferably a multi-walled carbon nanotube. The number of walls of the multi-walled carbon nanotube is not particularly limited, but is preferably 2 to 20.

[0036] The CNT web includes a plurality of CNT fibers. Each of the plurality of CNT fibers includes a plurality of CNTs. The CNT fiber is a plurality of CNTs aligned in one direction. In the CNT fiber, the longitudinal direction of the plurality of CNTs is aligned in one direction.

[0037] The CNT web-like object is preferably a CNT web obtained by extracting multiple CNTs from a CNT forest provided on a substrate, or a laminate of such CNT webs as long as the adhesive strength described above is exhibited. When the CNT web is viewed in plan, for example, the CNT web is an aggregate in which multiple CNT fibers extend in one direction and are aligned in a direction perpendicular to that direction. Hereinafter, the direction in which the CNT fibers extend in the CNT web is also referred to as the "longitudinal direction of the CNT fibers."

[0038] A CNT web can be produced, for example, by using a pinching tool such as tweezers to pull out an end-located CNT from a CNT forest in a direction parallel to the surface of the substrate on which the CNT forest is formed. When the end-located CNT is pulled out, the CNTs adjacent to the pulled CNT are successively pulled out due to van der Waals forces. The pulled CNTs are oriented so that their longitudinal directions are aligned in the direction of pulling. Therefore, the multiple CNTs that make up a CNT fiber are oriented in one direction. The multiple CNTs that make up a CNT fiber are bonded to each other by van der Waals forces. This results in a CNT web composed of multiple CNT fibers that extend in the direction the CNTs are pulled out.

[0039] A CNT web may be produced, for example, by contacting a rectangular tool with the sidewalls or top surfaces of the ends of the CNTs that make up the CNT forest, and then moving the tool away from the CNT forest in a direction parallel to the surface of the substrate on which the CNT forest is provided.

[0040] An example of a method for manufacturing a CNT web will be described with reference to the drawings. Fig. 3 is a top view illustrating the process of manufacturing a CNT web 50 using a CNT forest 42 provided on a substrate 40, and Fig. 4 is a cross-sectional view taken along line AA in Fig. 3.

[0041] 3 and 4 can be produced by pulling out, in a sheet form, multiple CNTs located at the end of a CNT forest 42 that is provided on a substrate 40 and oriented in a direction perpendicular to the surface of the substrate 40, away from the CNT forest 42 in a direction parallel to the surface of the substrate 40. When the CNT web 50 is viewed in a plan view, the CNT fibers 52 that make up the CNT web 50 extend in the direction in which the CNTs are pulled out, and multiple CNT fibers 52 are aligned in a direction perpendicular to that direction.

[0042] As will be described later, a CNT web 50 produced by pulling out multiple CNTs in parallel from a CNT forest 42 may be wound around a roller 60 to obtain a stack of CNT webs 50.

[0043] The composite preferably comprises, between the first and second members, a CNT web-like body, which is a CNT web obtained by extracting multiple CNTs from a CNT forest, or a laminate of such CNT webs.

[0044] A laminate of CNT webs can be produced, for example, by producing multiple sheet-shaped CNT webs obtained by extracting multiple CNTs from a CNT forest and then stacking these CNT webs, or by producing a roll by wrapping multiple CNT webs obtained by extracting multiple CNTs from a CNT forest around the circumferential surface of a roller, and then slicing the roll open along the direction of the roller's rotation axis. In the latter method, the number of layers of the CNT web is the number of times the CNT web is wrapped around the roller.

[0045] When a plurality of CNT webs are produced in sheet form and then stacked to produce a CNT web laminate, the CNT webs may be stacked so that the longitudinal direction of the CNT fibers constituting one CNT web is parallel to the longitudinal direction of the CNT fibers constituting another CNT web, or the CNT webs may be stacked so that they intersect (for example, orthogonal to) each other.

[0046] Examples of the shape of the CNT web include a rectangular shape, a trapezoidal shape, a parallelogram shape, a diamond shape, a kite shape, an elliptical shape, and a circular shape.

[0047] From the viewpoint of adhesiveness, the basis weight (mass per unit area) of the CNT web is preferably 0.00113 to 0.17 mg / cm 2 , more preferably 0.00113 to 0.017 mg / cm 2 , more preferably 0.00136 to 0.0136 mg / cm 2 From the viewpoint of ease of handling, the basis weight of the CNT web is preferably 0.00113 to 0.17 mg / cm 2 , more preferably 0.0113 to 0.17 mg / cm 2 , more preferably 0.0136 to 0.136 mg / cm 2 In the case where the CNT web is a CNT web laminate obtained by extracting CNTs from a CNT forest, the above basis weight is the basis weight of the laminate. The basis weight of the CNT web can be determined by measuring the mass of the CNT web using a scale such as a balance and dividing the mass by the area of ​​the CNT web.

[0048] When the CNT web-like object is a CNT web or a laminate of CNT webs, the number of layers of the CNT web is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3, from the viewpoint of adhesiveness.

[0049] In one embodiment, the CNT web is conductive only in the longitudinal direction of the CNT fibers and is substantially non-conductive in the transverse direction of the CNT fibers. In one embodiment, a laminate obtained by aligning the longitudinal directions of the CNT fibers and stacking CNT webs so that the CNT fibers are arranged in parallel is conductive only in the longitudinal direction of the CNT fibers and is substantially non-conductive in the transverse direction of the CNT fibers.

[0050] <Component Containing Carbon Material> The composite of the present disclosure includes a first component containing a first carbon material and a second component containing a second carbon material.

[0051] Examples of carbon materials include carbon nanotubes and carbon fibers. Examples of carbon fibers include pitch-based carbon fibers, polyacrylonitrile (PAN)-based carbon fibers, phenolic resin-based carbon fibers, cellulose-based carbon fibers, and polyvinyl alcohol-based carbon fibers. From the viewpoint of the electrical and mechanical properties of the composite, the carbon material is preferably carbon nanotubes. One type of carbon material may be used, or two or more types may be used.

[0052] Examples of the first and second members include carbon nanotube films, carbon fiber films, carbon fiber paper, carbon fiber felt, carbon fiber mats, and carbon fiber cloths. The first and second members preferably contain substantially only carbon materials. The first and second members are preferably carbon nanotube films.

[0053] In the above composite, at least a portion of the first component that comes into contact with the CNT web preferably contains a first carbon material, and at least a portion of the second component that comes into contact with the CNT web preferably contains a second carbon material.

[0054] The portions of the first and second members that are not in contact with the CNT web may be made of, for example, resin, fabric, metal, ceramic, glass, etc., or may be covered with resin, fabric, metal, ceramic, glass, etc. Furthermore, the entire composite may be covered with resin, etc.

[0055] Examples of the resin include epoxy resin, phenol resin, polyamide resin, polyolefin resin, polystyrene resin, polycarbonate resin, polymethyl methacrylate resin, polyethylene terephthalate resin, polyethersulfone resin, cellulose ester resin, benzocyclobutene resin, vinyl chloride resin, and acrylic resin. Examples of the material constituting the woven fabric include cotton, linen, wool, silk, nylon fiber, polyester fiber, polyacrylonitrile fiber, and polyurethane fiber.

[0056] In the above composite, all of the opposing surfaces of the first member and the second member may be bonded via the CNT web, or at least a portion of the opposing surfaces of the first member and the second member may be bonded via the CNT web.

[0057] The composite may include a plurality of first members and a plurality of second members, for example, a second member, a CNT web, a first member, a CNT web, a second member, a CNT web, and a first member in this order. Also, a plurality of first members may be adhered to one surface of the second member.

[0058] The first carbon material contained in the first member and the second carbon material contained in the second member may be the same or different. Furthermore, the first member and the second member may be the same or different. In this specification, the case where the first member and the second member are the same member is also included in the concept of a composite. From the viewpoint of adhesiveness, the first member and the second member are preferably carbon nanotube films. Hereinafter, the carbon nanotube film will also be referred to as a "CNT film."

[0059] Examples of CNT films include CNT films obtained by conventionally known methods. CNT films can be obtained, for example, by applying a dispersion of CNTs dispersed in a solvent to a substrate, drying the dispersion to remove the solvent, and peeling the dried product from the substrate; filtering the dispersion using a filter or the like and drying the CNT aggregate deposited on the surface of the filter; uniformly dispersing CNTs in an air current or the like and aggregating the CNTs on the surface of a wire mesh or the like; or by producing multiple carbon nanotube fibers (CNT fibers), gathering them together, and pressurizing the CNT fiber aggregate to bond the CNT fibers together. CNT films obtained by the above methods are typically films composed of CNTs or CNT fibers.

[0060] The CNT film may be, for example, a laminate of the above-mentioned CNT webs. In this case, the laminate has so many CNT webs stacked that it cannot be said to be a web-like body in appearance.

[0061] A laminate of CNT webs can be produced, for example, by producing multiple CNT webs in sheet form by extracting multiple CNTs from a CNT forest, and then stacking the CNT webs together; or by producing a roll by wrapping multiple CNT webs obtained by extracting multiple CNTs from a CNT forest around the periphery of a roller, and then cutting the roll open along the direction of the roller's rotational axis.

[0062] When a CNT film is produced by producing a plurality of CNT webs in sheet form and then stacking the CNT webs, the CNT webs may be stacked so that the longitudinal direction of the CNT fibers constituting one CNT web is parallel to the longitudinal direction of the CNT fibers constituting another CNT web, or the CNT webs may be stacked so that they intersect (for example, perpendicular to) each other.

[0063] Examples of the shape of the CNT film include a rectangular shape, a square shape, a trapezoid shape, a parallelogram shape, a diamond shape, a kite shape, an ellipse shape, and a circle shape.

[0064] The basis weight of the CNT film may be set depending on the purpose of the composite and is not particularly limited. However, from the viewpoints of productivity and adhesiveness, for example, it is preferably 0.0226 to 170 mg / cm 2 , more preferably 0.0339 to 85 mg / cm 2 , more preferably 0.0565 to 17 mg / cm 2 The basis weight of a CNT film is usually larger than the basis weight of a CNT web, preferably at least twice as large. The basis weight of a CNT film can be determined by measuring the mass of the CNT film using a balance and dividing the mass by the area of ​​the CNT film. When the CNT film is a laminate of CNT webs, the number of CNT web layers in the CNT film may be set depending on the purpose of the composite, and is not particularly limited. However, from the viewpoints of productivity, adhesiveness, etc., it is preferably 20 to 10,000, more preferably 30 to 5,000, and even more preferably 50 to 1,000.

[0065] The following describes a case where the first member and the second member are CNT films in which CNT webs are laminated so that the longitudinal directions of the CNT fibers are aligned and the CNT fibers are parallel, and the CNT web-like body is a CNT web or a laminate in which CNT webs are laminated so that the longitudinal directions of the CNT fibers are aligned and the CNT fibers are parallel. In this case, the composite may include the first member, the CNT web-like body, and the second member so that the CNT fibers in the first member, the CNT web-like body, and the second member are parallel, or so that the CNT fibers intersect (e.g., orthogonal). From the viewpoint of adhesive strength, it is preferable that the composite include the first member, the CNT web-like body, and the second member so that the CNT fibers in the first member, the CNT web-like body, and the second member are parallel.

[0066] In one embodiment, a CNT film in which CNT webs are laminated so that the longitudinal directions of the CNT fibers are aligned and parallel to one another has electrical conductivity only in the longitudinal direction of the CNT fibers and is substantially non-conductive in the transverse direction of the CNT fibers.

[0067] The following describes a case where the first member and the second member are CNT films in which CNT webs are laminated so that the longitudinal directions of the CNT fibers are aligned and the CNT fibers are parallel, and the CNT web-like body is a CNT web or a laminate in which CNT webs are laminated so that the longitudinal directions of the CNT fibers are aligned and the CNT fibers are parallel. In this case, the first member, the second member, and the CNT web-like body are conductive in the longitudinal direction of the CNT fibers. Therefore, a composite comprising the first member, the CNT web-like body, and the second member such that the CNT fibers in the first member, the CNT web-like body, and the second member are parallel is conductive in the longitudinal direction of the CNT fibers.

[0068] [Method for Producing Composite] Examples of methods for producing the composite include a step of preparing a first member containing a first carbon material, a CNT web, and a second member containing a second carbon material, and a step of bonding the first member and the second member via the CNT web.

[0069] Examples of processes for bonding a first member and a second member via a CNT web include a process of overlapping the first member, the CNT web, and the second member adjacent to each other in this order and then applying pressure to the overlapping portions, and a process of arranging the first member and the second member on one surface of the CNT web so that they do not overlap, applying pressure to the overlapping portions of the first member and the CNT web and the overlapping portions of the second member and the CNT web, and then folding the CNT web so that the other surfaces of the CNT web face each other and applying pressure. Methods for applying pressure to the overlapping portions include, for example, pressing the overlapping portions by hand or with a pressure roller, or placing a weight on the overlapping portions.

[0070] In one preferred embodiment of the process for preparing a first component containing a first carbon material, a CNT web, and a second component containing a second carbon material, the preparation of the CNT web is carried out immediately before the process for bonding the first component and the second component via the CNT web. "Immediately before" refers to, for example, 0 seconds to 2 hours, 0 seconds to 1 hour, or 0 seconds to 30 minutes before. Note that "0 seconds" refers to a mode in which the CNT web is formed directly on the first component or the second component and is then superimposed on the other component simultaneously with the formation of the CNT web.

[0071] [Article Comprising Carbon Material] The article comprising a carbon material of the present disclosure comprises a member comprising a carbon material having a first region and a second region, and a web of carbon nanotubes. The web of carbon nanotubes is located between the first region and the second region. The web of carbon nanotubes is in contact with both the first region and the second region.

[0072] The carbon nanotube web (CNT web) included in the above-mentioned article is a CNT web similar to the carbon nanotube web included in the above-mentioned composite, and can be manufactured by the same method as the CNT web included in the above-mentioned composite.

[0073] Examples of the carbon material contained in the member of the article include the same carbon material as the first and second members of the composite. Examples of the carbon material-containing member of the article include the same members as the first and second members of the composite.

[0074] In the above member, at least a portion of the first region and the second region that come into contact with the CNT web preferably contains a carbon material.

[0075] The portion of the component included in the article that is not in contact with the CNT web may be made of, for example, a resin, a fabric, a metal, a ceramic, or a glass, or may be covered with a resin, a fabric, a metal, a ceramic, or a glass. Examples of the resin include the same resin as the resin that may constitute the first and second components of the composite. Examples of the material that constitutes the fabric include the same material as the material that may constitute the first and second components of the composite.

[0076] The first region and the second region in the member containing a carbon material may be different regions on the same surface, or may be regions on different surfaces.

[0077] The following describes a case where the carbon material-containing member is a CNT film in which CNT webs are laminated so that the longitudinal directions of the CNT fibers are aligned and the CNT fibers are parallel, and the CNT web-like body is a CNT web or a laminate in which CNT webs are laminated so that the longitudinal directions of the CNT fibers are aligned and the CNT fibers are parallel. In this case, the article may include a CNT web-like body between a first region and a second region in the carbon material-containing member so that the CNT fibers in the first region, the CNT web-like body, and the second region are parallel, or so that the CNT fibers intersect (e.g., orthogonal). From the viewpoint of adhesive strength, the article preferably includes the first region, the CNT web-like body, and the second region so that the CNT fibers in the first region, the CNT web-like body, and the second region are parallel.

[0078] The above article can be produced, for example, by folding a member containing a carbon material so as to sandwich the CNT web therebetween, overlapping the first region, the CNT web, and the second region so that the CNT web is in contact with the first region and the second region, and then applying pressure to the overlapping portion. In the above article, different regions of the member containing a carbon material are bonded together without the use of an adhesive containing a resin.

[0079] [Uses of the Composite] The composite can be used, for example, as a heater. As a heater, for example, there is an embodiment in which the first member is mainly used as an electrode and the second member is mainly used as a heating element. Using the first member as an electrode means that an external power source and the second member, which is a heating element, are electrically connected via the first member.

[0080] One example of a method for manufacturing a heater is to first bond a first member and a second member via a CNT web to obtain a composite, and then contact the first member with a conductor or the like connected to an external power source to electrically connect the external power source and the composite.

[0081] The conductive wire may be fixed, for example, by extending from the outside of the composite into the inside of the first member, or by being fixed to the surface of the first member using a conductive adhesive, such as silver paste.

[0082] When the composite includes a plurality of first members, particularly when the second member is bonded to a plurality of first members, one of the first members may be used as the positive electrode and another of the first members may be used as the negative electrode.

[0083] One embodiment of the composite includes a plurality of first members used as electrodes and a film-like second member, one surface of which is also referred to as a "first surface" and the other surface of which is also referred to as a "second surface."

[0084] A composite including a first member A and a first member B as a first member that is an electrode, and a film-like second member will be described. The composite includes: a second member; a first member A provided on a first region (e.g., one end) of the second member via a CNT web; and a first member B provided on a second region (e.g., the other end) of the second member via a CNT web. The first member A and the first member B may be provided on the same surface of the second member, or the first member A may be provided on a first surface of the second member, and the first member B may be provided on a second surface of the second member.

[0085] A composite including a first electrode member, which includes a first member A, a first member B, a first member C, and a first member D, and a film-like second member, is described below. The composite includes: a second member; a first member A provided on a first surface of a first region (e.g., one end) of the second member via a CNT web; a first member C provided on a second surface of the first region (e.g., one end) of the second member via the CNT web; a first member B provided on a first surface of a second region (e.g., the other end) of the second member via the CNT web; and a first member D provided on a second surface of the second region (e.g., the other end) of the second member via the CNT web.

[0086] The composite includes, in the first region, a 1A component, a CNT web, a second component, a CNT web, and a 1C component, in this order in the stacking direction, and, in the second region, a 1B component, a CNT web, a second component, a CNT web, and a 1D component, in this order in the stacking direction.

[0087] The first member is provided on the second member via the CNT web, and is electrically connected to the second member. That is, members 1A to 1D are each electrically connected to the second member. By electrically connecting the first member to an external power source via a conductor or the like and applying a voltage to the second member to pass a current, the second member generates heat. Therefore, such a composite can be used as a heater.

[0088] From the viewpoint of heat generation performance of the heater, it is preferable that the first member and the second member are CNT films in which CNT webs are laminated so that the CNT fibers are parallel, the CNT web-like body is a CNT web or a laminate in which CNT webs are laminated so that the CNT fibers are parallel, and the composite includes the first member, the CNT web-like body, and the second member so that the CNT fibers in the first member, the CNT web-like body, and the second member are parallel. In this case, the carbon nanotube fibers contained in the second member are aligned so as to extend from the first region toward the second region of the second member, i.e., from the first A member toward the first B member.

[0089] The portion of the second member in the composite that is not in contact with the first member or the conductor may be covered with a resin, etc. Examples of the resin include epoxy resin, phenol resin, polyamide resin, polyolefin resin, polystyrene resin, polycarbonate resin, polymethyl methacrylate resin, polyethylene terephthalate resin, polyethersulfone resin, cellulose ester resin, benzocyclobutene resin, vinyl chloride resin, and acrylic resin.

[0090] When a CNT film is used as the first and second members, the heat generation amount of the heater can be adjusted by adjusting the thickness of the CNT film, for example, by adjusting the number of stacked CNT webs if the CNT film is a laminate of CNT webs.

[0091] In addition to heaters, the composite can be used in aerospace applications such as aircraft, sports and leisure applications such as shoes, fishing rods, golf shafts and tennis rackets, heat dissipation materials, electrode sheets, electromagnetic wave shields, electromagnetic wave absorbing sheets, antistatic sheets, battery components, electronic components, and electronic device applications such as housings for notebook computers, tablets and smartphones. The composite can also be used in building materials, bags, automobiles and wind power generators, for example.

[0092] In the composite, the first and second members are bonded together by the CNT web without using a resin-containing adhesive, and therefore, in one embodiment, the composite maintains the electrical properties and other characteristics of the carbon material.

[0093] The present disclosure has the following aspects: [1] A composite comprising: a first member containing a first carbon material, a second member containing a second carbon material, and a web-like body of carbon nanotubes located between the first member and the second member and in contact with each of the first member and the second member.

[0094] [2] The composite according to [1], wherein the web-like carbon nanotube body is a carbon nanotube web obtained by extracting a plurality of carbon nanotubes from a carbon nanotube forest, or a laminate of the carbon nanotube webs.

[0095] [3] The basis weight of the web-like carbon nanotube body is 0.00113 to 0.17 mg / cm 2 The complex according to [1] or [2],

[0096] [4] The composite according to any one of [1] to [3], wherein the first carbon material and the second carbon material are carbon nanotubes, and the first member and the second member are carbon nanotube films.

[0097] [5] The basis weight of the carbon nanotube film that is the first member is 0.0226 to 170 mg / cm 2 The weight of the carbon nanotube film that is the second member is 0.0226 to 170 mg / cm 2 The complex according to any one of [1] to [4],

[0098] [6] A method for producing a composite, comprising: preparing a first member containing a first carbon material, a web of carbon nanotubes, and a second member containing a second carbon material; and bonding the first member and the second member together via the web of carbon nanotubes.

[0099] [7] A composite obtained by bonding a first member containing a first carbon material and a second member containing a second carbon material via a web of carbon nanotubes.

[0100] [8] A heater comprising the composite according to any one of [1] to [5] and [7].

[0101] [9] A web-like body of carbon nanotubes for bonding a first member containing a first carbon material to a second member containing a second carbon material.

[0102]

[10] An article comprising a carbon material, comprising: a member comprising a carbon material having a first region and a second region; and a web-like body of carbon nanotubes located between the first region and the second region and in contact with each of the first region and the second region.

[0103] The composite of the present disclosure will be described in more detail below based on examples, but the composite of the present disclosure is not limited to these examples.

[0104] [Production Example 1] <Production of CNT Forest> A wafer coated with a catalyst for carbon nanotube growth was prepared, and vertically aligned carbon nanotubes were grown from the catalyst by chemical vapor deposition to produce a vertically aligned carbon nanotube forest aligned perpendicular to the wafer. The carbon nanotubes constituting the carbon nanotube forest were multi-walled carbon nanotubes, each with an average length of 250 μm, an average diameter of 6 to 10 nm, a carbon purity of 99.8% or more, and a crystallinity (D / G ratio) of 0.6 to 0.8.

[0105] <Production of CNT Web (1)> Among the CNT forests formed on the catalyst substrate, multiple CNTs located at the ends were picked with a picking tool and pulled out into a sheet. In this way, one layer of CNT web (1) was produced. The size of the CNT web (1) was 1 cm long and 2.5 cm wide, 2.5 cm long and 1 cm wide, or 1 cm long and 1 cm wide. The length of the CNT web refers to the length of the CNT web along the longitudinal direction of the CNT fibers, and the width of the CNT web refers to the length of the CNT web along the transverse direction of the CNT fibers. The basis weight of the CNT web (1) was 0.0034 mg / cm 2 It was.

[0106] [Manufacturing Example 2] <Manufacturing of CNT Film (1)> A CNT forest was manufactured in the same manner as in Manufacturing Example 1. After the CNT web was drawn out, the CNT web was wrapped around the circumferential surface of a roller with a diameter of 800 mm 50 times. Next, the wrapped CNT web was cut in the direction of the roller's rotation axis, unfolded, and removed from the roller. This resulted in a CNT film (1) with 50 layers of CNT web laminated together. The CNT film (1) was used after being cut to the desired size. The size of the CNT film (1) was 10 cm long and 2.5 cm wide, or 10 cm long and 1 cm wide. The length of the CNT film refers to the length of the CNT film along the longitudinal direction of the CNT fiber, and the width of the CNT film refers to the length of the CNT film along the transverse direction of the CNT fiber. The basis weight of the CNT film (1) was 0.17 mg / cm 2 It was.

[0107] [Production Example 3] <Production of CNT Film (2)> A CNT film (2) having 400 layers of CNT web laminated thereon was obtained in the same manner as in Production Example 2, except that the CNT web was wrapped around the peripheral surface of a roller 400 times. The CNT film (2) was used after being cut to the desired size. The size of the CNT film (2) was 10 cm long and 2.5 cm wide, or 10 cm long and 1 cm wide. The basis weight of the CNT film (2) was 1.36 mg / cm 2 It was.

[0108] Example 1: A CNT web (1) measuring 1 cm in length and 2.5 cm in width, a CNT film (1) measuring 10 cm in length and 2.5 cm in width, and a CNT film (2) measuring 10 cm in length and 2.5 cm in width were prepared. The longitudinal end of the CNT film (1) and the longitudinal end of the CNT film (2) were overlapped so that the longitudinal directions of the films were aligned and the overlapping area of ​​the two films was 1 cm (longitudinal direction) x 2.5 cm (transverse direction) when the composite was viewed in a plane. At this time, the CNT web (1) was positioned between the CNT film (1) and the CNT film (2) in the overlapping area so that the longitudinal direction of the CNT fibers constituting the CNT web (1) was parallel to the longitudinal direction of the film. Next, the overlapping portions of the CNT film (1), the CNT web (1), and the CNT film (2) were pressed together by hand to bond the CNT film (1) and the CNT film (2) via the CNT web (1), thereby producing a composite (1). In the composite (1), the longitudinal direction of the CNT fibers constituting the CNT films (1) and (2) was parallel to the longitudinal direction of the CNT fibers constituting the CNT web (1).

[0109] Example 2 A composite (2) was produced in the same manner as in Example 1, except that a CNT web (1) measuring 2.5 cm in length and 1 cm in width was prepared and placed between the CNT films (1) and (2) in the overlapping region such that the longitudinal direction of the CNT fibers constituting the CNT web (1) was parallel to the transverse direction of the films. In the composite (2), the longitudinal direction of the CNT fibers constituting the CNT films (1) and (2) was perpendicular to the longitudinal direction of the CNT fibers constituting the CNT web (1).

[0110] <Mechanical Property Evaluation> Using a tensile tester (Shimadzu Corporation, Autograph AGS-X), the CNT film (1) and the CNT film (2) in the composite (1) or (2) were pulled in opposite directions at a pulling rate of 5 mm / min, and the maximum shear load, which is the load at which the CNT film (1) and the CNT film (2) peeled off, was measured. For the composite (1), the maximum shear load was 3.7 N. The maximum shear stress calculated based on the maximum shear load was 14.8 kPa. For the composite (2), the maximum shear load was 2.4 N. The maximum shear stress calculated based on the maximum shear load was 9.6 kPa.

[0111] Comparative Example 1 The CNT film (1) and the CNT film (2) were overlapped in the same manner as in Example 1 or 2, except that the CNT web (1) was not placed between the CNT film (1) and the CNT film (2) in the overlapping region, and the overlapping portion was pressed together by hand to apply pressure. As a result, the CNT film (1) and the CNT film (2) did not adhere to each other.

[0112] Example 3: A CNT web (1) measuring 1 cm in length and 1 cm in width, a CNT film (1) measuring 10 cm in length and 1 cm in width, and a CNT film (2) measuring 10 cm in length and 1 cm in width were prepared. The longitudinal end of the CNT film (1) and the longitudinal end of the CNT film (2) were overlapped so that the longitudinal directions of the films were aligned and the overlapping area of ​​the two films was 1 cm x 1 cm when the composite was viewed in a plan view. At this time, the CNT web (1) was positioned between the CNT film (1) and the CNT film (2) in the overlapping area so that the longitudinal direction of the CNT fibers constituting the CNT web (1) was parallel to the longitudinal direction of the film. Next, the overlapping portions of the CNT film (1), the CNT web (1), and the CNT film (2) were pressed together by hand to bond the CNT film (1) and the CNT film (2) via the CNT web (1), thereby producing a composite (3). In the composite (3), the longitudinal direction of the CNT fibers constituting the CNT films (1) and (2) was parallel to the longitudinal direction of the CNT fibers constituting the CNT web (1).

[0113] <Evaluation of Electrical Properties> In the composite (3), electrodes were placed in contact with the longitudinal end of the CNT film (1) that was not bonded to the CNT web (1), and with the longitudinal end of the CNT film (2) that was not bonded to the CNT web (1), respectively, and the electrical resistance of the composite (3) was measured using an RG-7C manufactured by NAPSON Corporation, resulting in an electrical resistance value of 23.7 Ω. This confirmed that the CNT film (1) and the CNT film (2) were bonded and electrically connected via the CNT web (1).

[0114] [Example 4] <Production of heater> A CNT web (2) was produced in the same manner as in Production Example 1, except that the length and width of the CNT web were changed to 1.5 cm and 1.5 cm, respectively. A CNT film (3) in which 400 layers of CNT webs were laminated was produced in the same manner as in Production Example 3, except that the length and width of the CNT film were changed to 1.5 cm and 1.5 cm, respectively. Furthermore, a CNT film (4) in which 400 layers of CNT webs were laminated was produced in the same manner as in Production Example 3, except that the length and width of the CNT film were changed to 12 cm and 1.5 cm, respectively.

[0115] One end of the longitudinal direction on one surface of the CNT film (4) and the CNT film (3) were overlapped so that the longitudinal directions of the CNT fibers constituting each film were aligned and the overlapping area of ​​the two films was 1.5 cm x 1.5 cm when the composite was viewed in a plan view. At this time, the CNT web (2) was placed between the CNT films (3) and (4) in the overlapping area so that the longitudinal direction of the CNT fibers constituting the CNT web (2) was parallel to the longitudinal direction of the CNT film (4). Next, pressure was applied to the overlapping portions of the CNT film (3), CNT web (2), and CNT film (4) to bond the CNT film (3) and CNT film (4) together via the CNT web (2).

[0116] Similarly, a CNT film (3) was bonded to the other longitudinal end of one surface of the CNT film (4) and to both longitudinal ends of the other surface of the CNT film (4) via the CNT web (2). This resulted in a composite (4) in which a total of four CNT films (3) were bonded to both sides of the CNT film (4). In the composite (4), the longitudinal direction of the CNT fibers constituting the CNT films (3) and (4) was parallel to the longitudinal direction of the CNT fibers constituting the CNT web (2). The composite (4) comprises a CNT web (2) and CNT films (3) to (4) as shown in FIG. 2 .

[0117] A CBZ resin film manufactured by Japan U-Pica Corporation was laminated on the portion of the CNT film (4) where the CNT film (3) was not bonded, and an external power source was connected to the CNT film (3), thereby producing a heater (1).

[0118] <Evaluation of Heat Generation Characteristics> When a voltage of 5 V was applied to the heater (1), the CNT film (4) generated heat, and the resin film also generated heat. When the temperature distribution of the resin film was observed using a Pocket 2 (manufactured by HIKMICRO), the maximum temperature was 75.8°C.

[0119] REFERENCE SIGNS LIST 1... Composite 10... First member 20... Second member 30... CNT web-like body 40... Substrate 42... CNT forest 50... CNT web extracted from CNT forest 52... CNT fibers constituting the CNT web 60... Roller

Claims

a first member including a first carbon material; a second member including a second carbon material; a web-like body of carbon nanotubes located between the first member and the second member and in contact with each of the first member and the second member; A complex comprising: 　 The composite according to claim 1, wherein the web-like carbon nanotube body is a carbon nanotube web obtained by extracting a plurality of carbon nanotubes from a carbon nanotube forest, or a laminate of the carbon nanotube webs. 　 The web-like body of carbon nanotubes has a basis weight of 0.00113 to 0.17 mg / cm 2 The complex of claim 1, wherein 　 The composite of claim 1 , wherein the first carbon material and the second carbon material are carbon nanotubes, and the first member and the second member are carbon nanotube films. 　 The basis weight of the carbon nanotube film that is the first member is 0.0226 to 170 mg / cm 2 The weight of the carbon nanotube film that is the second member is 0.0226 to 170 mg / cm 2 The complex of claim 4, wherein 　 providing a first member including a first carbon material, a web of carbon nanotubes, and a second member including a second carbon material; a step of bonding the first member and the second member via the web of carbon nanotubes; A method for producing a composite, comprising: 　 A composite obtained by bonding a first member containing a first carbon material and a second member containing a second carbon material via a web of carbon nanotubes. 　 A heater comprising the composite of claim 1. 　 A web-like body of carbon nanotubes for bonding a first member containing a first carbon material to a second member containing a second carbon material. 　 a member including a carbon material, the member having a first region and a second region; a web of carbon nanotubes located between the first region and the second region and in contact with each of the first region and the second region; An article comprising a carbon material, comprising:

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