Carbon nanotube-resin composite and method for producing the carbon nanotube-resin composite

Abstract

A carbon nanotube-resin composite body which comprises a resin and a carbon nanotube assembly wire that contains a plurality of carbon nanotubes, wherein the carbon nanotubes are oriented at a degree of orientation of from 0.9 to 1 in the carbon nanotube assembly wire.

Description

[Technical Field]

[0001] The present disclosure relates to a carbon nanotube-resin composite and a method for producing the carbon nanotube-resin composite. This application claims priority to Japanese Patent Application No. 2019-160767, filed September 3, 2019. The entire contents of this Japanese patent application are incorporated herein by reference. [Background technology]

[0002] Carbon nanotubes (hereinafter referred to as "CNTs"), which are cylindrical graphene sheets made of hexagonally bonded carbon atoms, are a material that is one-fifth the weight of copper, 20 times stronger than steel, and has metallic conductivity, making them an excellent material. For this reason, electric wires made from carbon nanotubes are expected to contribute to the reduction of weight, size, and corrosion resistance of automobile motors in particular.

[0003] Carbon nanotubes can be obtained by a vapor phase growth method, as shown in Patent Document 1 (JP 2005-330175 A), in which a fine catalyst such as iron is heated while a raw material gas containing carbon is supplied to grow carbon nanotubes from the catalyst. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-330175 [Non-patent literature]

[0005] [Non-Patent Document 1] Agnieszka Lekawa-Raus et al. “Electrical Properties of Carbon Nanotube Based Fibers and Their Future Use in Electrical Wiring”, Advanced Functional Materials, Vo.24, pp3661-3682(2014).DOI:10.1002 / adfm.201303716 Summary of the Invention

[0006] A carbon nanotube-resin composite according to one embodiment of the present disclosure comprises: A carbon nanotube-resin composite comprising a carbon nanotube assembly wire containing a plurality of carbon nanotubes and a resin, In the carbon nanotube assembly wire, the carbon nanotubes are oriented with an orientation degree of 0.9 or more and 1 or less, in a carbon nanotube-resin composite.

[0007] A method for producing a carbon nanotube-resin composite according to one embodiment of the present disclosure is the method for producing the carbon nanotube-resin composite described above, a growing step of growing a plurality of carbon nanotubes by supplying a carbon-containing gas to a plurality of catalyst particles in a suspended state to grow one or more carbon nanotubes from each of the plurality of catalyst particles; a stretching step of stretching the plurality of carbon nanotubes by applying a tensile force to the plurality of carbon nanotubes in a suspended state; an assembling step of orienting and assembling the plurality of suspended carbon nanotubes in a direction along the flow of a carbon-containing gas to obtain a plurality of carbon nanotube assembled wires; a bonding step of bonding a volatile liquid containing a resin to the plurality of carbon nanotube assembly wires while orienting and bundling the plurality of carbon nanotube assembly wires in a direction along the longitudinal direction thereof; and an evaporation step of evaporating the volatile liquid attached to the plurality of carbon nanotube assembly wires to obtain a carbon nanotube-resin composite. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram illustrating a typical configuration example of a carbon nanotube assembly wire included in a carbon nanotube-resin composite according to an embodiment of the present disclosure. [Figure 2] FIG. 2 is a diagram showing an example of carbon nanotubes contained in a carbon nanotube-resin composite according to an embodiment of the present disclosure. [Figure 3] FIG. 3 is a diagram illustrating a typical configuration example of a carbon nanotube-resin composite manufacturing apparatus according to an embodiment of the present disclosure. [Figure 4] FIG. 4 is a diagram showing stress-strain curves of Samples 1 to 3. DETAILED DESCRIPTION OF THE INVENTION

[0009] [Problem to be solved by this disclosure] Carbon nanotubes obtained using current carbon nanotube production technology have diameters of approximately 0.4 nm to 20 nm and lengths of up to 55 cm. In order to use carbon nanotubes as electrical wires or high-strength materials, longer carbon nanotubes are required, and technologies that can lengthen carbon nanotubes are being investigated.

[0010] One possible method for lengthening carbon nanotubes is to align a plurality of carbon nanotubes in the longitudinal direction and collect them to form an assembled wire.

[0011] One such method being investigated is to obtain a CNT assembly wire by mixing multiple unoriented CNTs with a dispersant (such as a surfactant or polymer) and injection-molding the mixture into a fibrous form (Non-Patent Document 1).

[0012] However, the breaking strength of the CTN strand obtained by the above method tends to be lower than the inherent breaking strength of CNTs.

[0013] Therefore, an object of the present disclosure is to provide a carbon nanotube-resin composite having excellent breaking strength.

[0014] [Effects of this disclosure] According to the above aspect, it is possible to provide a carbon nanotube-resin composite having excellent breaking strength.

[0015] [Description of the embodiments of the present disclosure] First, embodiments of the present disclosure will be listed and described.

[0016] (1) The carbon nanotube-resin composite of the present disclosure is A carbon nanotube-resin composite comprising a carbon nanotube assembly wire containing a plurality of carbon nanotubes and a resin, In the carbon nanotube assembly wire, the carbon nanotubes are oriented with an orientation degree of 0.9 or more and 1 or less, in a carbon nanotube-resin composite.

[0017] According to the above aspect, it is possible to provide a carbon nanotube-resin composite having excellent breaking strength.

[0018] (2) The carbon nanotube-resin composite preferably contains the resin in an amount of 0.1% by mass or more and less than 100% by mass. This further improves the breaking strength of the carbon nanotube-resin composite.

[0019] (3) The resin is preferably a thermosetting resin or a photocurable resin.

[0020] Because the diameter of the individual CNTs that make up the carbon nanotube-resin composite is small, at the nanometer level, it can be suitably used in, for example, CFRP (Carbon Fiber Reinforced Plastics) products with large curvatures and complex shapes that are difficult to handle with existing carbon fibers (minimum filament diameter: approximately several μm).

[0021] (4) The thermosetting resin is preferably a novolac epoxy resin. This further improves the breaking strength of the carbon nanotube-resin composite.

[0022] (5) The resin is preferably a thermoplastic resin. Because the diameter of the individual CNTs that make up this carbon nanotube-resin composite is small, at the nanometer level, it can be used effectively in CFRP products with large curvatures and complex shapes that are difficult to handle with existing carbon fibers (minimum filament diameter: approximately several μm).

[0023] (6) The thermoplastic resin is preferably a polymethyl methacrylate resin. This further improves the breaking strength of the carbon nanotube-resin composite.

[0024] (7) In the Raman spectrum of the carbon nanotube-resin composite, the Raman shift is 1590±20 cm -1 The peak intensity G and the Raman shift 1350±20cm -1 It is preferable that the ratio D / G of the peak intensity D to the peak intensity D in the graph be 0 or more and 0.1 or less. This further improves the breaking strength of the carbon nanotube-resin composite.

[0025] (8) A method for producing a carbon nanotube-resin composite according to an embodiment of the present disclosure is the method for producing the carbon nanotube-resin composite described above, a growing step of growing a plurality of carbon nanotubes by supplying a carbon-containing gas to a plurality of catalyst particles in a suspended state to grow one or more carbon nanotubes from each of the plurality of catalyst particles; a stretching step of stretching the plurality of carbon nanotubes by applying a tensile force to the plurality of carbon nanotubes in a suspended state; an assembling step of orienting and assembling the plurality of suspended carbon nanotubes in a direction along the flow of a carbon-containing gas to obtain a plurality of carbon nanotube assembled wires; a bonding step of bonding a volatile liquid containing a resin to the plurality of carbon nanotube assembly wires while orienting and bundling the plurality of carbon nanotube assembly wires in a direction along the longitudinal direction thereof; and an evaporation step of evaporating the volatile liquid attached to the plurality of carbon nanotube assembly wires to obtain a carbon nanotube-resin composite.

[0026] This makes it possible to obtain a carbon nanotube-resin composite having excellent breaking strength.

[0027] [Details of the embodiment of the present invention] A specific example of a carbon nanotube-resin composite (hereinafter also referred to as a "CNT-resin composite") according to an embodiment of the present disclosure will be described below with reference to the drawings.

[0028] In the drawings of this disclosure, the same reference numerals represent the same or corresponding parts. Furthermore, dimensional relationships such as length, width, thickness, and depth have been appropriately changed for clarity and simplification of the drawings, and do not necessarily represent actual dimensional relationships.

[0029] In this specification, the expression "A to B" means the upper and lower limits of a range (i.e., A or more and B or less), and when no unit is specified for A and a unit is specified only for B, the units of A and B are the same. Furthermore, when the upper limit of a range is C, it means that the upper limit of the range is C or less, and when the lower limit of the range is D, it means that the lower limit of the range is D or more.

[0030] [Embodiment 1: Carbon nanotube-resin composite] A carbon nanotube-resin composite according to one embodiment of the present disclosure is a carbon nanotube-resin composite comprising a carbon nanotube assembly wire containing a plurality of carbon nanotubes and a resin, in which the carbon nanotubes in the carbon nanotube assembly wire are aligned with an orientation degree of 0.9 or more and 1 or less.

[0031] <Carbon nanotube strand> Fig. 1 is a diagram illustrating a typical configuration example of a carbon nanotube assembly wire (hereinafter also referred to as "CNT assembly wire") included in a carbon nanotube-resin composite. As shown in Fig. 1, the carbon nanotube assembly wire 1 includes a plurality of carbon nanotubes 2. In the CNT assembly wire, the plurality of carbon nanotubes 2 are aligned with an orientation degree of 0.9 or more and 1.0 or less.

[0032] (Shape of carbon nanotubes) The carbon nanotubes contained in the CNT assembly wire can be CNTs with known structures, such as single-walled carbon nanotubes, which have a single cylindrical carbon layer (graphene), and double-walled or multi-walled carbon nanotubes, which have a cylindrical structure of multiple stacked carbon layers.

[0033] The shape of the carbon nanotube is not particularly limited, and either one with a closed end or one with an open end can be used. Furthermore, as shown in Figure 2, the catalyst P used in producing the carbon nanotube may be attached to one or both ends of the tube portion T of the carbon nanotube 2. Furthermore, a cone portion C made of conical graphene may be formed at one or both ends of the tube portion T of the carbon nanotube 2.

[0034] The length of the carbon nanotubes can be selected appropriately depending on the application. The length of the carbon nanotubes is, for example, preferably 10 μm or more, more preferably 100 μm or more. In particular, a carbon nanotube length of 100 μm or more is suitable from the viewpoint of producing a CNT assembly wire. There is no particular upper limit to the length of the carbon nanotubes, but from the viewpoint of production, it is preferably 600 mm or less. The length of the CNTs is preferably 10 μm or more and 600 mm or less, more preferably 100 μm or more and 600 mm or less. The length of the CNTs can be measured by observation with a scanning electron microscope.

[0035] The diameter of the carbon nanotubes is preferably 0.6 nm to 20 nm, more preferably 1 nm to 10 nm, and even more preferably 1 nm to 2 nm. A carbon nanotube diameter of 1 nm to 10 nm is preferable from the viewpoint of heat resistance under oxidizing conditions. A carbon nanotube diameter of 0.6 nm to 2 nm is preferable from the viewpoint of improving breaking strength.

[0036] In this specification, the diameter of a carbon nanotube refers to the average outer diameter of a single CNT. The average outer diameter of a CNT is obtained by directly observing the cross section of a CNT at any two points using a transmission electron microscope, measuring the outer diameter, which is the distance between the two most distant points on the circumference of the CNT, and calculating the average of the obtained outer diameters. When a CNT includes a cone portion at one or both ends, the diameter is measured at a location excluding the cone portion.

[0037] (degree of carbon nanotube orientation) A method for calculating the degree of orientation of CNTs in a CNT assembly wire will be described below. In this specification, the degree of orientation of CNTs is a value calculated by the following steps (a1) to (a6).

[0038] (a1) Image of the CNT-resin composite Images of the CNT-resin composite are taken using the following equipment under the following conditions. The CNT-resin composite is then sliced ​​to nanometer order using a focused ion beam (FIB) or microtome.

[0039] Transmission electron microscope (TEM): JEOL "JEM2100" (product name) Imaging conditions: magnification 50,000 to 1.2 million times, accelerating voltage 60 kV to 200 kV.

[0040] Furthermore, as far as the applicant has measured, it has been confirmed that, as long as measurements are taken on the same sample, there is almost no variation in the measurement results, even if the orientation measurement results described below are calculated multiple times by changing the selected location of the measurement field.

[0041] (a2) Binarization of captured images The image captured in (a1) above is subjected to binarization processing using the following image processing program and following the procedure below.

[0042] Image processing program: Non-destructive paper surface fiber orientation analysis program "FiberOri8single03" (http: / / www.enomae.com / FiberOri / index.htm) Procedure: 1. Histogram average brightness correction 2. Background removal 3. Binarization using a single threshold 4. Brightness inversion.

[0043] (a3) Fourier transform of the binarized image The image obtained in (a2) above is subjected to a Fourier transform using the same image processing program as above (non-destructive paper surface fiber orientation analysis program "FiberOri8single03" (http: / / www.enomae.com / FiberOri / index.htm)).

[0044] (a4) Calculation of orientation angle and orientation strength In the Fourier transform image, the positive X-axis direction is set as 0°, and the average amplitude is calculated for the counterclockwise angle (θ°).

[0045] From the Fourier transform image, a graph showing the relationship between the orientation angle and the orientation strength is created. (a5) Measurement of half-width Based on the graph above, measure the full width at half maximum (FWHM).

[0046] (a6) Calculation of the degree of orientation Based on the full width at half maximum, the degree of orientation is calculated by the following formula (1).

[0047] Orientation degree=(180°-full width at half maximum) / 180° (1) An orientation degree of 0 means completely non-oriented, and an orientation degree of 1 means completely oriented.

[0048] In addition to the above-mentioned methods, the degree of orientation of CNTs in a CNT assembly wire can also be evaluated using polarized Raman analysis or small-angle X-ray scattering.

[0049] In the carbon nanotube assembled wire according to this embodiment, the plurality of carbon nanotubes are aligned with an orientation degree of 0.9 or more and 1.0 or less. This means that the CNTs are highly oriented in the CNT assembled wire according to this embodiment. This allows the CNT assembled wire according to this embodiment to be lengthened while maintaining the electrical conductivity and breaking strength properties of the CNTs.

[0050] If the degree of orientation of CNTs in the CNT assembly wire is less than 0.9, the electrical conductivity and breaking strength tend to decrease. The lower limit of the degree of orientation is preferably 0.93, more preferably 0.94, and even more preferably 0.95. The upper limit of the degree of orientation is preferably 0.99, and more preferably 1. The degree of orientation of CNTs in the CNT assembly wire can be 0.93 to 0.99, 0.94 to 0.99, 0.95 to 0.99, 0.93 to 1, 0.94 to 1, or 0.95 to 1.

[0051] (Carbon nanotube assembly wire shape) The carbon nanotube assembly wire has a thread-like shape in which a plurality of carbon nanotubes are assembled and aligned in the longitudinal direction.

[0052] The length of the carbon nanotube aggregate wire is not particularly limited and can be adjusted appropriately depending on the application. The length of the CNT aggregate wire is, for example, preferably 100 μm or more, more preferably 1000 μm or more, and even more preferably 10 cm or more. There is no particular upper limit to the length of the CNT aggregate wire, but from the viewpoint of production, it is preferably 1 m or less. The length of the CNT aggregate wire can be measured by observation with a scanning electron microscope, an optical microscope, or visually.

[0053] The diameter of the carbon nanotube aggregated wire is not particularly limited and can be adjusted appropriately depending on the application. The diameter of the CNT aggregated wire is, for example, preferably 0.1 μm or more, more preferably 1 μm or more. There is no particular upper limit to the diameter of the CNT aggregated wire, but from the viewpoint of production, it is preferably 100 μm or less. In this embodiment, the diameter of the CNT aggregated wire is smaller than the length of the CNT aggregated wire. In other words, the length direction of the CNT aggregated wire corresponds to the longitudinal direction.

[0054] In this specification, the diameter of a carbon nanotube aggregate wire refers to the average outer diameter of a single CNT aggregate wire. The average outer diameter of a single CNT aggregate wire is obtained by observing a cross section of a single CNT aggregate wire at any two points using a transmission electron microscope or a scanning electron microscope, measuring the outer diameter, which is the distance between the two most distant points on the circumference of the CNT aggregate wire, in the cross section, and calculating the average of the obtained outer diameters.

[0055] (catalyst-derived elements) The carbon nanotube assembly wire may contain at least one metal element selected from the group consisting of iron, nickel, cobalt, molybdenum, gold, silver, copper, yttrium, chromium, palladium, platinum, and tungsten. The metal element is preferably dispersed in the longitudinal direction of the carbon nanotube assembly wire. Here, "dispersion of the metal element in the longitudinal direction of the CNT assembly wire" means that the metal element is not unevenly distributed in the longitudinal direction of the CNT assembly wire.

[0056] These metal elements are derived from the catalysts (ferrocene (Fe(C5H5)2), nickelocene (Ni(C5H5)2), cobaltocene (Co(C5H5)2, etc.) used in the production of CNT assembly wire. When these metal elements are dispersed longitudinally in a CNT assembly wire, the metal elements do not affect the electrical conductivity properties of the CNTs, and the CNT assembly wire can be made long while maintaining its inherent electrical conductivity.

[0057] The types and contents of metal elements contained in the CNT assembly wire can be confirmed and measured by energy dispersive X-ray spectrometry (EDX). The total content of metal elements in the CNT assembly wire is preferably 0.1% to 50% in terms of the number of atoms, more preferably 1% to 40%, and even more preferably 5% to 20%.

[0058] The fact that the metal elements contained in the CNT assembly wire are dispersed in the longitudinal direction of the carbon nanotube assembly wire can be confirmed by EDX, which can be measured simultaneously with electron microscopes such as SEM and TEM, and electron energy loss spectrometry (EELS).

[0059] The carbon nanotube aggregate wire may contain elemental sulfur. The elemental sulfur is preferably dispersed in the longitudinal direction of the carbon nanotube aggregate wire. Here, "elemental sulfur dispersed in the longitudinal direction of the CNT aggregate wire" means that the elemental sulfur is not unevenly distributed in the longitudinal direction of the CNT aggregate wire.

[0060] The sulfur element comes from the auxiliary catalyst (CS2) used in the production of CNT assembly wire. When the sulfur element is dispersed in the longitudinal direction of the CNT assembly wire, the sulfur element does not affect the electrical conductivity, breaking strength, and other properties of the CNT, and the CNT assembly wire can be made long while maintaining these properties.

[0061] The sulfur content of the CNT aggregate wire and the sulfur content in the CNT aggregate wire can be confirmed and measured by EDX, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The sulfur content in the CNT aggregate wire is preferably 0.1% to 20%, more preferably 1% to 15%, and even more preferably 2% to 10%, based on the number of atoms.

[0062] The fact that the sulfur elements contained in the CNT assembly wire are dispersed in the longitudinal direction of the carbon nanotube assembly wire can be confirmed by EDX or EELS, which can be used for simultaneous measurements with an electron microscope such as SEM or TEM.

[0063] <Resin> In the CNT-resin composite, the resin is present between multiple CNT strands, which improves the breaking strength of the CNT-resin composite.

[0064] The resin may be any of a thermosetting resin, a photocurable resin, and a thermoplastic resin.

[0065] Examples of thermosetting resins include novolac epoxy resins, phenolic resins, melamine resins, urea resins, polyimides, unsaturated polyester resins, silicone resins, and polyurethanes. Among these, novolac epoxy resins are preferred because they have a benzene skeleton that has high affinity with the CNT surface and form a network structure with high crosslink density, allowing for the production of strong composite materials.

[0066] As the photo-curable resin, for example, an ultraviolet curable resin such as urethane acrylate can be used.

[0067] Examples of thermoplastic resins include polymethyl methacrylate resin, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polyamide, polyacetal, polycarbonate, and polyester. Among these, polymethyl methacrylate resin is preferred because it can be composited with CNTs without introducing defects and has excellent moldability.

[0068] The type of resin in a CNT-resin composite can be identified by infrared spectroscopy, Raman spectroscopy, and differential scanning calorimetry.

[0069] The CNT-resin composite preferably contains 0.1 mass % or more and less than 100 mass % of resin, which further improves the breaking strength of the carbon nanotube-resin composite.

[0070] The resin content in the CNT-resin composite is preferably 0.1% by mass or more and less than 100% by mass, and more preferably 1% by mass or more and 80% by mass or less.

[0071] The resin content in the CNT-resin composite can be measured by thermogravimetric analysis.

[0072] (D / G ratio of carbon nanotube-resin composite) In the Raman spectrum of the CNT-resin composite, the Raman shift was 1590±20cm -1 The peak intensity G and the Raman shift 1350±20cm -1 It is preferable that the ratio D / G of the peak intensity D to the peak intensity D in the graph be 0 or more and 0.1 or less.

[0073] The G band is a band with a Raman shift of 1590 cm in the Raman spectrum obtained by Raman spectroscopy. -1 The D band is a peak derived from CNTs that appears around the Raman shift of 1350 cm in the Raman spectrum obtained by Raman spectroscopy. -1 These peaks are due to amorphous carbon, graphite, and CNT defects found near the center. Therefore, the smaller the D / G ratio, the higher the crystallinity of the carbon nanotube, and the smaller the amount of amorphous carbon and defective graphite contained in the carbon nanotube.

[0074] When the D / G ratio of a CNT-resin composite is 0.1 or less, the amorphous carbon and graphite have few defects and the crystallinity is high. Therefore, the CNT-resin composite can have high tensile strength and high electrical conductivity. When the D / G ratio of a CNT-resin composite exceeds 0.1, the CNTs may not have sufficient tensile strength and high electrical conductivity. The D / G ratio is preferably 0.1 or less, and more preferably 0.01 or less. The lower limit of the D / G ratio is not particularly limited, but can be, for example, 0 or more. The D / G ratio of a CNT-resin composite can be 0 or more and 0.1 or less, or 0 or more and 0.01 or less.

[0075] In this specification, the D / G ratio of a CNT-resin composite is a value measured by the following method.

[0076] The CNT-resin composite is subjected to Raman spectroscopic analysis under the following conditions to obtain a Raman spectrum (hereinafter also referred to as the Raman spectrum of the CNT-resin composite). In the Raman spectrum of the CNT-resin composite, the D / G ratio is calculated from the peak intensity of the G band and the peak intensity of the D band. Raman spectroscopic analysis conditions Wavelength: 532nm Laser power: 17mW Exposure time: 1 second Average number of times: 3 Objective lens magnification: 50x

[0077] [Embodiment 2: Method for producing carbon nanotube-resin composite] The CNT-resin composite of the first embodiment can be produced, for example, by a carbon nanotube-resin composite production apparatus (hereinafter also referred to as the "CNT-resin composite production apparatus") 500 shown in Figure 3. The carbon nanotube-resin composite production apparatus 500 can include a tubular carbon nanotube growth section (hereinafter also referred to as the "CNT growth section") 21, a gas supply section 22 that supplies a carbon-containing gas into the CNT growth section 21 from one end of the CNT growth section 21 (the right end in Figure 3), a catalyst supply section 23 that supplies catalyst particles P into the CNT growth section 21, a carbon nanotube assembly section 24 (hereinafter also referred to as the CNT assembly section) that is disposed on the other end side of the CNT growth section 21 (the left end in Figure 3) and aligns and assembles a plurality of carbon nanotubes obtained in the CNT growth section 21 in a direction along the flow of the carbon-containing gas, and a carbon nanotube-resin composite formation section 50 downstream of the carbon nanotube assembly section 24. The carbon nanotube-resin composite forming section 50 can include a liquid applying device 51 that applies a volatile liquid 53 to the CNT assembly wire obtained in the CNT assembly section 24, and a winding device 52 that applies tension to the carbon nanotube assembly wire while passing the plurality of carbon nanotube assembly wires through a squeeze 55, and then orients the carbon nanotube assembly wires in a direction along their longitudinal direction, bundles them, and winds them up.

[0078] The method for producing a CNT-resin composite includes a growth step of growing a plurality of carbon nanotubes by supplying a carbon-containing gas to a plurality of catalyst particles in a suspended state, thereby growing one or more carbon nanotubes from each of the plurality of catalyst particles; an elongation step of applying a tensile force to the plurality of carbon nanotubes in a suspended state to elongate the plurality of carbon nanotubes; an assembly step of orienting and assembling the plurality of suspended carbon nanotubes in a direction along the flow of the carbon-containing gas to obtain a plurality of carbon nanotube assembly wires; an attachment step of attaching a volatile liquid containing resin to the carbon nanotube assembly wire while orienting and bundling the plurality of carbon nanotube assembly wires in a direction along their longitudinal direction; and an evaporation step of evaporating the volatile liquid attached to the plurality of carbon nanotube assembly wires to obtain a carbon nanotube-resin composite.

[0079] <Growth process> First, a carbon-containing gas is supplied to a plurality of catalyst particles in a suspended state, thereby growing one or more carbon nanotubes from each of the plurality of catalyst particles.

[0080] The growth step is carried out inside the CNT growth section 21. The growth step is preferably carried out under temperature conditions of 800°C or higher and 1200°C or lower. If the temperature is lower than 800°C, the CNT growth rate tends to slow down. On the other hand, if the temperature exceeds 1200°C, the content of impurity carbon tends to increase. The temperature condition for the growth step is more preferably 900°C or higher and 1150°C or lower, and even more preferably 950°C or higher and 1050°C or lower.

[0081] The catalyst particles P are supplied into the CNT growth section 21 when the catalyst 27 arranged inside the catalyst supply section 23 collapses due to the wind pressure of the carbon-containing gas supplied from the gas supply section 22 to the catalyst supply section 23 and the CNT growth section 21, becoming catalyst particles P.

[0082] For example, iron, nickel, cobalt, molybdenum, gold, silver, copper, palladium, and platinum can be used as the catalyst particles P. Among these, iron is preferred from the viewpoint of mass production of long CNTs.

[0083] The carbon-containing gas is supplied to the CNT growth unit 21 from the gas supply unit 22 via the catalyst supply unit 23. A reducing gas such as a hydrocarbon gas is used as the carbon-containing gas. Examples of such a carbon-containing gas include a mixed gas of methane and argon, a mixed gas of ethylene and argon, and a mixed gas of ethanol and argon. The carbon-containing gas preferably contains carbon disulfide (CS2) as an auxiliary catalyst.

[0084] The lower limit of the average flow velocity of the carbon-containing gas supplied from the gas supply unit 22 within the CNT growth region is 0.05 cm / sec, preferably 0.10 cm / sec, and more preferably 0.20 cm / sec. On the other hand, the upper limit of the average flow velocity within the CNT growth region 21 is preferably 10.0 cm / sec, and more preferably 5.0 cm / sec. If the average flow velocity of the carbon-containing gas within the CNT growth region 21 is less than the above lower limit, the carbon source gas supplied to the catalyst particles P will be insufficient, and the growth of carbon nanotubes formed between the catalyst particles P will tend to stagnate. Conversely, if the average flow velocity of the carbon-containing gas within the CNT growth region 21 exceeds the above upper limit, the carbon nanotubes will peel off from the catalyst particles P, stopping their growth and inhibiting the formation of carbon nanotubes.

[0085] The lower limit of the Reynolds number of the flow of the carbon-containing gas supplied from the gas supply unit 22 within the CNT growth unit 21 is preferably 0.01, more preferably 0.05. On the other hand, the upper limit of the Reynolds number is 1000, preferably 100, more preferably 10. If the Reynolds number is less than the lower limit, the design of the apparatus is excessively restricted, which may result in the carbon nanotube-resin composite production apparatus 20 becoming unnecessarily expensive and the carbon nanotube production efficiency unnecessarily decreasing. If the Reynolds number exceeds the upper limit, the flow of the carbon-containing gas becomes turbulent, which tends to inhibit the generation of carbon nanotubes between the catalyst particles P.

[0086] The length of the CNTs obtained by the growth step is preferably 0.1 μm or more and 20 μm or less. If the length of the CNTs obtained by the growth step is less than 0.1 μm, adjacent CNTs tend to be tangled rather than aligned in the longitudinal direction, forming secondary particles. On the other hand, if the length of the CNTs exceeds 20 μm, the time required to perform the elongation step increases, which tends to unnecessarily reduce the production efficiency of carbon nanotubes. The length of the CNTs obtained by the growth step is more preferably 0.5 μm or more and 15 μm or less, and even more preferably 1 μm or more and 10 μm or less. The length of the CNTs can be measured by observation with a scanning electron microscope.

[0087] <Extension process> Next, a tensile force is applied to the plurality of carbon nanotubes in a suspended state produced in the CNT growth section, thereby stretching the plurality of carbon nanotubes.

[0088] The elongation step is carried out inside the CNT growth section 21 and the CNT assembly section 24, or inside the CNT assembly section 24. When the elongation step is carried out inside the CNT growth section 21, it is preferable that the elongation step be carried out on the downstream side of the carbon-containing gas of the CNT growth section 21, i.e., on the CNT assembly side.

[0089] The tensile force is preferably applied to the carbon nanotubes by changing the flow rate of the carbon-containing gas. For example, by making the average flow rate of the carbon-containing gas downstream greater than the average flow rate of the carbon-containing gas upstream, a tensile force can be applied to the CNTs in the downstream direction. When the tensile force acts on the ends of the carbon nanotubes, the carbon nanotubes extending from the catalyst particles P are pulled, undergoing plastic deformation and shrinking in diameter while being elongated in the longitudinal direction.

[0090] In the elongation step, the carbon nanotubes are preferably elongated while being oriented in the direction along the flow of the carbon-containing gas. This is thought to make it possible to obtain straight carbon nanotubes that are less likely to bend and in which the tube portion T is made up of only carbon in a six-membered ring. Carbon nanotubes made up of only carbon in a six-membered ring are less likely to deteriorate and can maintain their quality.

[0091] The average flow velocity of the carbon-containing gas downstream is preferably 0.051 cm / sec or more and 10.001 cm / sec or less, and more preferably 0.201 cm / sec or more and 5.001 cm / sec or less. If the average flow velocity of the carbon-containing gas downstream is less than 0.051 cm / sec, the extension rate of the carbon nanotubes tends to be insufficiently fast compared to the growth rate. On the other hand, if the average flow velocity of the carbon-containing gas downstream is more than 10.001 cm / sec, the carbon nanotubes tend to peel off from the catalyst particles P, stopping their growth and inhibiting the formation of carbon nanotubes.

[0092] The average flow velocity of the carbon-containing gas on the upstream side is preferably 0.050 cm / sec or more and 10,000 cm / sec or less, and more preferably 0.200 cm / sec or more and 5,000 cm / sec or less. If the average flow velocity of the carbon-containing gas on the upstream side is less than 0.050 cm / sec, the wind pressure tends to be insufficient, and the growth of carbon nanotubes formed between the catalyst particles P tends to stagnate. On the other hand, if the average flow velocity of the carbon-containing gas on the upstream side is more than 10,000 cm / sec, the carbon nanotubes tend to peel off from the catalyst particles P, stopping their growth and inhibiting the formation of carbon nanotubes.

[0093] One way to increase the average flow velocity of the carbon-containing gas downstream compared to the average flow velocity of the carbon-containing gas upstream is to make the cross-sectional area of ​​the hollow portion through which the carbon-containing gas passes smaller on the downstream side of the carbon-containing gas than on the upstream side of the carbon-containing gas. More specifically, the cross-sectional area of ​​the hollow portion through which the carbon-containing gas passes in the CNT assembly section (corresponding to the downstream side) can be made smaller than the cross-sectional area of ​​the hollow portion through which the carbon-containing gas passes in the CNT growth section (corresponding to the upstream side). This generates an acceleration field near the region where the cross-sectional area of ​​the hollow portion is smaller, increasing the flow velocity of the carbon-containing gas.

[0094] While the carbon nanotube is being stretched by the tensile force, a carbon nanotube with its original diameter grows on the catalyst particle P. Therefore, the carbon nanotube produced through the stretching process can have a tubular tube portion T and a conical cone portion C whose diameter expands continuously from the end of the tube portion, as shown in Figure 2.

[0095] In other words, in the elongation process, the carbon nanotubes formed by vapor phase growth are stretched by tensile force at the same time as they are formed, so that some of the hexagonal cells of the carbon nanotubes are rearranged into pentagonal cells to form a conical part, and then the hexagonal cells are rearranged again to form a tube part, which is a carbon nanotube with a smaller diameter.

[0096] In the elongation process, the carbon nanotubes grown on the catalyst particles P are grown while being stretched using a tensile force, so that the tube portions can be formed at a rate that is extremely faster than the growth rate of the carbon nanotubes on the catalyst particles P. Therefore, long carbon nanotubes can be formed in a relatively short time. Therefore, even if the time for which the conditions for continuous growth of carbon nanotubes on the catalyst particles P can be maintained is short, sufficiently long carbon nanotubes can be formed.

[0097] In the elongation process, it is believed that the incorporation of carbon atoms into the growth points of the carbon nanotubes is promoted by applying a tensile force to the carbon nanotubes on the catalyst particles P. This is believed to increase the growth rate of the carbon nanotubes and, in turn, the rate at which the length of the resulting carbon nanotubes increases.

[0098] In the elongation process, it is believed that applying a tensile force to the carbon nanotubes on the catalyst particles P makes it difficult for the carbon nanotubes to bend, and that straight carbon nanotubes can be obtained, with the tube portion T being a cylindrical body made up of a sheet consisting only of carbon in a six-membered ring. Carbon nanotubes consisting only of carbon in a six-membered ring are less susceptible to deterioration and can maintain their quality.

[0099] The length of the CNTs obtained by the elongation step is preferably 10 μm or more, more preferably 100 μm or more. In particular, a carbon nanotube length of 100 μm or more is suitable from the viewpoint of producing a CNT assembly wire. There is no particular upper limit to the length of the carbon nanotubes, but from the viewpoint of production, it is preferably 600 mm or less. The length of the CNTs can be measured by observation with a scanning electron microscope.

[0100] <Assembling process> Next, the plurality of suspended carbon nanotubes are aligned in the direction along the flow of the carbon-containing gas and assembled to obtain a plurality of carbon nanotube assembled wires.

[0101] One method for orienting and assembling multiple suspended CNTs in the direction along the flow of the carbon-containing gas is to bring multiple carbon nanotubes close to each other in an aligned state. For example, the cross-sectional area of ​​the hollow portion of the CNT assembly portion through which the carbon-containing gas passes can be made smaller than the cross-sectional area of ​​the hollow portion of the CNT growth portion or the CNT elongation portion through which the carbon-containing gas passes. More specifically, the CNT assembly portion can be formed into a honeycomb structure, and the honeycomb structure can be arranged so that the longitudinal direction of the through-holes is aligned with the flow of the carbon-containing gas.

[0102] In this specification, the honeycomb structure means a porous body having a large number of thin cylindrical through-holes, as shown in honeycomb structure 29 in FIG.

[0103] When the CNT assembly part is made of a honeycomb structure, the cross-sectional area of ​​one through hole is 0.05 mm 2 More than 100mm 2 Less than 0.1 mm is preferable 2 More than 50mm 2 Less than 0.5mm is preferable 2 More than 10mm 2 More preferably, the cross-sectional area of ​​one through hole is 0.05 mm 2 If the cross-sectional area of ​​one through-hole is less than 100 mm, the CNTs tend to clog the inside of the through-hole. 2 If the distance exceeds this value, the CNTs tend not to come close enough to each other and cannot aggregate.

[0104] When the CNT aggregate portion is made of a honeycomb structure, the length in the direction along the through-holes (longitudinal direction) of the honeycomb structure is preferably 1 mm to 1 m, more preferably 10 mm to 50 cm, and even more preferably 15 mm to 10 cm. If the length in the direction along the through-holes of the honeycomb structure is less than 1 mm, the CNTs floating in the gas phase tend not to be sufficiently accelerated, and the growth promotion effect tends to be suppressed. On the other hand, if the length in the direction along the through-holes of the honeycomb structure exceeds 1 m, the amount of CNTs deposited on the inner walls of the through-holes increases, making it difficult to recover the CNTs.

[0105] The average flow velocity of the carbon-containing gas at the CNT assembly is preferably 0.05 cm / sec or more and 10 cm / sec or less, and more preferably 0.2 cm / sec or more and 5 cm / sec or less. If the average flow velocity of the carbon-containing gas is less than 0.05 cm / sec, a thin film of unoriented CNTs tends to be obtained. On the other hand, if the average flow velocity of the carbon-containing gas exceeds 10 cm / sec, the carbon-containing gas that reaches the CNT assembly without reacting undergoes an incomplete decomposition reaction, and tar tends to adhere.

[0106] Although the above describes the case where the aggregation step is performed after the elongation step, the elongation step and aggregation step can also be performed simultaneously. Furthermore, the elongation step and aggregation step can also be performed simultaneously after the elongation step. For example, when a honeycomb structure is used as the CNT aggregation portion, the CNTs are elongated and aggregated simultaneously within the through-holes of the honeycomb structure.

[0107] According to the above manufacturing method, by continuously supplying a carbon-containing gas to the catalyst supply section, the CNT growth section, and the CNT assembly section, it becomes possible to continuously manufacture a CNT assembly wire without any length restrictions. The length of the CNT assembly wire can be adjusted appropriately by adjusting the flow rate, supply time, etc. of the carbon-containing gas.

[0108] The length of the CNT aggregated wire obtained by the assembly step is preferably 100 μm or more, more preferably 1000 μm or more, and even more preferably 10000 μm or more. There is no particular upper limit to the length of the CNT aggregated wire, but from the viewpoint of production, it is preferably 1 m or less. The length of the CNT aggregated wire can be measured by observation with an optical microscope or visual observation.

[0109] <Attachment process> Next, the plurality of carbon nanotube assembly wires obtained in the assembly step are oriented in the longitudinal direction and bundled together, and a volatile liquid containing a resin is applied to the carbon nanotube assembly wire.

[0110] As a method for orienting and bundling a plurality of CNT aggregate wires in the longitudinal direction, there is a method in which the plurality of CNT aggregate wires are passed through a restrictor 55 and then wound up by a winding device 52 while applying tension.

[0111] As a method for attaching the volatile liquid containing resin to the carbon nanotube assembly wire, for example, the volatile liquid is atomized into vapor 55, and the vapor 55 is sprayed onto the carbon nanotube assembly wire.

[0112] Examples of the volatile liquid that can be used include methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, xylene, anisole, toluene, cresol, pyrrolidone, carbitol, carbitol acetate, water, epoxy monomers, and acrylic monomers.

[0113] 3, the attachment step is performed before bundling a plurality of carbon nanotube aggregate wires by orienting them in the longitudinal direction (i.e., upstream of the aperture 55), but is not limited thereto. The attachment step can also be performed after bundling a plurality of carbon nanotube aggregate wires by orienting them in the longitudinal direction (i.e., downstream of the aperture 55).

[0114] The volatile liquid includes a resin, and the resin described in the first embodiment can be used as the resin.

[0115] The content of the resin in the volatile liquid is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less.

[0116] <Evaporation process> Next, the volatile liquid that has been attached to the carbon nanotube assembly wires in the attachment step is evaporated to obtain a carbon nanotube-resin composite 3.

[0117] The evaporation step can be carried out by natural drying.

[0118] [Appendix 1] In the carbon nanotube-resin composite of the present disclosure, the length of the carbon nanotubes is preferably 10 μm or more and 600 mm or less. The length of the carbon nanotube is preferably 100 μm or more and 600 mm or less.

[0119] [Appendix 2] In the carbon nanotube-resin composite of the present disclosure, the diameter of the carbon nanotubes is preferably 0.6 nm or more and 20 nm or less. The diameter of the carbon nanotubes is preferably 1 nm or more and 10 nm or less. The diameter of the carbon nanotubes is preferably 1 nm or more and 2 nm or less.

[0120] [Appendix 3] In the CNT assembly wire of the carbon nanotube-resin composite of the present disclosure, the carbon nanotubes are preferably aligned with an orientation degree of 0.93 or more and 0.99 or less. The degree of orientation is preferably 0.94 or more and 0.99 or less. The degree of orientation is preferably 0.95 or more and 0.99 or less. The degree of orientation is preferably 0.93 or more and 1 or less. The degree of orientation is preferably 0.94 or more and 1 or less. The degree of orientation is preferably 0.95 or more and 1 or less.

[0121] [Appendix 4] In the CNT aggregate wire of the carbon nanotube-resin composite of the present disclosure, the carbon nanotube aggregate wire contains elemental sulfur, and the content of elemental sulfur in the carbon nanotube aggregate wire is preferably 0.1% to 20% in terms of the number of atoms. The content of sulfur element in the carbon nanotube assembly wire is preferably 1% or more and 15% or less. The content of sulfur element in the carbon nanotube assembly wire is preferably 2% or more and 10% or less.

[0122] [Appendix 5] The resin content in the CNT assembly wire of the carbon nanotube-resin composite of the present disclosure is preferably 1% by mass or more and 80% by mass or less.

[0123] [Appendix 6] In the Raman spectrum of the carbon nanotube-resin composite of the present disclosure, the Raman shift is 1590±20 cm -1 The peak intensity G and the Raman shift 1350±20cm -1 The ratio D / G of the peak intensity D to the peak intensity D in the graph is preferably 0 or more and 0.01 or less. [Example]

[0124] The present embodiment will be described in more detail with reference to examples, although the present embodiment is not limited to these examples.

[0125] [Sample 1 and Sample 2] <Preparation of carbon nanotube-resin composite manufacturing equipment> A carbon nanotube-resin composite manufacturing apparatus having the same configuration as the carbon nanotube-resin composite manufacturing apparatus shown in FIG. 3 was prepared. Specifically, a carbon nanotube growing section 21 and a carbon nanotube gathering section 24 were placed inside an electric furnace 28. The CNT growing section was made of a quartz tube with an inner diameter of 20 mm and a length of 800 mm. As the carbon nanotube gathering section 24, a ceramic honeycomb structure was placed inside the quartz tube that was continuous with the CNT growing section. The honeycomb structure had about 200 through holes per inch, with each through hole having a cross-sectional area of ​​0.8 mm. 2 is.

[0126] A catalyst supply unit 23 is placed on the side of the CNT growth unit 21 opposite to the side connected to the CNT assembly unit 24. The catalyst supply unit 23 is made of a quartz tube with an inner diameter of 20 mm and a length of 200 mm, and is placed continuous with the CNT growth unit. Ferrocene is placed as a catalyst on a catalyst holder 26 inside the catalyst supply unit 23. The catalyst supply unit 23 is heated by a heater 25.

[0127] A gas supply unit 22 is disposed on the side of the catalyst supply unit 23 opposite to the side connected to the CNT growth unit 21 .

[0128] A liquid applying device 51 that applies a volatile liquid 53 containing a resin to the CNT assembly wire obtained in the CNT assembly part 24, and a winding device 52 that applies tension to the carbon nanotube assembly wire, aligns the multiple carbon nanotube assembly wires in the longitudinal direction, bundles them, and winds them up are disposed downstream of the CNT assembly part 24. The liquid applying device is disposed upstream of the aperture 55.

[0129] <Preparation of carbon nanotube-resin composite> For Sample 1, argon gas with an argon gas concentration of 100% by volume was first supplied from the gas supply unit into the CNT growth unit at a flow rate of 1000 cc / min (flow rate of 3.4 cm / sec) for 50 minutes, while the temperature inside the electric furnace was raised to 1000°C. Next, in addition to the argon gas, methane gas was supplied at a flow rate of 50 cc / min (flow rate of 0.17 cm / sec) and carbon disulfide (CS2) gas was supplied at a flow rate of 1 cc / min (flow rate of 0.003 cm / sec) for 120 minutes. The total flow rate of the mixed gas (carbon-containing gas) containing argon gas, methane gas, and carbon disulfide was 3.6 cm / sec.

[0130] By supplying the argon, methane, and carbon disulfide gases, the catalyst collapsed and the catalyst particles were released into the CNT growth region. CNTs then grew within the region.

[0131] Thereafter, the CNTs elongated and aggregated within the CNT assembly portion, yielding a CNT-aggregated wire. A volatile liquid was applied to the resulting CNT-aggregated wire while it was being wound up by a winding device, and the volatile liquid was then evaporated to yield a CNT-resin composite of Sample 1. The volatile liquid used in Sample 1 contained 1 mass% novolac resin. Sample 1 corresponds to an example.

[0132] For Sample 2, a CNT-resin composite was produced under the same conditions as for Sample 1, except that the volatile liquid contained 4 mass% polymethyl methacrylate resin instead of novolac resin. Sample 2 corresponds to an example.

[0133] [Sample 3] As sample 3, a CNT-assembled wire bundle was prepared by winding and bundling a plurality of CNT-assembled wires obtained in the CNT assembly section of device 1 using a winding device. This CNT-assembled wire bundle did not contain resin. Sample 3 corresponds to a comparative example.

[0134] <Measurement of carbon nanotube assembly wire> (Orientation degree) The degree of orientation of CNTs was measured for the CNT-resin composites of Sample 1 and Sample 2 and the CNT-assembled wire bundle of Sample 3. The method for calculating the degree of orientation was the same as the method described in Embodiment 1, and therefore, the description thereof will not be repeated. In all of Samples 1 to 3, the degree of orientation was 0.9 or more and 1 or less.

[0135] (D / G ratio) The D / G ratio was measured for the CNT-resin composites of Sample 1 and Sample 2 and the CNT-assembled wire bundle of Sample 3. The method for measuring the D / G ratio was the same as the method described in the first embodiment, and therefore the description thereof will not be repeated. In all of Samples 1 to 3, the D / G ratio was 0 or more and 0.1 or less.

[0136] (Resin content) The resin contents of the CNT-resin composites of Samples 1 and 2 and the CNT assembled wire bundle of Sample 3 were measured.

[0137] The resin content of Sample 1 was 10% by mass, the resin content of Sample 2 was 20% by mass, and the resin content of Sample 3 was 0%.

[0138] (breaking strength) The stress-strain curves were measured for the CNT-resin composites of Sample 1 and Sample 2 and the CNT assembled wire bundle of Sample 3. The method for measuring the stress-strain curves is as follows.

[0139] A CNT-assembled wire approximately 3 cm long was prepared, and both ends of the wire were fixed to a tensile jig plate with adhesive. The tensile stress until the 1 cm-long portion of the CNT-assembled wire not fixed with adhesive broke was measured using a load cell (measuring device: Imada Co., Ltd. "ZTS-5N"). The resulting stress-strain curve is shown in Figure 4. In the stress-strain curve, a larger stress (vertical axis) indicates a larger breaking strength, and a larger strain (horizontal axis) indicates a larger elongation.

[0140] It was confirmed that the breaking strength of Sample 1 was 15 times or more higher than that of Sample 3. It was confirmed that the breaking strength of Sample 2 was approximately 10 times higher than that of Sample 3.

[0141] Although the embodiments and examples of the present disclosure have been described above, it is originally intended that the configurations of the above-described embodiments and examples may be appropriately combined or modified in various ways.

[0142] The embodiments and examples disclosed herein are illustrative in all respects and should not be considered limiting. The scope of the present invention is defined by the claims, not by the embodiments and examples described above, and is intended to include meanings equivalent to the claims and all modifications within the scope of the claims. [Explanation of symbols]

[0143] 1, 1a, 1b, 1c, 1d carbon nanotube assembly wire, 2 carbon nanotube, 3 carbon nanotube-resin composite, 21 CNT growth section, 22 gas supply section, 23 catalyst supply section, 24, 24a carbon nanotube assembly section, 25 heater, 26 catalyst holder, 27 catalyst, 28 electric furnace, 29 honeycomb structure, 50 carbon nanotube-resin composite forming section, 51 liquid deposition device, 52 winding device, 53 volatile liquid, 54 steam, 55 squeeze, 500 carbon nanotube-resin composite manufacturing device, T tube section, C cone section, P catalyst particles

Claims

1. A carbon nanotube-resin composite comprising a plurality of carbon nanotube assembly wires and a resin, each of the carbon nanotube assembly wires includes a plurality of carbon nanotubes; In each of the carbon nanotube assembly wires, the carbon nanotubes are aligned with an orientation degree of 0.9 or more and 1 or less, The carbon nanotube includes a tube portion and a cone portion located at one or both ends of the tube portion, The carbon nanotube-resin composite has a plurality of carbon nanotube assembly wires that are bundled together and oriented in a direction along the longitudinal direction of the carbon nanotubes.

2. 2. The carbon nanotube-resin composite according to claim 1, wherein the resin is present between the plurality of carbon nanotube assembly wires.

3. 3. The carbon nanotube-resin composite according to claim 1, wherein the carbon nanotube-resin composite contains the resin in an amount of 0.1% by mass or more and less than 100% by mass.

4. 4. The carbon nanotube-resin composite according to claim 1, wherein the resin is a thermosetting resin or a photocurable resin.

5. 5. The carbon nanotube-resin composite according to claim 4, wherein the thermosetting resin is a novolac epoxy resin.

6. 4. The carbon nanotube-resin composite according to claim 1, wherein the resin is a thermoplastic resin.

7. 7. The carbon nanotube-resin composite according to claim 6, wherein the thermoplastic resin is a polymethyl methacrylate resin.

8. In the Raman spectrum of the carbon nanotube-resin composite, the Raman shift was 1590±20 cm －１ Peak intensity G and Raman shift 1350 ± 20 cm －１ 8. The carbon nanotube-resin composite according to claim 1, wherein a ratio D / G of a peak intensity D to a peak intensity D at the carbon nanotube-resin composite is 0 or more and 0.1 or less.

9. 9. The carbon nanotube-resin composite according to claim 1, wherein the carbon nanotube-resin composite contains the resin in an amount of 0.1% by mass or more and 20% by mass or less.

10. A method for producing a carbon nanotube-resin composite according to any one of claims 1 to 9, a growing step of growing a plurality of carbon nanotubes by supplying a carbon-containing gas to a plurality of catalyst particles in a suspended state to grow one or a plurality of carbon nanotubes from each of the plurality of catalyst particles; a stretching step of stretching the plurality of carbon nanotubes by applying a tensile force to the plurality of carbon nanotubes in a suspended state; an assembling step of orienting and assembling the plurality of suspended carbon nanotubes in a direction along the flow of a carbon-containing gas to obtain a plurality of carbon nanotube assembled wires; a bonding step of bonding a volatile liquid containing a resin to the plurality of carbon nanotube assembly wires while orienting and bundling the plurality of carbon nanotube assembly wires in a direction along the longitudinal direction thereof; an evaporation step of evaporating the volatile liquid attached to the plurality of carbon nanotube assembly wires to obtain a carbon nanotube-resin composite.

11. A method for producing a carbon nanotube-resin composite according to any one of claims 1 to 9, a growing step of growing a plurality of carbon nanotubes by supplying a carbon-containing gas to a plurality of catalyst particles in a suspended state to grow one or a plurality of carbon nanotubes from each of the plurality of catalyst particles; a stretching step of stretching the plurality of carbon nanotubes by applying a tensile force to the plurality of carbon nanotubes in a suspended state; an assembling step of orienting and assembling the plurality of suspended carbon nanotubes in a direction along the flow of a carbon-containing gas to obtain a plurality of carbon nanotube assembled wires; a step of adhering a volatile liquid containing a resin to the plurality of carbon nanotube assembly wires before orienting and bundling the plurality of carbon nanotube assembly wires in a direction along the longitudinal direction thereof; an evaporation step of evaporating the volatile liquid attached to the plurality of carbon nanotube assembly wires to obtain a carbon nanotube-resin composite.

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