JP2020181687A - Carbon nanotube wire material, carbon nanotube wire material connecting structure, and manufacturing method of carbon nanotube wire material - Google Patents

Carbon nanotube wire material, carbon nanotube wire material connecting structure, and manufacturing method of carbon nanotube wire material Download PDF

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JP2020181687A
JP2020181687A JP2019083413A JP2019083413A JP2020181687A JP 2020181687 A JP2020181687 A JP 2020181687A JP 2019083413 A JP2019083413 A JP 2019083413A JP 2019083413 A JP2019083413 A JP 2019083413A JP 2020181687 A JP2020181687 A JP 2020181687A
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carbon nanotube
wire rod
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nanotube wire
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英樹 會澤
Hideki Aizawa
英樹 會澤
山下　智
Satoshi Yamashita
智 山下
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Furukawa Electric Co Ltd
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Abstract

To provide a carbon nanotube wire material capable of reducing contact resistance between carbon nanotube bundles and suppressing the occurrence of excess current.SOLUTION: A CNT wire material 1 is a CNT wire material constituted by twisting a plurality of CNT bundles 11, 11, ... and provided with a plating part 12 arranged along a longer direction of the CNT wire material 1 and arranged inside and on a surface part of the CNT wire material. In a cross section in a direction vertical to the longer direction of the CNT wire material 1, a ratio of a value obtained by dividing the number of the CNT bundles where a ratio of a length of a part where the plating part having a thickness of 1 μm or larger is formed on a surface of the CNT bundle, relative to an entire length of surfaces of the CNT bundle 11 is 0.5 or larger by a total number of the plurality of the CNT bundles 11, 11, ... is 70% or larger, and a degree of twisting of the plurality of the carbon nanotube bundles 11, 11, ... is 10 to 3000 T/m.SELECTED DRAWING: Figure 1

Description

本発明は、複数のカーボンナノチューブを束ねてなるカーボンナノチューブ束の複数を撚り合わせて構成されるカーボンナノチューブ線材、カーボンナノチューブ線材と該線材に接続されるはんだ部とを備えるカーボンナノチューブ線材接続構造体、及びカーボンナノチューブ線材の製造方法に関する。 The present invention is a carbon nanotube wire rod formed by twisting a plurality of carbon nanotube bundles formed by bundling a plurality of carbon nanotubes, and a carbon nanotube wire rod connecting structure including a carbon nanotube wire rod and a solder portion connected to the wire rod. And a method for producing a carbon nanotube wire rod.

従来、自動車や産業機器などの様々な分野における電力線や信号線として、一又は複数の線材からなる芯線と、該芯線を被覆する絶縁被覆とからなる電線が用いられている。芯線を構成する線材の材料としては、通常、電気特性の観点から銅又は銅合金が使用されるが、近年、軽量化の観点からアルミニウム又はアルミニウム合金が提案されている。例えば、アルミニウムの比重は銅の比重の約１／３、アルミニウムの導電率は銅の導電率の約２／３（純銅を１００％ＩＡＣＳの基準とした場合、純アルミニウムは約６６％ＩＡＣＳ）であり、アルミニウム線材に、銅線材と同じ電流を流すためには、アルミニウム線材の断面積を、銅の線材の断面積の約１．５倍と大きくする必要があるが、そのように断面積を大きくしたアルミニウム線材を用いたとしても、アルミニウム線材の質量は、純銅の線材の質量の半分程度であることから、アルミニウム線材を使用することは、軽量化の観点から有利である。 Conventionally, as a power line or a signal line in various fields such as automobiles and industrial equipment, an electric wire composed of a core wire made of one or a plurality of wires and an insulating coating covering the core wire has been used. Copper or a copper alloy is usually used as a material for a wire rod constituting a core wire from the viewpoint of electrical characteristics, but in recent years, aluminum or an aluminum alloy has been proposed from the viewpoint of weight reduction. For example, the specific gravity of aluminum is about 1/3 of the specific gravity of copper, and the conductivity of aluminum is about 2/3 of the conductivity of copper (when pure copper is used as the standard for 100% IACS, pure aluminum is about 66% IACS). In order to pass the same current as the copper wire through the aluminum wire, it is necessary to increase the cross-sectional area of the aluminum wire to about 1.5 times the cross-sectional area of the copper wire. Even if a large aluminum wire is used, the mass of the aluminum wire is about half the mass of the pure copper wire, so that the use of the aluminum wire is advantageous from the viewpoint of weight reduction.

上記のような背景のもと、昨今では、自動車、産業機器等の高性能化・高機能化が進められており、これに伴い、各種電気機器、制御機器などの配設数が増加するとともに、これら機器に使用される電気配線体の配線数も増加する傾向にある。また、その一方で、環境対応のために自動車等の移動体の燃費を向上させるため、線材の軽量化が強く望まれている。 Against the background described above, in recent years, the performance and functionality of automobiles, industrial equipment, etc. have been improved, and along with this, the number of arrangements of various electric equipment, control equipment, etc. has increased. , The number of wires of the electric wiring body used for these devices also tends to increase. On the other hand, in order to improve the fuel efficiency of moving objects such as automobiles for environmental friendliness, it is strongly desired to reduce the weight of wire rods.

こうした更なる軽量化を達成するための新たな手段の一つとして、カーボンナノチューブを線材として活用する技術が新たに提案されている。カーボンナノチューブは、六角形格子の網目構造を有する筒状体の単層、あるいは略同軸で配された多層で構成される３次元網目構造体であり、軽量であると共に、導電性、電流容量、弾性、機械的強度等の特性に優れるため、電力線や信号線に使用されている金属に代替する材料として注目されている。 As one of the new means for achieving such further weight reduction, a new technique for utilizing carbon nanotubes as a wire rod has been proposed. Carbon nanotubes are a three-dimensional network structure composed of a single layer of a tubular body having a hexagonal lattice network structure or multiple layers arranged substantially coaxially, and are lightweight, conductive, and have a current capacity. Since it has excellent properties such as elasticity and mechanical strength, it is attracting attention as a material that replaces metals used in power lines and signal lines.

カーボンナノチューブの比重は、銅の比重の約１／５（アルミニウムの約１／２）であり、また、カーボンナノチューブ単体は、銅（抵抗率１．６８×１０−６Ω・ｃｍ）よりも高導電性を示す。したがって理論的には、複数のカーボンナノチューブを撚り合わせてカーボンナノチューブ集合体を形成すれば、更なる軽量化、高導電率の実現が可能となる。しかしながら、ｎｍ単位のカーボンナノチューブを撚り合わせて、μｍ〜ｍｍ単位のカーボンナノチューブ線材を作製した場合、構成単位となる１本当たりの外径が非常に小さいため、カーボンナノチューブ間の接触抵抗や内部欠陥形成が要因となり、線材全体の抵抗値が増大してしまうという問題がある。そのため、カーボンナノチューブをそのまま線材として使用することが困難であった。また、接続の観点から、カーボンナノチューブ線材とはんだからなるカーボンナノチューブ接続構造体を作製する場合、カーボンナノチューブ線材とはんだの相性が悪く、接続強度や電気特性を確保することが困難であった。 The specific gravity of carbon nanotubes is about 1/5 of the specific gravity of copper (about 1/2 of aluminum), and carbon nanotubes alone are higher than copper (resistivity 1.68 x 10-6 Ω · cm). Shows conductivity. Therefore, theoretically, if a plurality of carbon nanotubes are twisted to form a carbon nanotube aggregate, further weight reduction and high conductivity can be realized. However, when carbon nanotubes in units of nm are twisted to produce carbon nanotube wires in units of μm to mm, the outer diameter of each carbon nanotube as a constituent unit is very small, so that contact resistance and internal defects between carbon nanotubes are observed. There is a problem that the resistance value of the entire wire rod increases due to the formation. Therefore, it has been difficult to use the carbon nanotubes as they are as a wire rod. Further, from the viewpoint of connection, when a carbon nanotube connection structure made of a carbon nanotube wire and a solder is produced, the compatibility between the carbon nanotube wire and the solder is poor, and it is difficult to secure the connection strength and the electrical characteristics.

カーボンナノチューブ撚線（線材）の端部でＣＶＤ（Chemical Vapor Deposition）等によってＣＮＴを成長させ、当該端部から伸びた成長ＣＮＴを他のカーボンナノチューブ撚線或いはその成長ＣＮＴと接続することにより、カーボンナノチューブ撚線同士の接続強度や電気的特性を実現することが可能な製造方法が提案されている（特許文献１）。 CNTs are grown at the ends of carbon nanotube stranded wires (wires) by CVD (Chemical Vapor Deposition) or the like, and the grown CNTs extending from the ends are connected to other carbon nanotube stranded wires or their grown CNTs to form carbon. A manufacturing method capable of realizing connection strength and electrical characteristics between nanotube stranded wires has been proposed (Patent Document 1).

複数のカーボンナノチューブ線を撚り合わせて構成したカーボンナノチューブ線材の表面を金属被覆し、導電性の向上やソレノイド材料として使用した場合に渦電流を低減できるカーボンナノチューブ線材が提案されている（特許文献２)。 A carbon nanotube wire rod having a metal coating on the surface of a carbon nanotube wire rod formed by twisting a plurality of carbon nanotube wires to improve conductivity and reduce an eddy current when used as a solenoid material has been proposed (Patent Document 2). ).

特開２０１３−４７４０２号公報JP 2013-47402 特許第５９３４６４３号公報Japanese Patent No. 5934643

しかしながら、特許文献１では、複数のカーボンナノチューブを撚り合わせてなるカーボンナノチューブ線材の端部同士を、成長ＣＮＴを介して接続することが開示されているにすぎない。カーボンナノチューブ束を撚り合わせて作成したカーボンナノチューブ線材では、カーボンナノチューブ束間の接触抵抗が高く、特定のカーボンナノチューブ束に電流が集中する、いわゆる過電流が生じやすい問題がある。 However, Patent Document 1 merely discloses that the ends of carbon nanotube wires obtained by twisting a plurality of carbon nanotubes are connected to each other via a growth CNT. The carbon nanotube wire rod produced by twisting the carbon nanotube bundles has a problem that the contact resistance between the carbon nanotube bundles is high and the current concentrates on a specific carbon nanotube bundle, so-called overcurrent is likely to occur.

特許文献２では、複数のカーボンナノチューブ線を撚り合わせてなるカーボンナノチューブ線材の一部に金属被覆し、はんだとの接合性を改善しているものの、カーボンナノチューブ線材は金属線よりも柔らかいため線材の形状が安定しにくく、撚線にする際に撚線を構成するカーボンナノチューブ線が表面に露出しやすい。そのため金属被覆されていない部分でカーボンナノチューブ線間の接触抵抗が向上し、渦電流が発生しやすくなる。また、複数のカーボンナノチューブ線を撚線化した場合に、一定の撚り度にしないと、カーボンナノチューブ線間の接触抵抗が大きくなり、撚線の許容電流が小さくなる問題、カーボンナノチューブ線材の端末を端子にはんだ付けした際に、はんだがカーボンナノチューブ線になじみにくくなる問題、そしてカーボンナノチューブ線の強度自体が低下する問題があるが、特許文献２では撚り度について言及されていない。さらに、金属被覆として使用しためっきが薄い場合、カーボンナノチューブ線はめっきと異種材料であるため、めっき剥がれが金属線へのめっきに比べて起こりやすい。そのため、カーボンナノチューブ線からのめっきの剥がれが生じやすくなり、大きな電流が流れた際にめっきの薄い部分、カーボンナノチューブが露出した部分等で発熱が生じ、カーボンナノチューブ線材の耐久性が低くなる問題がある。また、このような薄いめっき厚を有するカーボンナノチューブ線材の端末を端子にはんだ付けする場合、めっきがはんだに溶解することでカーボンナノチューブが露出し、カーボンナノチューブ線材とはんだとの接続性が悪化し、接続抵抗が増大する問題もある。しかしながら、特許文献２ではめっきの厚さについて言及されていない。そのため、特許文献２には、撚り度とめっき厚に起因する上記問題点の改善については開示されていない。 In Patent Document 2, although a part of the carbon nanotube wire made by twisting a plurality of carbon nanotube wires is coated with metal to improve the bondability with the solder, the carbon nanotube wire is softer than the metal wire, so that the wire is made of wire. The shape is difficult to stabilize, and the carbon nanotube wires that make up the stranded wire are easily exposed to the surface when the stranded wire is formed. Therefore, the contact resistance between the carbon nanotube wires is improved in the portion not coated with metal, and eddy currents are likely to be generated. In addition, when a plurality of carbon nanotube wires are twisted, if the twist degree is not constant, the contact resistance between the carbon nanotube wires will increase and the allowable current of the stranded wires will decrease. When soldered to the terminals, there is a problem that the solder does not easily fit into the carbon nanotube wire, and there is a problem that the strength of the carbon nanotube wire itself decreases, but Patent Document 2 does not mention the degree of twist. Further, when the plating used as the metal coating is thin, the carbon nanotube wire is a different material from the plating, so that the plating peeling is more likely to occur than the plating on the metal wire. Therefore, the plating is likely to peel off from the carbon nanotube wire, and when a large current flows, heat is generated in the thin portion of the plating, the exposed portion of the carbon nanotube, etc., and the durability of the carbon nanotube wire is lowered. is there. Further, when the terminal of the carbon nanotube wire having such a thin plating thickness is soldered to the terminal, the carbon nanotube is exposed by dissolving the plating in the solder, and the connectivity between the carbon nanotube wire and the solder deteriorates. There is also a problem that the connection resistance increases. However, Patent Document 2 does not mention the thickness of the plating. Therefore, Patent Document 2 does not disclose the improvement of the above-mentioned problems caused by the twist degree and the plating thickness.

本発明の目的は、カーボンナノチューブ束間の接触抵抗を低減させ、過電流の発生を抑制することができるカーボンナノチューブ線材、及びカーボンナノチューブ接続構造体を提供することにある。 An object of the present invention is to provide a carbon nanotube wire rod capable of reducing the contact resistance between carbon nanotube bundles and suppressing the generation of overcurrent, and a carbon nanotube connection structure.

本発明の要旨構成は、以下の通りである。
［１］複数のカーボンナノチューブ束を撚り合わせて構成されるカーボンナノチューブ線材であって、
前記カーボンナノチューブ線材の長手方向に沿って設けられ、前記カーボンナノチューブ線材の内部及び表層部に配されためっき部を備え、
前記カーボンナノチューブ線材の長手方向に垂直な方向の断面において、カーボンナノチューブ束の表面全長に対する、当該カーボンナノチューブ束の表面に厚さ１μｍ以上のめっき部が形成された部分の長さの比が０．５以上であるカーボンナノチューブ束の個数を、前記複数のカーボンナノチューブ束の総数で除した値の比率が、７０％以上であり、
前記複数のカーボンナノチューブ束の撚り度が１０〜３０００Ｔ／ｍであることを特徴とするカーボンナノチューブ線材。
［２］前記めっき部が、前記複数のカーボンナノチューブ束のうちの隣接する複数のカーボンナノチューブ束間に３次元的に形成されていることを特徴とする上記［１］に記載のカーボンナノチューブ線材。
［３］前記複数のカーボンナノチューブ束の撚り度が、５０〜１０００Ｔ／ｍであることを特徴とする、上記［１］又は［２］に記載のカーボンナノチューブ線材。
［４］前記複数のカーボンナノチューブ束の撚り度が、１００〜４００Ｔ／ｍであることを特徴とする、上記［３］に記載のカーボンナノチューブ線材。
［５］前記複数のカーボンナノチューブ束の撚り本数が１０〜１０００本であることを特徴とする、上記［１］〜［４］のいずれかに記載のカーボンナノチューブ線材。
［６］前記複数のカーボンナノチューブ束の撚り本数が５０〜３００本であることを特徴とする、上記［５］に記載のカーボンナノチューブ線材。
［７］前記めっき部は、銅（Ｃｕ）、銀（Ａｇ）、金（Ａｕ）、スズ（Ｓｎ）、白金（Ｐｔ）、チタン（Ｔｉ）、鉄（Ｆｅ）、クロム（Ｃｒ）及びニッケル（Ｎｉ）からなる群から選択される金属或いはこれらの金属の少なくとも１種を含む合金で形成されることを特徴とする、上記［１］〜［６］のいずれかに記載のカーボンナノチューブ線材。
［８］異種元素がドープされていることを特徴とする、上記［１］〜［７］のいずれかに記載のカーボンナノチューブ線材。
［９］前記カーボンナノチューブ線材を構成するカーボンナノチューブが、２層又は３層の層構造を有することを特徴とする、上記［１］〜［８］のいずれかに記載のカーボンナノチューブ線材。
［１０］複数のカーボンナノチューブ束を１０〜３０００Ｔ／ｍの撚り度で撚り合わせて構成されるカーボンナノチューブ線材と、前記カーボンナノチューブ線材に接続されるはんだ部とを備えるカーボンナノチューブ線材接続構造体であって、
前記カーボンナノチューブ線材は、該カーボンナノチューブ線材の長手方向に沿って設けられ、前記カーボンナノチューブ線材の内部及び表層部に配されためっき部を備え、
前記カーボンナノチューブ線材の長手方向に垂直な方向の断面において、カーボンナノチューブ束の表面全長に対する、当該カーボンナノチューブ束の表面に厚さ１μｍ以上のめっき部が形成された部分の長さの比が０．５以上であるカーボンナノチューブ束の個数を、前記複数のカーボンナノチューブ束の総数で除した値の比率が、７０％以上であることを特徴とするカーボンナノチューブ線材接続構造体。
［１１］複数のカーボンナノチューブ束で構成されるカーボンナノチューブ線材本体に無電界めっき処理を施して下地部を形成する工程と、
前記無電界めっき処理を施したカーボンナノチューブ線材本体に電界めっき処理を施して、前記カーボンナノチューブ線材本体の長手方向に沿って、該カーボンナノチューブ線材本体の内部及び表層部にめっき部を形成する工程と、
前記電界めっきを施す工程の後に、前記複数のカーボンナノチューブ束を１０〜３０００Ｔ／ｍの撚り度で撚り合わせる工程と、
を有することを特徴とする、カーボンナノチューブ線材の製造方法。 The gist structure of the present invention is as follows.
[1] A carbon nanotube wire rod formed by twisting a plurality of carbon nanotube bundles.
A plated portion provided along the longitudinal direction of the carbon nanotube wire rod and arranged inside and on the surface layer portion of the carbon nanotube wire rod is provided.
In the cross section in the direction perpendicular to the longitudinal direction of the carbon nanotube wire rod, the ratio of the length of the portion where the plated portion having a thickness of 1 μm or more is formed on the surface of the carbon nanotube bundle to the total surface length of the carbon nanotube bundle is 0. The ratio of the value obtained by dividing the number of carbon nanotube bundles of 5 or more by the total number of the plurality of carbon nanotube bundles is 70% or more.
A carbon nanotube wire rod having a twist degree of 10 to 3000 T / m for the plurality of carbon nanotube bundles.
[2] The carbon nanotube wire rod according to the above [1], wherein the plated portion is three-dimensionally formed between a plurality of adjacent carbon nanotube bundles among the plurality of carbon nanotube bundles.
[3] The carbon nanotube wire rod according to the above [1] or [2], wherein the twist degree of the plurality of carbon nanotube bundles is 50 to 1000 T / m.
[4] The carbon nanotube wire rod according to the above [3], wherein the twist degree of the plurality of carbon nanotube bundles is 100 to 400 T / m.
[5] The carbon nanotube wire rod according to any one of [1] to [4] above, wherein the number of twists of the plurality of carbon nanotube bundles is 10 to 1000.
[6] The carbon nanotube wire rod according to the above [5], wherein the number of twists of the plurality of carbon nanotube bundles is 50 to 300.
[7] The plated portion includes copper (Cu), silver (Ag), gold (Au), tin (Sn), platinum (Pt), titanium (Ti), iron (Fe), chromium (Cr) and nickel ( The carbon nanotube wire rod according to any one of the above [1] to [6], which is formed of a metal selected from the group consisting of Ni) or an alloy containing at least one of these metals.
[8] The carbon nanotube wire rod according to any one of [1] to [7] above, which is doped with a different element.
[9] The carbon nanotube wire rod according to any one of [1] to [8] above, wherein the carbon nanotubes constituting the carbon nanotube wire rod have a two-layer or three-layer structure.
[10] A carbon nanotube wire connecting structure including a carbon nanotube wire formed by twisting a plurality of carbon nanotube bundles at a twist degree of 10 to 3000 T / m and a solder portion connected to the carbon nanotube wire. hand,
The carbon nanotube wire rod is provided along the longitudinal direction of the carbon nanotube wire rod, and includes a plated portion arranged inside and on the surface layer portion of the carbon nanotube wire rod.
In the cross section in the direction perpendicular to the longitudinal direction of the carbon nanotube wire rod, the ratio of the length of the portion where the plated portion having a thickness of 1 μm or more is formed on the surface of the carbon nanotube bundle to the total surface length of the carbon nanotube bundle is 0. A carbon nanotube wire rod connecting structure, wherein the ratio of the value obtained by dividing the number of carbon nanotube bundles of 5 or more by the total number of the plurality of carbon nanotube bundles is 70% or more.
[11] A step of forming a base portion by subjecting a carbon nanotube wire rod main body composed of a plurality of carbon nanotube bundles to a fieldless plating treatment.
A step of subjecting the carbon nanotube wire rod main body subjected to the electric field plating treatment to an electric field plating treatment to form a plated portion inside and on the surface layer portion of the carbon nanotube wire rod main body along the longitudinal direction of the carbon nanotube wire rod main body. ,
After the step of applying the electric field plating, a step of twisting the plurality of carbon nanotube bundles at a twist degree of 10 to 3000 T / m and a step of twisting the plurality of carbon nanotube bundles.
A method for producing a carbon nanotube wire rod, which comprises.

本発明によれば、カーボンナノチューブ線材における過電流の発生を低減することができる。 According to the present invention, it is possible to reduce the occurrence of overcurrent in the carbon nanotube wire rod.

本発明の実施形態に係るカーボンナノチューブ線材の構成の一例を示す模式図であり、（ａ）は斜視図、（ｂ）は断面図である。It is a schematic diagram which shows an example of the structure of the carbon nanotube wire rod which concerns on embodiment of this invention, (a) is a perspective view, (b) is a sectional view. 本発明の実施形態に係るカーボンナノチューブ線材接続構造体の構成の一例を示す断面図である。It is sectional drawing which shows an example of the structure of the carbon nanotube wire rod connection structure which concerns on embodiment of this invention.

以下、本発明の実施形態を、図面を参照しながら詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

＜カーボンナノチューブ線材の構成＞
図１は、本発明の実施形態に係るカーボンナノチューブ線材の構成の一例を示す模式図であり、（ａ）は斜視図、（ｂ）はカーボンナノチューブ線材の長手方向に垂直な方向（径方向）の断面図である。なお、図１におけるカーボンナノチューブ線材は、その一例を示すものであり、本発明に係る各構成の形状、寸法等は、図１のものに限られないものとする。 <Structure of carbon nanotube wire>
FIG. 1 is a schematic view showing an example of the configuration of the carbon nanotube wire rod according to the embodiment of the present invention. FIG. 1A is a perspective view, and FIG. 1B is a direction (diameter direction) perpendicular to the longitudinal direction of the carbon nanotube wire rod. It is a cross-sectional view of. The carbon nanotube wire rod in FIG. 1 shows an example thereof, and the shape, dimensions, etc. of each configuration according to the present invention are not limited to those in FIG.

図１（ａ）及び（ｂ）に示すように、カーボンナノチューブ線材１（以下、ＣＮＴ線材ともいう）は、複数のカーボンナノチューブ束１１，１１，・・・（以下、ＣＮＴ束という）を撚り合わせて構成されるＣＮＴ線材であって、ＣＮＴ線材１の長手方向に沿って設けられ、ＣＮＴ線材１の内部１ｂ及び表層部１ａに配されためっき部１２を備え、ＣＮＴ線材１の長手方向に垂直な方向の断面（以下、単に「断面」ともいう）において、ＣＮＴ束１１（以下、ＣＮＴ束を「素線」ともいう）の表面全長に対する、当該ＣＮＴ束の表面に厚さ１μｍ以上のめっき部が形成された部分の長さの比が０．５以上であるＣＮＴ束の個数を、複数のＣＮＴ束１１，１１，・・・の総数で除した値の比率が、７０％以上である。 As shown in FIGS. 1A and 1B, the carbon nanotube wire rod 1 (hereinafter, also referred to as CNT wire rod) is obtained by twisting a plurality of carbon nanotube bundles 11, 11, ... (Hereinafter referred to as CNT bundles). The CNT wire rod is provided along the longitudinal direction of the CNT wire rod 1, includes a plating portion 12 arranged inside 1b of the CNT wire rod 1 and a surface layer portion 1a, and is perpendicular to the longitudinal direction of the CNT wire rod 1. A plated portion having a thickness of 1 μm or more on the surface of the CNT bundle with respect to the total surface length of the CNT bundle 11 (hereinafter, the CNT bundle is also referred to as “wire”) in the cross section in the above direction (hereinafter, also simply referred to as “cross section”). The ratio of the value obtained by dividing the number of CNT bundles in which the ratio of the lengths of the portions formed by is 0.5 or more by the total number of a plurality of CNT bundles 11, 11, ... Is 70% or more.

内部１ｂ及び表層部１ａに配されためっき部１２は、具体的には、以下のように定義することができる。ＣＮＴ線材１の断面において、めっき部１２まで含めたＣＮＴ線材１の断面形状の重心をＸ、めっき部１２を含まない各ＣＮＴ束の断面形状の重心をＹｉ、重心Ｘと重心Ｙｉの双方を通る直線とめっき部１２まで含めたＣＮＴ線材１の断面形状の外縁との交点をＺｉとしたとき、線分Ｘ−Ｙｉの長さを線分Ｘ−Ｚｉの長さで除した値が０．７以上となる領域に存在する各ＣＮＴ束１１ａに形成されためっき部を表層部１ａに配されためっき部とし、ＣＮＴ線材１から各ＣＮＴ束１１ａを除いた領域に存在する各ＣＮＴ束１１ｂに形成されためっき部を内部１ｂに配されためっき部とする。 Specifically, the plating portion 12 arranged on the inner portion 1b and the surface layer portion 1a can be defined as follows. In the cross section of the CNT wire rod 1, the center of gravity of the cross-sectional shape of the CNT wire rod 1 including the plated portion 12 is X, the center of gravity of the cross-sectional shape of each CNT bundle not including the plated portion 12 is Yi, and the center of gravity X and the center of gravity Yi are both passed through. When the intersection of the straight line and the outer edge of the cross-sectional shape of the CNT wire 1 including the plated portion 12 is Zi, the value obtained by dividing the length of the line segment X-Yi by the length of the line segment X-Zi is 0.7. The plated portion formed on each CNT bundle 11a existing in the above region is used as a plated portion arranged on the surface layer portion 1a, and is formed on each CNT bundle 11b existing in the region excluding each CNT bundle 11a from the CNT wire rod 1. The plated portion is used as the plated portion arranged inside 1b.

めっき部１２は、複数のＣＮＴ束１１，１１，・・・のうちの隣接する複数のＣＮＴ束間に３次元的に形成されているのが好ましい。例えば、めっき部１２は、複数のＣＮＴ束１１，１１，・・・間に連通して形成された３次元構造を有している。また、めっき部１２の一部が、各ＣＮＴ束１１の外周面の一部又は全体にめっき層として配置されているのが好ましい。 The plating portion 12 is preferably formed three-dimensionally between a plurality of adjacent CNT bundles among the plurality of CNT bundles 11, 11, .... For example, the plating portion 12 has a three-dimensional structure formed by communicating between a plurality of CNT bundles 11, 11, .... Further, it is preferable that a part of the plating portion 12 is arranged as a plating layer on a part or the whole of the outer peripheral surface of each CNT bundle 11.

めっき部１２は、好ましくはＣＮＴ線材１の長手方向に垂直な方向の断面において、ＣＮＴ線材１の全体に偏り無く配されており、均一に分散して配置されている。図１では、めっき部１２は、複数のＣＮＴ束１１，１１の表面に別個に形成されているが、表層部１ａにおいて、めっき部１２は、複数のＣＮＴ束１１ａ，１１ａ，・・・の表面に一体で形成されてもよい。また、めっき部１２は、隣接する複数のＣＮＴ間、例えば隣接する２つのＣＮＴ１１，１１間に形成されるのが好ましい。更に、めっき部１２は、隣接する複数のＣＮＴ間に、当該隣接する複数のＣＮＴのいずれとも密着した状態で形成されるのがより好ましい。 The plated portions 12 are preferably evenly distributed over the entire CNT wire rod 1 in a cross section in a direction perpendicular to the longitudinal direction of the CNT wire rod 1, and are uniformly dispersed. In FIG. 1, the plating portion 12 is separately formed on the surfaces of the plurality of CNT bundles 11, 11, but in the surface layer portion 1a, the plating portion 12 is the surface of the plurality of CNT bundles 11a, 11a, ... It may be integrally formed with. Further, the plating portion 12 is preferably formed between a plurality of adjacent CNTs, for example, between two adjacent CNTs 11 and 11. Further, it is more preferable that the plating portion 12 is formed between the plurality of adjacent CNTs in a state of being in close contact with any of the plurality of adjacent CNTs.

めっき部１２は、はんだとＣＮＴ線材１との相性の観点から銅（Ｃｕ）、銀（Ａｇ）、金（Ａｕ）、スズ（Ｓｎ）、白金（Ｐｔ）、チタン（Ｔｉ）、鉄（Ｆｅ）、クロム（Ｃｒ）及びニッケル（Ｎｉ）からなる群から選択される金属或いはこれらの金属の少なくとも１種を含む合金で形成されているのが好ましく、銅又はスズで形成されているのがより好ましい。 The plated portion 12 includes copper (Cu), silver (Ag), gold (Au), tin (Sn), platinum (Pt), titanium (Ti), and iron (Fe) from the viewpoint of compatibility between the solder and the CNT wire rod 1. It is preferably formed of a metal selected from the group consisting of chromium (Cr) and nickel (Ni) or an alloy containing at least one of these metals, and more preferably formed of copper or tin. ..

ＣＮＴ線材１は、めっき部１２以外の他の金属部を有していてもよい。例えば、ＣＮＴ線材１は、銅（Ｃｕ）、銀（Ａｇ）、金（Ａｕ）、スズ（Ｓｎ）、白金（Ｐｔ）、チタン（Ｔｉ）、鉄（Ｆｅ）、クロム（Ｃｒ）及びニッケル（Ｎｉ）からなる群から選択される金属或いはこれらの金属の少なくとも１種を含む合金で形成されためっき部と、該めっき部の下地を構成し、鉄（Ｆｅ）、ニッケル（Ｎｉ）及びコバルト（Ｃｏ）から選択される金属或いはこれらの金属の少なくとも１種を含む合金で形成された下地部とを備えてもよい。下地部は、好ましくはめっきで形成されており、この場合、上記めっき部とは異なる他のめっき部を構成する。また、ＣＮＴ線材１にめっき部及び下地部の双方が形成される場合、下地部の一部が、ＣＮＴ束１１の外表面に形成され、めっき部の一部が、下地部の外表面に更に形成されるのが好ましい。このとき、ＣＮＴ束１１の重心から見て内側に位置する下地部を第１層、外側に位置するめっき部を第２層とすることができる。更に、ＣＮＴ線材１にめっき部及び下地部の双方が形成される場合、上記下地部の複層が設けられてもよいし、上記めっき部の複層が形成されてもよい。ＣＮＴ線材１或いはＣＮＴ束１１に下地部が設けられることで、下地部とめっきとの濡れ性が向上し、ＣＮＴ線材１とめっき部１２との接着強度を向上させることができる。 The CNT wire rod 1 may have a metal portion other than the plating portion 12. For example, the CNT wire rod 1 includes copper (Cu), silver (Ag), gold (Au), tin (Sn), platinum (Pt), titanium (Ti), iron (Fe), chromium (Cr) and nickel (Ni). A metal selected from the group consisting of () or an alloy containing at least one of these metals forms a base for the plated portion, and iron (Fe), nickel (Ni) and cobalt (Co) are formed. ), Or a base portion formed of an alloy containing at least one of these metals. The base portion is preferably formed by plating, and in this case, another plating portion different from the plating portion is formed. Further, when both the plated portion and the base portion are formed on the CNT wire rod 1, a part of the base portion is formed on the outer surface of the CNT bundle 11, and a part of the plated portion is further formed on the outer surface of the base portion. It is preferably formed. At this time, the base portion located inside the CNT bundle 11 from the center of gravity can be used as the first layer, and the plated portion located outside can be used as the second layer. Further, when both the plated portion and the base portion are formed on the CNT wire rod 1, a plurality of layers of the base portion may be provided, or a plurality of layers of the plated portion may be formed. By providing the base portion on the CNT wire rod 1 or the CNT bundle 11, the wettability between the base portion and the plating can be improved, and the adhesive strength between the CNT wire rod 1 and the plating portion 12 can be improved.

めっき部１２の厚さは、母材（ＣＮＴ束）の保護及びコスト等を考慮し、０．３μｍ〜３．０μｍである。めっき部と下地部の双方が形成される場合、めっき部と下地部の合計厚さは、０．３μｍ〜３．０μｍである。このとき、ＣＮＴ束の１層目に相当する下地部の材料は、ＣＮＴ束との密着力に優れた金属、２層目に相当するめっき部の材料は、電気伝導の優れた金属であることが好ましい。 The thickness of the plated portion 12 is 0.3 μm to 3.0 μm in consideration of protection of the base material (CNT bundle) and cost. When both the plated portion and the base portion are formed, the total thickness of the plated portion and the base portion is 0.3 μm to 3.0 μm. At this time, the material of the base portion corresponding to the first layer of the CNT bundle is a metal having excellent adhesion to the CNT bundle, and the material of the plating portion corresponding to the second layer is a metal having excellent electrical conductivity. Is preferable.

複数のＣＮＴ束の撚り線において、めっきされていないＣＮＴ束同士では接触抵抗が大きく、素線間の導通がとりにくい。そのため、端末から電流を流す場合に、撚り線を構成する素線全部に電流が流れない場合があり、特に大電流を流した場合、特定の素線にのみ電流が流れ、素線の許容電流量を超え、素線が切断してしまう場合がある。 In the stranded wires of a plurality of CNT bundles, the contact resistance between the unplated CNT bundles is large, and it is difficult to obtain continuity between the strands. Therefore, when a current is passed from the terminal, the current may not flow through all the strands that make up the stranded wire. Especially when a large current is passed, the current flows only through a specific strand, and the allowable current of the strands The amount may be exceeded and the wire may be cut.

ＣＮＴ束である素線がめっき処理されている場合、めっきされていない素線と素線同士に比べて、めっきされた素線同士では１／１００程度、めっきされた素線とめっきされていない素線では１／１０程度に接触抵抗が下がるため、素線同士の導通が向上し、素線全体に電流が流れるようになる。その結果、大電流を流した場合でも特定の素線にのみ過剰な電流が流れて素線が切断されることがない。 When the wires that are CNT bundles are plated, the plated wires are about 1/100 of the unplated wires and the wires, and the plated wires are not plated. Since the contact resistance of the strands is reduced to about 1/10, the continuity between the strands is improved and the current flows through the entire strands. As a result, even when a large current is passed, an excessive current flows only in a specific wire and the wire is not cut.

そこで、本実施形態では、ＣＮＴ線材１の長手方向に垂直な方向の断面において、ＣＮＴ束１１の表面（外縁）全長に対する、当該ＣＮＴ束の表面（外縁）に厚さ１μｍ以上のめっき部が形成された部分の長さの比が０．５以上であるＣＮＴ束の個数を、複数のＣＮＴ束１１，１１，・・・の総数で除した値の比率が７０％以上であり、７５％以上が好ましく、８０％以上がより好ましい。上記値の比率が７０％未満であると、素線間の接触抵抗が十分下がらず、大きな電流が流れたときに特性の素線に過電流が生じやすい。上記値の比率の下限値が７０％以上であることにより、ＣＮＴ束間の接触抵抗を低減させ、過電流の発生を抑制することができる。また、上記値の比率の上限値は９９％以下であることが好ましく、９０％以下であることがより好ましい。特に、上記値の比率が９０％以下であることにより、ＣＮＴ線材１とはんだとの間に良好な接合性を付与しつつ、めっき部の増大に伴う線材の重量が増大を抑制し、電線の軽量化を図ることができる。 Therefore, in the present embodiment, in the cross section in the direction perpendicular to the longitudinal direction of the CNT wire rod 1, a plated portion having a thickness of 1 μm or more is formed on the surface (outer edge) of the CNT bundle with respect to the total length of the surface (outer edge) of the CNT bundle 11. The ratio of the value obtained by dividing the number of CNT bundles having a length ratio of 0.5 or more by the total number of a plurality of CNT bundles 11, 11, ... Is 70% or more, and 75% or more. Is preferable, and 80% or more is more preferable. If the ratio of the above values is less than 70%, the contact resistance between the strands does not decrease sufficiently, and an overcurrent is likely to occur in the characteristic strands when a large current flows. When the lower limit of the ratio of the above values is 70% or more, the contact resistance between the CNT bundles can be reduced and the occurrence of overcurrent can be suppressed. Further, the upper limit of the ratio of the above values is preferably 99% or less, and more preferably 90% or less. In particular, when the ratio of the above values is 90% or less, good bondability is imparted between the CNT wire rod 1 and the solder, and the weight of the wire rod increases due to the increase in the plated portion, and the weight of the wire rod increases. The weight can be reduced.

ＣＮＴ線材１の長手方向に垂直な方向の断面において、ＣＮＴ束１１の表面（外縁）全長に対する、当該ＣＮＴ束の表面（外縁）に厚さ１μｍ以上のめっき部が形成された部分の長さの比は、０．５以上であり、０．６５以上がより好ましく、０．８以上が更に好ましい。上記比が０．５未満であると、はんだ付けの際にはんだの濡れ性が悪くなる傾向にある。さらに、めっきされていない素線同士での接触割合が多いため、素線同士の導通の向上が図れず、特定の素線に過電流が生じやすい。また、ＣＮＴ束の表面（外縁）に形成されるめっき部の厚さが１μｍ未満であると、はんだ付けの際にめっきが剥がれてＣＮＴが露出し、ＣＮＴ線材１とはんだとの間に良好な接合性が付与されないおそれがあり、めっきの剥離に伴い、特定の部分において過電流が発生しやすくなる。 In the cross section in the direction perpendicular to the longitudinal direction of the CNT wire rod 1, the length of the portion where the plated portion having a thickness of 1 μm or more is formed on the surface (outer edge) of the CNT bundle with respect to the total length of the surface (outer edge) of the CNT bundle 11. The ratio is 0.5 or more, more preferably 0.65 or more, still more preferably 0.8 or more. If the above ratio is less than 0.5, the wettability of the solder tends to deteriorate during soldering. Further, since the contact ratio between the unplated strands is high, the continuity between the strands cannot be improved, and an overcurrent is likely to occur in a specific strand. Further, if the thickness of the plated portion formed on the surface (outer edge) of the CNT bundle is less than 1 μm, the plating is peeled off during soldering and the CNT is exposed, which is good between the CNT wire 1 and the solder. Bondability may not be imparted, and overcurrent is likely to occur in a specific portion as the plating peels off.

各ＣＮＴ束の断面が円形であるか或いは円相当直径が算出可能である場合、ＣＮＴ線材１の長手方向に垂直な方向の断面において、ＣＮＴ束１１の外周全長に対する、当該ＣＮＴ束の外周に厚さ１μｍ以上のめっき部が形成された部分の長さの比が０．５以上であるカーボンナノチューブ束の個数を、複数のカーボンナノチューブ束１１，１１，・・・の総数で除した値の比率が、７０％以上９９％以下であることが好ましく、７０％以上９０％以下であることがより好ましい。上記値の比率が７０％未満であると、素線間の接触抵抗が十分下がらず、大きな電流が流れたときに特性の素線に過電流が生じやすい傾向にある。また、９０％を超えると、線材の重量が重くなり、電線の軽量化が難しくなる傾向にある。 When the cross section of each CNT bundle is circular or the equivalent diameter of the circle can be calculated, the thickness of the outer circumference of the CNT bundle is thicker than the total outer circumference of the CNT bundle 11 in the cross section in the direction perpendicular to the longitudinal direction of the CNT wire 1. The ratio of the number of carbon nanotube bundles in which the ratio of the lengths of the portions formed with plated portions of 1 μm or more is 0.5 or more divided by the total number of the plurality of carbon nanotube bundles 11, 11, ... However, it is preferably 70% or more and 99% or less, and more preferably 70% or more and 90% or less. If the ratio of the above values is less than 70%, the contact resistance between the strands does not decrease sufficiently, and an overcurrent tends to occur in the characteristic strands when a large current flows. On the other hand, if it exceeds 90%, the weight of the wire becomes heavy, and it tends to be difficult to reduce the weight of the electric wire.

めっき部１２は、ＣＮＴ線材１の長手方向の全長の一部に形成されてもよいし、ＣＮＴ線材１の長手方向の全長に亘って形成されてもよい。このめっき部１２では、ＣＮＴ束１１の外縁全長に対する、当該ＣＮＴ束の表面（外縁）に厚さ１μｍ以上のめっき部が形成された部分の長さの比が０．５以上であるＣＮＴ束の個数を、複数のＣＮＴ束１１，１１，・・・の総数で除した値の比率が、ＣＮＴ線材１の長手方向に関してばらつきが小さいのが好ましい。例えば、長さ１．０ｍのＣＮＴ線材を概ね１０箇所で切断して各断面をＳＥＭで観察し、上述の算出方法を用いて各ＣＮＴ束の上記値を算出する。得られた複数の上記比の値を平均することで、めっき部１２の長手方向における上記値の平均値を得ることができる。また、１０箇所で得られた上記値の標準偏差を求めることで、ＣＮＴ線材１の長手方向に関する上記値のばらつきを確認することができる。 The plated portion 12 may be formed on a part of the entire length of the CNT wire 1 in the longitudinal direction, or may be formed over the entire length of the CNT wire 1 in the longitudinal direction. In the plated portion 12, the ratio of the length of the portion where the plated portion having a thickness of 1 μm or more is formed on the surface (outer edge) of the CNT bundle to the total length of the outer edge of the CNT bundle 11 is 0.5 or more. It is preferable that the ratio of the value obtained by dividing the number by the total number of the plurality of CNT bundles 11, 11, ... Is small in the longitudinal direction of the CNT wire 1. For example, a CNT wire having a length of 1.0 m is cut at approximately 10 points, each cross section is observed by SEM, and the above value of each CNT bundle is calculated using the above calculation method. By averaging the obtained values of the plurality of the above ratios, the average value of the above values in the longitudinal direction of the plating portion 12 can be obtained. Further, by obtaining the standard deviation of the above values obtained at 10 points, it is possible to confirm the variation of the above values in the longitudinal direction of the CNT wire rod 1.

ＣＮＴ線材１は、１層以上の層構造を有するＣＮＴの複数が束ねられてなるＣＮＴ束１１同士を撚り合わせて構成された撚り線である。撚り線としたＣＮＴ線材１の円相当直径は、例えば、０．０１ｍｍ〜５ｍｍである。 The CNT wire rod 1 is a stranded wire formed by twisting CNT bundles 11 formed by bundling a plurality of CNTs having a layer structure of one or more layers. The circle-equivalent diameter of the CNT wire rod 1 as a stranded wire is, for example, 0.01 mm to 5 mm.

撚り線としたＣＮＴ線材１において、複数のＣＮＴ束１１（ＣＮＴ線材１）の撚り度は、複数のＣＮＴ束１１を撚り合わせた際のＣＮＴ線材１の単位長さ当たりの巻き数で表される。すなわち、撚り度は、複数のＣＮＴ束１１のひねった回数（Ｔ）をＣＮＴ線材１の長さ（ｍ）で除した値（単位：Ｔ／ｍ）で表すことができる。複数のＣＮＴ束１１の撚り度は、１０〜３０００Ｔ／ｍであり、５０〜１０００Ｔ／ｍであることが好ましく、１００〜４００Ｔ／ｍであることがより好ましい。撚り度が小さすぎると、素線同士の接触が弱いため、ＣＮＴ線材に大きな電流が流れた場合、ＣＮＴ線材にめっきされてない部分があると、他の線材に電流が逃げられないため、特定の素線に過電流を生じやすい。そのため、特定の素線への過電流の発生を抑制させる観点から、複数のＣＮＴ束１１の撚り度の下限値は１０Ｔ／ｍ以上であり、５０Ｔ／ｍ以上であることが好ましく、１００Ｔ／ｍ以上であることがより好ましい。また、撚り度が大きすぎると、はんだがＣＮＴ線材１になじみにくく、良好な接合性が得られない。ＣＮＴ線材１に良好な接合性を付与させる観点から、撚り度の上限値は３０００Ｔ／ｍ以下であり、１０００Ｔ／ｍ以下であることが好ましく、４００Ｔ／ｍ以下であることがさらに好ましい。このように、撚り度が１０〜３０００Ｔ／ｍであることにより、特定の素線への過電流の発生を抑制できると共に、はんだ付けの際にＣＮＴ線材１とはんだとの間に良好な接合性を付与させることができ、特に、撚り度が１００〜４００Ｔ／ｍであることにより、特定の素線への過電流の発生を抑制しやすい上、優れた接合性を示す。また、複数のＣＮＴ束１１の撚り本数は、１０〜１０００本であることが好ましく、５０〜３００本であることがより好ましい。撚線の本数が多い程、めっきがＣＮＴ線材１に浸み込みやすく、接合性を向上させることができる。そのため、接合性の向上と生産性のバランスの観点から、複数のＣＮＴ束１１の撚り本数は１０〜１０００本であることが好ましい。 In the CNT wire 1 as a stranded wire, the degree of twist of the plurality of CNT bundles 11 (CNT wire 1) is represented by the number of turns per unit length of the CNT wire 1 when the plurality of CNT bundles 11 are twisted together. .. That is, the degree of twist can be expressed by a value (unit: T / m) obtained by dividing the number of twists (T) of the plurality of CNT bundles 11 by the length (m) of the CNT wire rod 1. The twist degree of the plurality of CNT bundles 11 is 10 to 3000 T / m, preferably 50 to 1000 T / m, and more preferably 100 to 400 T / m. If the degree of twist is too small, the contact between the strands is weak, so if a large current flows through the CNT wire, if there is an unplated part in the CNT wire, the current cannot escape to other wires. Overcurrent is likely to occur in the wire. Therefore, from the viewpoint of suppressing the generation of overcurrent to a specific wire, the lower limit of the twist degree of the plurality of CNT bundles 11 is 10 T / m or more, preferably 50 T / m or more, preferably 100 T / m. The above is more preferable. Further, if the degree of twist is too large, the solder does not easily fit into the CNT wire rod 1, and good bondability cannot be obtained. From the viewpoint of imparting good bondability to the CNT wire rod 1, the upper limit of the twist degree is 3000 T / m or less, preferably 1000 T / m or less, and more preferably 400 T / m or less. As described above, when the twist degree is 10 to 3000 T / m, it is possible to suppress the generation of overcurrent to a specific wire, and at the time of soldering, good bondability between the CNT wire 1 and the solder is obtained. In particular, when the degree of twist is 100 to 400 T / m, it is easy to suppress the occurrence of an overcurrent to a specific wire, and it exhibits excellent bondability. The number of twists of the plurality of CNT bundles 11 is preferably 10 to 1000, more preferably 50 to 300. As the number of stranded wires increases, the plating easily penetrates into the CNT wire rod 1, and the bondability can be improved. Therefore, from the viewpoint of improving bondability and balancing productivity, the number of twists of the plurality of CNT bundles 11 is preferably 10 to 1000.

ＣＮＴ線材１は、複数のＣＮＴが纏められた束状体となっている。ＣＮＴ線材１は、異種元素がドープされていてもよい。この場合、ＣＮＴ束１１に異種元素がドープされてなるカーボンナノチューブ複合体の複数を撚り合わせて構成されてもよい。 The CNT wire rod 1 is a bundle of a plurality of CNTs. The CNT wire rod 1 may be doped with a different element. In this case, a plurality of carbon nanotube composites obtained by doping the CNT bundle 11 with different elements may be twisted together.

ＣＮＴ線材１を構成するＣＮＴは、単層構造又は複層構造を有する筒状体であり、それぞれＳＷＮＴ（Single-walled nanotube）、ＭＷＮＴ（Multi-walled nanotube）と呼ばれる。例えば、２層構造を有するＣＮＴは、六角形格子の網目構造を有する２つの筒状体が略同軸で配された３次元網目構造体となっており、ＤＷＮＴ（Double-walled nanotube）と呼ばれる。構成単位である六角形格子は、その頂点に炭素原子が配された六員環であり、他の六員環と隣接してこれらが連続的に結合している。 The CNTs constituting the CNT wire rod 1 are tubular bodies having a single-walled structure or a multi-walled structure, and are called SWNTs (Single-walled nanotubes) and MWNTs (Multi-walled nanotubes), respectively. For example, a CNT having a two-walled structure is a three-dimensional network structure in which two tubular bodies having a network structure of a hexagonal lattice are arranged substantially coaxially, and is called a DWNT (Double-walled nanotube). The hexagonal lattice, which is a constituent unit, is a six-membered ring in which carbon atoms are arranged at its vertices, and these are continuously bonded adjacent to other six-membered rings.

ＣＮＴの性質は、上記のような筒状体のカイラリティ（chirality）に依存する。カイラリティは、アームチェア型、ジグザグ型、及びそれ以外のカイラル型に大別され、アームチェア型は金属性、カイラル型は半導体性、ジグザグ型はその中間の挙動を示す。よってＣＮＴの導電性はいずれのカイラリティを有するかによって大きく異なり、ＣＮＴ集合体の導電性を向上させるには、金属性の挙動を示すアームチェア型のＣＮＴの割合を増大させることが重要とされてきた。一方、半導体性を有するカイラル型のＣＮＴに電子供与性もしくは電子受容性を持つ物質（異種元素）をドープすることにより、金属的挙動を示すことが分かっている。また、一般的な金属では、異種元素をドープすることによって金属内部での伝導電子の散乱が起こって導電性が低下するが、これと同様に、金属性ＣＮＴに異種元素をドープした場合には、導電性の低下を引き起こす。 The properties of CNTs depend on the chirality of the tubular body as described above. Chirality is roughly classified into armchair type, zigzag type, and other chiral types. The armchair type is metallic, the chiral type is semiconducting, and the zigzag type is intermediate. Therefore, the conductivity of CNTs varies greatly depending on which chirality they have, and in order to improve the conductivity of CNT aggregates, it has been important to increase the proportion of armchair-type CNTs that exhibit metallic behavior. It was. On the other hand, it is known that by doping a chiral type CNT having a semiconductor property with a substance having an electron donating property or an electron accepting property (dissimilar element), it exhibits metallic behavior. Further, in a general metal, by doping a dissimilar element, conduction electrons are scattered inside the metal and the conductivity is lowered. Similarly, when a dissimilar element is doped in a metallic CNT, the dissimilar element is doped. , Causes a decrease in conductivity.

このように、金属性ＣＮＴ及び半導体性ＣＮＴへのドーピング効果は、導電性の観点からはトレードオフの関係にあると言えることから、理論的には金属性ＣＮＴと半導体性ＣＮＴとを別個に作製し、半導体性ＣＮＴにのみドーピング処理を施した後、これらを組み合わせることが望ましい。しかし、現状の製法技術では金属性ＣＮＴと半導体性ＣＮＴとを選択的に作り分けることは困難であり、金属性ＣＮＴと半導体性ＣＮＴが混在した状態で作製される。このため、金属性ＣＮＴと半導体性ＣＮＴの混合物からなるＣＮＴ線材の導電性を向上させるには、異種元素・分子によるドーピング処理が効果的となるＣＮＴ構造を選択することが好ましい。 As described above, since it can be said that the doping effect on the metallic CNT and the semiconductor CNT has a trade-off relationship from the viewpoint of conductivity, the metallic CNT and the semiconductor CNT are theoretically manufactured separately. However, it is desirable to combine these after doping the semiconductor CNTs only. However, it is difficult to selectively produce metallic CNTs and semiconducting CNTs with the current manufacturing method technology, and metallic CNTs and semiconducting CNTs are produced in a mixed state. Therefore, in order to improve the conductivity of the CNT wire rod composed of a mixture of metallic CNT and semiconductor CNT, it is preferable to select a CNT structure in which doping treatment with different elements / molecules is effective.

ＣＮＴ線材１を構成するＣＮＴは、２層又は３層の層構造を有するのが好ましい。具体的には、ＣＮＴ線材１を構成するＣＮＴ束１１において、複数のＣＮＴの個数に対する、２層構造又は３層構造を有するＣＮＴの個数の和の比率が５０％以上であるのが好ましく、７５％以上であるのがより好ましい。すなわち、一のＣＮＴ束を構成する全ＣＮＴの総数をＮTOTAL、上記全ＣＮＴのうち２層構造を有するＣＮＴ（２）の数の和をＮCNT(2)、上記全ＣＮＴのうち３層構造を有するＣＮＴ（３）の数の和をＮCNT(3)としたとき、下記式（１）で表すことができる。
｛（ＮCNT(2)＋ＮCNT(3)）／ＮTOTAL｝×１００（％）≧５０（％） ・・・（１） The CNTs constituting the CNT wire rod 1 preferably have a two-layer or three-layer structure. Specifically, in the CNT bundle 11 constituting the CNT wire rod 1, the ratio of the sum of the number of CNTs having a two-layer structure or a three-layer structure to the number of a plurality of CNTs is preferably 50% or more, and is 75. More preferably, it is% or more. That is, the total number of all CNTs constituting one CNT bundle is N TOTAL , the sum of the number of CNTs (2) having a two-walled structure among all the CNTs is N CNT (2) , and the three-walled structure among all the CNTs. When the sum of the numbers of CNTs (3) having is N CNT (3) , it can be expressed by the following equation (1).
{(N CNT (2) + N CNT (3) ) / N TOTAL } × 100 (%) ≧ 50 (%) ・ ・ ・ (1)

２層構造又は３層構造のような層数が少ないＣＮＴは、それより層数の多いＣＮＴよりも比較的導電性が高い。また、ドーパントは、ＣＮＴの最内層の内部、もしくは複数のＣＮＴで形成されるＣＮＴ間の隙間に導入される。ＣＮＴの層間距離はグラファイトの層間距離である０．３３５ｎｍと同等であり、多層ＣＮＴの場合その層間にドーパントが入り込むことはサイズ的に困難である。このことからドーピング効果はＣＮＴの内部および外部にドーパントが導入されることで発現するが、多層ＣＮＴの場合は最外層および最内層に接していない内部に位置するチューブのドープ効果が発現しにくくなる。以上のような理由により、複層構造のＣＮＴにそれぞれドーピング処理を施した際には、２層構造又は３層構造を有するＣＮＴでのドーピング効果が最も高い。また、ドーパントは、強い求電子性もしくは求核性を示す、反応性の高い試薬であることが多い。単層構造のＣＮＴは多層よりも剛性が弱く、耐薬品性に劣るためにドーピング処理を施すと、ＣＮＴ自体の構造が破壊されてしまうことがある。よって、ＣＮＴ束に含まれる２層構造又は３層構造を有するＣＮＴの個数に着目する。また、２層又は３層構造のＣＮＴの個数の和の比率が５０％未満であると、単層構造或いは４層以上の複層構造を有するＣＮＴの比率が高くなり、ＣＮＴ集合体全体としてドーピング効果が小さくなり、高導電率が得にくくなる。よって、２層又は３層構造のＣＮＴの個数の和の比率を上記範囲内の値とすることが好ましい。 A CNT having a small number of layers, such as a two-layer structure or a three-layer structure, has relatively higher conductivity than a CNT having a larger number of layers. Further, the dopant is introduced inside the innermost layer of CNTs or in a gap between CNTs formed by a plurality of CNTs. The interlayer distance of CNTs is equivalent to 0.335 nm, which is the interlayer distance of graphite, and in the case of multi-walled CNTs, it is difficult for the dopant to enter between the interlayers in terms of size. From this, the doping effect is exhibited by introducing the dopant inside and outside the CNT, but in the case of the multi-walled CNT, the doping effect of the tube located inside not in contact with the outermost layer and the innermost layer is less likely to be exhibited. .. For the above reasons, when the CNTs having a multi-layer structure are individually doped, the doping effect of the CNTs having a two-layer structure or a three-layer structure is the highest. In addition, the dopant is often a highly reactive reagent that exhibits strong electrophile or nucleophile. A CNT having a single-walled structure has a weaker rigidity than a multi-walled one, and is inferior in chemical resistance. Therefore, when doping treatment is performed, the structure of the CNT itself may be destroyed. Therefore, attention is paid to the number of CNTs having a two-layer structure or a three-layer structure contained in the CNT bundle. Further, when the ratio of the sum of the number of CNTs having a two-layer or three-layer structure is less than 50%, the ratio of CNTs having a single-walled structure or a multi-walled structure having four or more layers becomes high, and the CNT aggregate as a whole is doped. The effect is reduced and it becomes difficult to obtain high conductivity. Therefore, it is preferable to set the ratio of the sum of the number of CNTs having a two-layer or three-layer structure to a value within the above range.

ＣＮＴにドープされるドーパントは、導電性が向上すれば特に限定はないが、例えば硝酸、硫酸、ヨウ素、臭素、カリウム、ナトリウム、ホウ素及び窒素からなる群から選択される１つ以上の異種元素もしくは分子である。 The dopant doped in CNT is not particularly limited as long as the conductivity is improved, and is, for example, one or more dissimilar elements selected from the group consisting of nitric acid, sulfuric acid, iodine, bromine, potassium, sodium, boron and nitrogen. It is a molecule.

また、ＣＮＴ束１１を構成するＣＮＴの最外層の外径は５．０ｎｍ以下であるのが好ましい。ＣＮＴ束１１を構成するＣＮＴの最外層の外径が５．０ｎｍを超えると、ＣＮＴ間および最内層の隙間に起因する空孔率が大きくなり、導電性が低下してしまうため、好ましくない。 Further, the outer diameter of the outermost layer of the CNTs constituting the CNT bundle 11 is preferably 5.0 nm or less. If the outer diameter of the outermost layer of the CNTs constituting the CNT bundle 11 exceeds 5.0 nm, the porosity due to the gaps between the CNTs and the innermost layer increases and the conductivity decreases, which is not preferable.

ＣＮＴ線材１は、線材全体の強度及び導電性の観点から、その当該線材に分散配置された他の金属部材を有していてもよい。他の金属部材は、例えば長尺状の線材或いは粒子であり、このような形状を有する他の金属部材がＣＮＴに混合されている。上記他の金属部材の金属は、例えば銅、銅合金、アルミニウム、アルミニウム合金を主成分とする材料である。 The CNT wire rod 1 may have other metal members dispersedly arranged on the wire rod from the viewpoint of the strength and conductivity of the entire wire rod. Other metal members are, for example, long wire rods or particles, and other metal members having such a shape are mixed with CNT. The metal of the other metal member is, for example, a material containing copper, a copper alloy, aluminum, or an aluminum alloy as a main component.

＜カーボンナノチューブ線材の製造方法＞
本実施形態に係るカーボンナノチューブ線材の製造方法は、複数のカーボンナノチューブ束で構成されるカーボンナノチューブ線材本体に無電界めっき処理を施す工程と、上記無電界めっき処理を施したカーボンナノチューブ線材本体に電界めっき処理を施して、上記カーボンナノチューブ線材本体の長手方向に沿って、該カーボンナノチューブ線材本体の内部及び表層部にめっき部を形成する工程と、電界めっきを施す工程の後に、複数のカーボンナノチューブ束を１０〜３０００Ｔ／ｍの撚り度で撚り合わせる工程と、を有する。 <Manufacturing method of carbon nanotube wire>
The method for producing the carbon nanotube wire rod according to the present embodiment includes a step of subjecting the carbon nanotube wire rod main body composed of a plurality of carbon nanotube bundles to an electric field plating treatment and an electric field on the carbon nanotube wire rod main body subjected to the electric field plating treatment. After the step of performing plating treatment to form a plated portion inside and the surface layer portion of the carbon nanotube wire rod main body along the longitudinal direction of the carbon nanotube wire rod main body and the step of performing electroplating, a plurality of carbon nanotube bundles It has a step of twisting with a twist degree of 10 to 3000 T / m.

具体的には、先ず、複数のＣＮＴ束で構成されるＣＮＴ線材本体を準備し、鉄（Ｆｅ）、ニッケル（Ｎｉ）及びコバルト（Ｃｏ）から選択される金属或いはこれらの金属の少なくとも１種を含む合金を含有するめっき浴に所定時間浸漬して、ＣＮＴ線材本体にめっき部の下地となる下地部を形成する。これにより、ＣＮＴ線材の内部及び表層部に下地部が形成される。ＣＮＴ線材本体に下地部を形成することで、ＣＮＴ線材本体とめっき部との接着性を向上できる点で優れている。 Specifically, first, a CNT wire rod main body composed of a plurality of CNT bundles is prepared, and a metal selected from iron (Fe), nickel (Ni) and cobalt (Co) or at least one of these metals is used. Immerse in a plating bath containing the containing alloy for a predetermined time to form a base portion to be a base of the plating portion on the CNT wire rod main body. As a result, a base portion is formed inside the CNT wire rod and on the surface layer portion. By forming the base portion on the CNT wire rod main body, it is excellent in that the adhesiveness between the CNT wire rod main body and the plated portion can be improved.

次に、下地部が形成されたＣＮＴ線材本体を、銅（Ｃｕ）、銀（Ａｇ）、金（Ａｕ）、スズ（Ｓｎ）、白金（Ｐｔ）、チタン（Ｔｉ）、鉄（Ｆｅ）、クロム（Ｃｒ）及びニッケル（Ｎｉ）からなる群から選択される金属或いはこれらの金属の少なくとも１種を含む合金を含有するめっき浴に所定時間浸漬して、ＣＮＴ線材本体にめっき部を形成する。これにより、ＣＮＴ線材の内部及び表層部にめっき部が形成される。本電界めっき処理により、ＣＮＴ線材の内部及び表層部にめっき部が形成される。 Next, the CNT wire rod main body on which the base portion is formed is subjected to copper (Cu), silver (Ag), gold (Au), tin (Sn), platinum (Pt), titanium (Ti), iron (Fe), and chromium. A plated portion is formed on the CNT wire rod main body by immersing it in a plating bath containing a metal selected from the group consisting of (Cr) and nickel (Ni) or an alloy containing at least one of these metals for a predetermined time. As a result, a plated portion is formed inside the CNT wire rod and on the surface layer portion. By this electric field plating treatment, a plated portion is formed inside the CNT wire rod and on the surface layer portion.

上記無電界めっき或いは電界めっき処理によって形成されるめっき部の深さ方向の割合、すなわちＣＮＴ線材の外縁から重心までの長さに対するめっき部の厚さの比は、複数のＣＮＴ束の撚り度に依存する。めっき部の深さ方向の割合を好ましい範囲内の値にするには、上記無電界めっきを施す工程の後に、複数のＣＮＴ束を所定の撚り度に撚り合わせる工程を行うことが好ましい。無電界めっき処理を撚り線化する前の複数のＣＮＴ束に行うことで、めっき浴のめっきが複数のＣＮＴ束間を介してＣＮＴ線材本体全体に浸透しやすくなり、ＣＮＴ線材の表層部に位置するＣＮＴ束に加えて、ＣＮＴ線材の内部に位置するＣＮＴ束にもめっき部を形成することができる。このような工程により、内部及び表層部の両方にめっき部１２を形成することができる。 The ratio in the depth direction of the plated portion formed by the above-mentioned electroless plating or electroplating treatment, that is, the ratio of the thickness of the plated portion to the length from the outer edge of the CNT wire to the center of gravity is determined by the twist degree of the plurality of CNT bundles. Dependent. In order to set the ratio of the plated portion in the depth direction to a value within a preferable range, it is preferable to perform a step of twisting a plurality of CNT bundles to a predetermined twist degree after the step of performing the electroless plating. By performing the electroless plating treatment on a plurality of CNT bundles before being stranded, the plating in the plating bath can easily permeate the entire CNT wire body through the plurality of CNT bundles, and is located on the surface layer of the CNT wire. In addition to the CNT bundle to be formed, a plated portion can be formed on the CNT bundle located inside the CNT wire rod. By such a step, the plating portion 12 can be formed both inside and on the surface layer portion.

次いで、下地部及びめっき部が形成された複数のカーボンナノチューブ束を撚り合わせる。これにより、内部１ｂ及び表層部１ａの両方に配されためっき部１２を備えるＣＮＴ線材１が得られる。 Next, a plurality of carbon nanotube bundles in which the base portion and the plating portion are formed are twisted together. As a result, the CNT wire rod 1 having the plating portions 12 arranged on both the inner portion 1b and the surface layer portion 1a can be obtained.

＜カーボンナノチューブ線材接続構造体の構成＞
図２は、本実施形態に係るカーボンナノチューブ線材接続構造体の構成の一例を示す断面図である。なお、図２におけるカーボンナノチューブ線材接続構造体は、その一例を示すものであり、本発明に係る各構成の形状、寸法等は、図２のものに限られないものとする。 <Structure of carbon nanotube wire connection structure>
FIG. 2 is a cross-sectional view showing an example of the configuration of the carbon nanotube wire rod connecting structure according to the present embodiment. The carbon nanotube wire rod connecting structure in FIG. 2 shows an example thereof, and the shape, dimensions, etc. of each configuration according to the present invention are not limited to those in FIG.

図２に示すように、カーボンナノチューブ線材接続構造体１０（以下、ＣＮＴ線材接続構造体ともいう）は、複数のＣＮＴ束１１，１１，・・・を１０〜３０００Ｔ／ｍの撚り度で撚り合わせて構成される上記のＣＮＴ線材１と、ＣＮＴ線材１に接続されるはんだ部２とを備える。はんだ部２は、めっき部１２を介してＣＮＴ線材１と接続されると共に、銅板などの被接続部材２０と接続されている。 As shown in FIG. 2, the carbon nanotube wire connecting structure 10 (hereinafter, also referred to as a CNT wire connecting structure) twists a plurality of CNT bundles 11, 11, ... With a twist degree of 10 to 3000 T / m. Includes the above-mentioned CNT wire 1 and a solder portion 2 connected to the CNT wire 1. The solder portion 2 is connected to the CNT wire rod 1 via the plating portion 12 and is also connected to the connected member 20 such as a copper plate.

はんだ部２は、例えば、銅（Ｃｕ）、スズ（Ｓｎ）、鉛（Ｚｎ）、銀（Ａｇ）、ニッケル（Ｎｉ）、クロム（Ｃｒ）から選択される金属或いはこれらの金属の少なくとも１種を含む合金で形成されている。はんだ部２は、例えばリフロー方式や、糸状はんだとはんだごてを用いた方法で形成することができる。 The solder portion 2 is, for example, a metal selected from copper (Cu), tin (Sn), lead (Zn), silver (Ag), nickel (Ni), chromium (Cr), or at least one of these metals. It is made of a containing alloy. The solder portion 2 can be formed by, for example, a reflow method or a method using a thread-like solder and a soldering iron.

はんだ部２は、めっき部１２と同様、ＣＮＴ線材１の長手方向に沿って設けられ、ＣＮＴ線材１の内部１ｂ及び表層部１ａに配される。めっき部１２は、上述のように、カーボンナノチューブ線材の長手方向に垂直な方向の断面において、カーボンナノチューブ束の表面全長に対する、当該カーボンナノチューブ束の表面に厚さ１μｍ以上のめっき部が形成された部分の長さの比が０．５以上であるカーボンナノチューブ束の個数を、複数のカーボンナノチューブ束の総数で除した値の比率が、７０％以上である。そして、はんだ部２は、ＣＮＴ線材１の内部１ｂ及び表層部１ａに上述の割合で配されためっき部１２と接合されている。これにより、はんだ部２とめっき部１２とが良好に接着し、はんだ部２とＣＮＴ線材１との機械的接続及び電気的接続が確保される。 Like the plating portion 12, the solder portion 2 is provided along the longitudinal direction of the CNT wire rod 1, and is arranged in the inner 1b and the surface layer portion 1a of the CNT wire rod 1. As described above, in the plated portion 12, a plated portion having a thickness of 1 μm or more is formed on the surface of the carbon nanotube bundle with respect to the total surface length of the carbon nanotube bundle in the cross section in the direction perpendicular to the longitudinal direction of the carbon nanotube wire rod. The ratio of the value obtained by dividing the number of carbon nanotube bundles having a portion length ratio of 0.5 or more by the total number of a plurality of carbon nanotube bundles is 70% or more. Then, the solder portion 2 is joined to the plating portion 12 arranged at the above ratio in the inner 1b of the CNT wire rod 1 and the surface layer portion 1a. As a result, the solder portion 2 and the plating portion 12 are well adhered to each other, and the mechanical connection and the electrical connection between the solder portion 2 and the CNT wire rod 1 are secured.

図１では、はんだ部２は、ＣＮＴ線材１の長手方向に垂直な方向の断面において、ＣＮＴ線材１の表層部１ａに配されためっき部１２の表面全体に形成されているが、ＣＮＴ線材１との良好な接続性が確保できる範囲で、めっき部１２の一部に形成されていてもよい。また、はんだ部２は、ＣＮＴ線材１の表層部１ａの表面全体に形成されているが、ＣＮＴ線材１との良好な接続性が確保できる範囲で、ＣＮＴ線材１の表層部１ａの一部に形成されていてもよい。 In FIG. 1, the solder portion 2 is formed on the entire surface of the plated portion 12 arranged on the surface layer portion 1a of the CNT wire rod 1 in the cross section in the direction perpendicular to the longitudinal direction of the CNT wire rod 1, but the CNT wire rod 1 It may be formed in a part of the plating portion 12 as long as good connectivity with the solder can be ensured. Further, the solder portion 2 is formed on the entire surface of the surface layer portion 1a of the CNT wire rod 1, but is formed on a part of the surface layer portion 1a of the CNT wire rod 1 within a range in which good connectivity with the CNT wire rod 1 can be ensured. It may be formed.

上述したように、本実施形態によれば、複数のＣＮＴ束１１，１１，・・・が所定の撚り度で撚り合わされたＣＮＴ線材１は、該ＣＮＴ線材の長手方向に沿って設けられ、且つＣＮＴ線材１の内部１ｂ及び表層部１ａに配されためっき部１２を備え、ＣＮＴ線材１の長手方向に垂直な方向の断面において、ＣＮＴ束１１の表面全長に対する、当該ＣＮＴ束の表面に厚さ１μｍ以上のめっき部が形成された部分の長さの比が０．５以上であるカーボンナノチューブ束の個数を、複数のＣＮＴ束１１，１１，・・・の総数で除した値の比率が７０％以上であるので、めっき部１２の介在によってＣＮＴ束間の接触抵抗が低減し、ＣＮＴ線材１を構成する複数のＣＮＴ束１１，１１，・・・のほぼ全体に電流を流すことができる。これにより、ＣＮＴ束間の接触抵抗を低減させ、過電流の発生を抑制することができる。 As described above, according to the present embodiment, the CNT wire rod 1 in which a plurality of CNT bundles 11, 11, ... Are twisted together at a predetermined twist degree is provided along the longitudinal direction of the CNT wire rod and is provided. A plated portion 12 arranged on the inner 1b of the CNT wire rod 1 and the surface layer portion 1a is provided, and the thickness of the surface of the CNT bundle is relative to the total surface length of the CNT bundle 11 in the cross section in the direction perpendicular to the longitudinal direction of the CNT wire 1. The ratio of the value obtained by dividing the number of carbon nanotube bundles in which the ratio of the lengths of the portions where the plated portions of 1 μm or more are formed is 0.5 or more by the total number of a plurality of CNT bundles 11, 11, ... Is 70. Since it is more than%, the contact resistance between the CNT bundles is reduced by the intervention of the plating portion 12, and the current can flow through almost the entire CNT bundles 11, 11, ... Consisting of the CNT wire rod 1. As a result, the contact resistance between the CNT bundles can be reduced and the occurrence of overcurrent can be suppressed.

また、ＣＮＴ線材接続構造体１０が、複数のＣＮＴ束１１，１１，・・・を所定の撚り度で撚り合わせて構成されるＣＮＴ線材１と、ＣＮＴ線材１に接続されるはんだ部２とを備え、はんだ部２が、めっき部１２を介してＣＮＴ線材１と接続されているので、ＣＮＴ線材１と被接続部材２０との良好な接続を実現することが可能となる。 Further, the CNT wire connecting structure 10 comprises a CNT wire 1 formed by twisting a plurality of CNT bundles 11, 11, ... With a predetermined twist degree, and a solder portion 2 connected to the CNT wire 1. Since the solder portion 2 is connected to the CNT wire rod 1 via the plating portion 12, it is possible to realize a good connection between the CNT wire rod 1 and the connected member 20.

以上、本発明の実施形態に係るＣＮＴ線材、ＣＮＴ接続構造体およびその製造方法について述べたが、本発明は記述の実施形態に限定されるものではなく、本発明の技術思想に基づいて各種の変形および変更が可能である。 Although the CNT wire rod, the CNT connection structure and the manufacturing method thereof according to the embodiment of the present invention have been described above, the present invention is not limited to the described embodiment, and various types are based on the technical idea of the present invention. It can be transformed and changed.

以下、本発明の実施例を説明する。 Hereinafter, examples of the present invention will be described.

（実施例１〜６）
先ず、浮遊触媒気相成長（ＦＣＣＶＤ）法を用い、電気炉によって１３００℃に加熱された、内径φ６０ｍｍ、長さ１６００ｍｍのアルミナ管内部に、炭素源であるデカヒドロナフタレン、触媒であるフェロセン、及び反応促進剤であるチオフェンを、体積比率にてそれぞれ１００：４：１で含む原料溶液Ｌを、スプレー噴霧により供給した。キャリアガスは、水素を９．５Ｌ／ｍｉｎで供給した。得られたＣＮＴを回収機にてシート状に回収し、これらを集めてＣＮＴ集合体を製造し、更にＣＮＴ集合体を束ねてＣＮＴ線材を製造し、大気下において５００℃に加熱し、さらに酸処理を施すことによって高純度化を行った。 (Examples 1 to 6)
First, using the floating catalytic vapor phase growth (FCCVD) method, decahydronaphthalene as a carbon source, ferrocene as a catalyst, and ferrocene as a catalyst are inside an alumina tube having an inner diameter of φ60 mm and a length of 1600 mm heated to 1300 ° C. by an electric furnace. A raw material solution L containing thiophene, which is a reaction accelerator, in a volume ratio of 100: 4: 1 was supplied by spray spraying. As the carrier gas, hydrogen was supplied at 9.5 L / min. The obtained CNTs are collected in a sheet form by a recovery machine, and these are collected to produce a CNT aggregate, and the CNT aggregates are bundled to produce a CNT wire rod, which is heated to 500 ° C. in the air, and further acid. High purity was achieved by applying the treatment.

得られたＣＮＴ５０ｍｇとコール酸ナトリウム４５０ｍｇを２４．５ｇの水に加え超音波攪拌装置を用いて３０分攪拌した後、超音波ホモジナイザーを用いて分散液とした。続いて、内径１ｍｍの注入ノズルを介して、前記ＣＮＴ分散液をイソプロピルアルコール中に注入し、糸状に凝集させ、さらに乾燥させることで、円相当直径が０．１ｍｍであるＣＮＴからなる３ｍの素線（ＣＮＴ束）を得た。同様の操作を行い、合計１８本の素線を作製した。 50 mg of the obtained CNT and 450 mg of sodium cholic acid were added to 24.5 g of water and stirred for 30 minutes using an ultrasonic stirrer, and then a dispersion was prepared using an ultrasonic homogenizer. Subsequently, the CNT dispersion liquid is injected into isopropyl alcohol via an injection nozzle having an inner diameter of 1 mm, aggregated into a thread, and further dried to form a 3 m element composed of CNTs having a diameter equivalent to a circle of 0.1 mm. A wire (CNT bundle) was obtained. The same operation was performed to prepare a total of 18 strands.

得られた各素線を硫酸銅、ホルマリン、ロシェル塩からなるめっき液に浸漬し、無電解銅めっきした。その後、硫酸銅と硫酸の水溶液からなるめっき液にＣＮＴ線材本体を浸漬し、１Ａで５０分電解めっきすることで、電解めっきされた１８本の素線を作製した。続いて銅めっきされた１８本の素線を表１に示す撚り度で撚り、ＣＮＴ線材本体に電界めっき処理が施されたＣＮＴ線材を作製した。 Each of the obtained strands was immersed in a plating solution composed of copper sulfate, formalin, and Rochelle salt, and electroless copper plating was performed. Then, the CNT wire rod main body was immersed in a plating solution composed of an aqueous solution of copper sulfate and sulfuric acid, and electroplated at 1A for 50 minutes to prepare 18 electroplated strands. Subsequently, 18 copper-plated strands were twisted at the twist degrees shown in Table 1 to prepare a CNT wire having an electric field plating treatment on the main body of the CNT wire.

（実施例７〜１２）
めっき処理として、無電解銅めっきの代わりに、塩化スズからなるめっき液を用いた無電解スズめっきを行った以外は実施例１〜６と同様の方法を行い、ＣＮＴ線材本体に電界めっき処理が施されたＣＮＴ線材を作製した。 (Examples 7 to 12)
As the plating treatment, the same method as in Examples 1 to 6 was performed except that electroless tin plating using a plating solution made of tin chloride was performed instead of electroless copper plating, and the CNT wire rod body was subjected to electroplating treatment. The applied CNT wire rod was produced.

（実施例１３〜１７）
ＣＮＴ線材本体として、円相当直径が０．０５ｍｍであるＣＮＴからなる素線を７２本作製し、７２本の素線を表１に示す撚り度で撚り合わせたＣＮＴ線材本体を用いた以外は実施例１〜５と同様の方法を行い、ＣＮＴ線材本体に電界めっき処理が施されたＣＮＴ線材を作製した。 (Examples 13 to 17)
As the CNT wire main body, 72 strands made of CNT having a diameter equivalent to a circle of 0.05 mm were prepared, and the CNT wire main body was used in which the 72 strands were twisted at the twist degree shown in Table 1. The same method as in Examples 1 to 5 was carried out to prepare a CNT wire rod in which the CNT wire rod main body was electroplated.

（比較例１）
実施例２と同様の方法で作製した円相当直径が０．１ｍｍであるＣＮＴからなる素線を用いて、銅めっきされていない素線１０本と、銅めっきされた素線８本をそれぞれ１００Ｔ／ｍで撚り合わせた、ＣＮＴ線材本体の一部に電界めっき処理が施されたＣＮＴ線材を作製した。 (Comparative Example 1)
Using the strands made of CNTs having a circle-equivalent diameter of 0.1 mm produced by the same method as in Example 2, 10 non-copper-plated strands and 8 copper-plated strands are 100T each. A CNT wire rod twisted at / m and subjected to electroplating treatment on a part of the CNT wire rod main body was produced.

（比較例２）
実施例１７と同様の方法で作製した円相当直径が０．０５ｍｍであるＣＮＴからなる素線を用いて、銅めっきされていない素線２６本と、銅めっきされた素線４６本を５００Ｔ／ｍで撚り合わせた、ＣＮＴ線材本体の一部に電界めっき処理が施されたＣＮＴ線材を作製した。 (Comparative Example 2)
Using the strands made of CNTs having a circle-equivalent diameter of 0.05 mm produced by the same method as in Example 17, 26 non-copper-plated strands and 46 copper-plated strands were 500T / A CNT wire rod twisted at m was produced by subjecting a part of the CNT wire rod main body to electroplating.

（参考例１）
実施例１と同様の方法で得たＣＮＴ線材本体を、実施例１と同じめっき液を用いて０．２Ａで５０分電解めっきすることで、めっき部の厚さが０．６μｍ、ＣＮＴ線材の各素線の表面の全長に対するめっき部が形成されている部分の長さの比（被覆割合）が０．７のＣＮＴ線材を作製した。 (Reference example 1)
The CNT wire rod body obtained by the same method as in Example 1 was electroplated at 0.2 A for 50 minutes using the same plating solution as in Example 1, so that the thickness of the plated portion was 0.6 μm, and the CNT wire rod had a thickness of 0.6 μm. A CNT wire rod having a ratio (covering ratio) of the length of the portion where the plated portion was formed to the total length of the surface of each strand was 0.7 was produced.

（参考例２）
実施例１と同様の方法で得たＣＮＴ線材本体を、実施例１と同じめっき液を用いて１Ａで１５分電解めっきすることで、めっき部の厚さが１．２μｍ、被覆割合が０．３のＣＮＴ線材を作製した。 (Reference example 2)
The CNT wire rod main body obtained by the same method as in Example 1 was electroplated at 1A for 15 minutes using the same plating solution as in Example 1, so that the thickness of the plated portion was 1.2 μm and the coating ratio was 0. 3 CNT wire rods were produced.

（ａ）めっきされた素線の割合の測定
（ＣＮＴ線材の表層部及び内部にめっき部が形成されている素線（ＣＮＴ束）の確認）
１．０ｍのＣＮＴ撚り線を長手方向に１０ｃｍ毎に測定した断面写真において、めっき部まで含めたＣＮＴ撚り線の断面形状の重心を求め、これをＸとした。続いて、各素線に、めっき部を含まない素線の断面形状から、各素線の重心を求めこれをＹｉとした。続いて、重心Ｘと重心Ｙｉを通る直線を引き、この直線とＣＮＴ撚り線の断面形状の外縁との交点をＺｉとした。線分Ｘ−Ｙｉの長さ及び線分Ｘ−Ｚｉの長さを測定し、線分Ｘ−Ｙｉの長さを線分Ｘ−Ｚｉの長さで除した値が０．７以上である素線を表層部に配された素線とし、それ以外の素線を内部に配された素線とし、各断面において表層部及び内部にめっき部が形成されている素線を確認した。 (A) Measurement of the ratio of plated strands (confirmation of the strands (CNT bundles) in which the plated portion is formed on the surface layer and inside of the CNT wire)
In a cross-sectional photograph of a 1.0 m CNT stranded wire measured every 10 cm in the longitudinal direction, the center of gravity of the cross-sectional shape of the CNT stranded wire including the plated portion was obtained and designated as X. Subsequently, the center of gravity of each wire was obtained from the cross-sectional shape of the wire not including the plated portion for each wire, and this was designated as Yi. Subsequently, a straight line passing through the center of gravity X and the center of gravity Yi was drawn, and the intersection of this straight line with the outer edge of the cross-sectional shape of the CNT stranded wire was defined as Zi. The length of the line segment X-Yi and the length of the line segment X-Zi are measured, and the value obtained by dividing the length of the line segment X-Yi by the length of the line segment X-Zi is 0.7 or more. The wire segment was defined as the wire segment arranged on the surface layer portion, the other strands were defined as the strands arranged inside, and the strands having the surface layer portion and the plated portion formed inside were confirmed in each cross section.

（めっき部が形成された素線（ＣＮＴ束）の本数の測定）
１．０ｍのＣＮＴ撚り線（ＣＮＴ線材）を長手方向に１０ｃｍ毎に垂直な面で切断し、イオンミリングによって断面を研磨した。つづいてＳＥＭ観察を行った。ＣＮＴ線材の各素線の表面の全長を求めこれをＡとした。つづいて、当該素線の表面のうち厚さ１μｍ以上のめっき部が形成されている部分の長さをＢとした。Ｂ／Ａが０．５以上の素線を、めっき部が形成されている素線とし、その本数を求めた。 (Measurement of the number of strands (CNT bundles) on which the plated part is formed)
A 1.0 m CNT stranded wire (CNT wire rod) was cut in a vertical plane every 10 cm in the longitudinal direction, and the cross section was polished by ion milling. Subsequently, SEM observation was performed. The total length of the surface of each wire of the CNT wire was obtained and designated as A. Subsequently, the length of the portion of the surface of the wire on which the plated portion having a thickness of 1 μm or more was formed was defined as B. The strands having a B / A of 0.5 or more were defined as the strands on which the plated portion was formed, and the number thereof was determined.

上記にて求めた厚さ１μｍ以上のめっき部が形成された素線の本数を、ＣＮＴ線材全体の素線の総数で除した値の比率を、めっきされた素線の割合（％）とした。 The ratio of the value obtained by dividing the number of strands having a plated portion having a thickness of 1 μm or more obtained above by the total number of strands of the entire CNT wire rod was defined as the ratio of the plated strands (%). ..

（ｂ）はんだとの接合性
ＣＮＴ撚り線の末端と銅板をはんだにて接続して、はんだ部が形成されたＣＮＴ接続構造体を作製し、銅板とＣＮＴ撚り線の間の接続抵抗（ｍΩ）を測定した。接続抵抗が５０ｍΩ以下である場合を接合性が良好であると評価した。 (B) Bondability with Solder The end of the CNT stranded wire and the copper plate are connected with solder to prepare a CNT connection structure in which the solder portion is formed, and the connection resistance (mΩ) between the copper plate and the CNT stranded wire is formed. Was measured. When the connection resistance was 50 mΩ or less, the bondability was evaluated as good.

（ｃ）許容電流
ＣＮＴ撚り線１０ｃｍのサンプルを用い、直流電源（ケースレー社製 ２２６８シリーズ）を用いて、１Ａの電流を１分間通電した。ＣＮＴ撚り線が断線しなかった場合、１分間室温で静置後、電流値を０．１Ａ上げて１分通電した。同様の操作をＣＮＴ撚り線が断線する電流値まで繰り返した。断線しないで１分間通電できた最大の電流値をＣＮＴ撚り線の断面積で割った値を算出し、許容電流（Ａ／ｍｍ２）を測定した。許容電流が２５Ａ／ｍｍ２以上である場合を過電流の発生が抑制されていると評価した。 (C) Allowable current A sample of 10 cm of CNT stranded wire was used, and a current of 1 A was applied for 1 minute using a DC power supply (2268 series manufactured by Keithley). When the CNT stranded wire was not broken, the CNT stranded wire was allowed to stand at room temperature for 1 minute, and then the current value was increased by 0.1 A to energize for 1 minute. The same operation was repeated until the current value at which the CNT stranded wire was broken. The maximum current value that could be energized for 1 minute without disconnection was divided by the cross-sectional area of the CNT stranded wire to calculate the allowable current (A / mm 2 ). When the allowable current was 25 A / mm 2 or more, it was evaluated that the occurrence of overcurrent was suppressed.

（ｄ）ＣＮＴ撚り線の密度
密度勾配管を用いて、上記ＣＮＴ撚り線の密度を測定した。長手方向の長さが２ｃｍのサンプルを用いた。ＣＮＴ撚り線の密度は、アルミの密度と同等の２．７ｇ／ｃｍ３未満である場合を、軽量電線として有効であると評価した。 (D) Density of CNT stranded wire The density of the CNT stranded wire was measured using a density gradient tube. A sample having a length of 2 cm in the longitudinal direction was used. When the density of the CNT stranded wire was less than 2.7 g / cm 3, which is equivalent to the density of aluminum, it was evaluated to be effective as a lightweight electric wire.

上記実施例１〜１７及び比較例１〜２の測定、評価結果を表１に示す。 Table 1 shows the measurement and evaluation results of Examples 1 to 17 and Comparative Examples 1 and 2.

Figure 2020181687
Figure 2020181687

表１に示すように、実施例１〜１７では、ＣＮＴ線材の内部及び表層部にめっき部が設けられており、ＣＮＴ線材において、めっきされた素線の割合がいずれも７０％以上であった。また、過電流の発生も抑えられていることから、耐久性に優れていた。また、はんだとの接合性もいずれも良好であり、さらにはＣＮＴ撚り線の密度もいずれも２．０以下であるため、軽量電線として有効であった。特に、撚り度が１００Ｔ／ｍ以上４００Ｔ／ｍ以下である実施例２〜４、８〜１０、１４〜１６では、いずれも接続抵抗が１５ｍΩ以下であり、優れた接合性を示した。また、撚り本数が多い実施例１３〜１７では、いずれも高い接合性を示し、特に実施例１４は接合性が顕著に優れていた。 As shown in Table 1, in Examples 1 to 17, plated portions were provided inside the CNT wire rod and on the surface layer portion, and the ratio of the plated strands in the CNT wire rod was 70% or more. .. In addition, since the generation of overcurrent is suppressed, the durability is excellent. In addition, the bondability with the solder was good, and the density of the CNT stranded wires was 2.0 or less, so that it was effective as a lightweight electric wire. In particular, in Examples 2 to 4, 8 to 10 and 14 to 16 in which the twist degree was 100 T / m or more and 400 T / m or less, the connection resistance was 15 mΩ or less, and excellent bondability was exhibited. Further, in Examples 13 to 17 having a large number of twists, all showed high bondability, and in particular, Example 14 was remarkably excellent in bondability.

一方、比較例１、２では、いずれもＣＮＴ撚り線の密度が２．０以下であるため、軽量電線として有効であったものの、ＣＮＴ線材において、めっきされた素線の割合が不十分であり、過電流が頻繁に発生し、耐久性に劣っていた。また、接続抵抗が実施例１〜１７と比較して格段に大きいことから、ＣＮＴ撚り線のはんだとの接合性も不良であった。参考例１では、めっき部の厚さが１μｍ未満であるため、はんだ付けの際にめっきが剥がれてＣＮＴが露出し、ＣＮＴ線材とはんだとの間に良好な接合性を付与させることができなかった。また、めっきの剥離に伴い、過電流が発生した。参考例２では、めっき部の厚さは１μｍ以上であるものの、被覆割合が０．５未満であるため、はんだ付けの際にはんだの濡れ性が悪く、参考例１と同様、ＣＮＴ線材とはんだとの間に良好な接合性を付与させることができなかった。また、めっきされていない素線同士での接触割合が多いため、素線同士の導通の向上が図れず、過電流が発生した。 On the other hand, in Comparative Examples 1 and 2, since the density of the CNT stranded wire was 2.0 or less, it was effective as a lightweight electric wire, but the ratio of the plated strands in the CNT wire was insufficient. , Overcurrent occurred frequently and the durability was inferior. Further, since the connection resistance was remarkably large as compared with Examples 1 to 17, the bondability of the CNT stranded wire with the solder was also poor. In Reference Example 1, since the thickness of the plated portion is less than 1 μm, the plating is peeled off during soldering and the CNTs are exposed, so that good bondability cannot be imparted between the CNT wire and the solder. It was. In addition, an overcurrent was generated due to the peeling of the plating. In Reference Example 2, although the thickness of the plated portion is 1 μm or more, the coating ratio is less than 0.5, so that the wettability of the solder is poor during soldering, and as in Reference Example 1, the CNT wire and the solder are soldered. It was not possible to impart good bondability to and from. In addition, since the contact ratio between the unplated strands is high, the continuity between the strands cannot be improved, and an overcurrent occurs.

１ カーボンナノチューブ線材（ＣＮＴ線材）
１ａ 表層部
１ｂ 内部
２ はんだ部
１０ カーボンナノチューブ線材接続構造体（ＣＮＴ線材接続構造体）
１１ カーボンナノチューブ束（ＣＮＴ束）
１１ａ カーボンナノチューブ束（ＣＮＴ束）
１１ｂ カーボンナノチューブ束（ＣＮＴ束）
１２ めっき部
２０ 被接続部材 1 Carbon nanotube wire (CNT wire)
1a Surface layer 1b Inside 2 Solder part 10 Carbon nanotube wire connection structure (CNT wire connection structure)
11 Carbon nanotube bundle (CNT bundle)
11a Carbon nanotube bundle (CNT bundle)
11b Carbon nanotube bundle (CNT bundle)
12 Plating part 20 Connected member

Claims (11)

複数のカーボンナノチューブ束を撚り合わせて構成されるカーボンナノチューブ線材であって、
前記カーボンナノチューブ線材の長手方向に沿って設けられ、前記カーボンナノチューブ線材の内部及び表層部に配されためっき部を備え、
前記カーボンナノチューブ線材の長手方向に垂直な方向の断面において、カーボンナノチューブ束の表面全長に対する、当該カーボンナノチューブ束の表面に厚さ１μｍ以上のめっき部が形成された部分の長さの比が０．５以上であるカーボンナノチューブ束の個数を、前記複数のカーボンナノチューブ束の総数で除した値の比率が、７０％以上であり、
前記複数のカーボンナノチューブ束の撚り度が１０〜３０００Ｔ／ｍであることを特徴とするカーボンナノチューブ線材。 It is a carbon nanotube wire rod composed by twisting a plurality of carbon nanotube bundles.
A plated portion provided along the longitudinal direction of the carbon nanotube wire rod and arranged inside and on the surface layer portion of the carbon nanotube wire rod is provided.
In the cross section in the direction perpendicular to the longitudinal direction of the carbon nanotube wire rod, the ratio of the length of the portion where the plated portion having a thickness of 1 μm or more is formed on the surface of the carbon nanotube bundle to the total surface length of the carbon nanotube bundle is 0. The ratio of the value obtained by dividing the number of carbon nanotube bundles of 5 or more by the total number of the plurality of carbon nanotube bundles is 70% or more.
A carbon nanotube wire rod having a twist degree of 10 to 3000 T / m for the plurality of carbon nanotube bundles. 前記めっき部が、前記複数のカーボンナノチューブ束のうちの隣接する複数のカーボンナノチューブ束間に３次元的に形成されていることを特徴とする請求項１に記載のカーボンナノチューブ線材。 The carbon nanotube wire rod according to claim 1, wherein the plated portion is three-dimensionally formed between a plurality of adjacent carbon nanotube bundles among the plurality of carbon nanotube bundles. 前記複数のカーボンナノチューブ束の撚り度が、５０〜１０００Ｔ／ｍであることを特徴とする、請求項１又は２に記載のカーボンナノチューブ線材。 The carbon nanotube wire rod according to claim 1 or 2, wherein the twist degree of the plurality of carbon nanotube bundles is 50 to 1000 T / m. 前記複数のカーボンナノチューブ束の撚り度が、１００〜４００Ｔ／ｍであることを特徴とする、請求項３に記載のカーボンナノチューブ線材。 The carbon nanotube wire rod according to claim 3, wherein the twist degree of the plurality of carbon nanotube bundles is 100 to 400 T / m. 前記複数のカーボンナノチューブ束の撚り本数が１０〜１０００本であることを特徴とする、請求項１〜４のいずれか１項に記載のカーボンナノチューブ線材。 The carbon nanotube wire rod according to any one of claims 1 to 4, wherein the number of twists of the plurality of carbon nanotube bundles is 10 to 1000. 前記複数のカーボンナノチューブ束の撚り本数が５０〜３００本であることを特徴とする、請求項５に記載のカーボンナノチューブ線材。 The carbon nanotube wire rod according to claim 5, wherein the number of twists of the plurality of carbon nanotube bundles is 50 to 300. 前記めっき部は、銅（Ｃｕ）、銀（Ａｇ）、金（Ａｕ）、スズ（Ｓｎ）、白金（Ｐｔ）、チタン（Ｔｉ）、鉄（Ｆｅ）、クロム（Ｃｒ）及びニッケル（Ｎｉ）からなる群から選択される金属或いはこれらの金属の少なくとも１種を含む合金で形成されることを特徴とする、請求項１〜６のいずれか１項に記載のカーボンナノチューブ線材。 The plated portion is made of copper (Cu), silver (Ag), gold (Au), tin (Sn), platinum (Pt), titanium (Ti), iron (Fe), chromium (Cr) and nickel (Ni). The carbon nanotube wire rod according to any one of claims 1 to 6, wherein the carbon nanotube wire rod is formed of a metal selected from the above group or an alloy containing at least one of these metals. 異種元素がドープされていることを特徴とする、請求項１〜７のいずれか１項に記載のカーボンナノチューブ線材。 The carbon nanotube wire rod according to any one of claims 1 to 7, wherein the carbon nanotube wire rod is doped with a different element. 前記カーボンナノチューブ線材を構成するカーボンナノチューブが、２層又は３層の層構造を有することを特徴とする、請求項１〜８のいずれか１項に記載のカーボンナノチューブ線材。 The carbon nanotube wire rod according to any one of claims 1 to 8, wherein the carbon nanotubes constituting the carbon nanotube wire rod have a two-layer or three-layer structure. 複数のカーボンナノチューブ束を１０〜３０００Ｔ／ｍの撚り度で撚り合わせて構成されるカーボンナノチューブ線材と、前記カーボンナノチューブ線材に接続されるはんだ部とを備えるカーボンナノチューブ線材接続構造体であって、
前記カーボンナノチューブ線材は、該カーボンナノチューブ線材の長手方向に沿って設けられ、前記カーボンナノチューブ線材の内部及び表層部に配されためっき部を備え、
前記カーボンナノチューブ線材の長手方向に垂直な方向の断面において、カーボンナノチューブ束の表面全長に対する、当該カーボンナノチューブ束の表面に厚さ１μｍ以上のめっき部が形成された部分の長さの比が０．５以上であるカーボンナノチューブ束の個数を、前記複数のカーボンナノチューブ束の総数で除した値の比率が、７０％以上であることを特徴とするカーボンナノチューブ線材接続構造体。 A carbon nanotube wire connecting structure including a carbon nanotube wire formed by twisting a plurality of carbon nanotube bundles at a twist degree of 10 to 3000 T / m and a solder portion connected to the carbon nanotube wire.
The carbon nanotube wire rod is provided along the longitudinal direction of the carbon nanotube wire rod, and includes a plated portion arranged inside and on the surface layer portion of the carbon nanotube wire rod.
In the cross section in the direction perpendicular to the longitudinal direction of the carbon nanotube wire rod, the ratio of the length of the portion where the plated portion having a thickness of 1 μm or more is formed on the surface of the carbon nanotube bundle to the total surface length of the carbon nanotube bundle is 0. A carbon nanotube wire rod connecting structure, wherein the ratio of the value obtained by dividing the number of carbon nanotube bundles of 5 or more by the total number of the plurality of carbon nanotube bundles is 70% or more. 複数のカーボンナノチューブ束で構成されるカーボンナノチューブ線材本体に無電界めっき処理を施して下地部を形成する工程と、
前記無電界めっき処理を施したカーボンナノチューブ線材本体に電界めっき処理を施して、前記カーボンナノチューブ線材本体の長手方向に沿って、該カーボンナノチューブ線材本体の内部及び表層部にめっき部を形成する工程と、
前記電界めっきを施す工程の後に、前記複数のカーボンナノチューブ束を１０〜３０００Ｔ／ｍの撚り度で撚り合わせる工程と、
を有することを特徴とする、カーボンナノチューブ線材の製造方法。 A process of forming a base portion by subjecting a carbon nanotube wire rod body composed of a plurality of carbon nanotube bundles to a fieldless plating process.
A step of subjecting the carbon nanotube wire rod main body subjected to the electric field plating treatment to an electric field plating treatment to form a plated portion inside and on the surface layer portion of the carbon nanotube wire rod main body along the longitudinal direction of the carbon nanotube wire rod main body. ,
After the step of applying the electric field plating, a step of twisting the plurality of carbon nanotube bundles at a twist degree of 10 to 3000 T / m and a step of twisting the plurality of carbon nanotube bundles.
A method for producing a carbon nanotube wire rod, which comprises.
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