WO2019083029A1 - Fil électrique revêtu de nanotubes de carbone - Google Patents

Fil électrique revêtu de nanotubes de carbone

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Publication number
WO2019083029A1
WO2019083029A1 PCT/JP2018/039971 JP2018039971W WO2019083029A1 WO 2019083029 A1 WO2019083029 A1 WO 2019083029A1 JP 2018039971 W JP2018039971 W JP 2018039971W WO 2019083029 A1 WO2019083029 A1 WO 2019083029A1
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Prior art keywords
wire
cnt
carbon nanotube
less
covering layer
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PCT/JP2018/039971
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English (en)
Japanese (ja)
Inventor
英樹 會澤
山崎　悟志
山下　智
憲志 畑本
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古河電気工業株式会社
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Application filed by 古河電気工業株式会社 filed Critical 古河電気工業株式会社
Priority to JP2019550340A priority Critical patent/JP7306995B2/ja
Publication of WO2019083029A1 publication Critical patent/WO2019083029A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/42—Insulated conductors or cables characterised by their form with arrangements for heat dissipation or conduction

Definitions

  • the present invention relates to a carbon nanotube coated electric wire in which a carbon nanotube wire composed of a plurality of carbon nanotubes is coated with an insulating material.
  • Carbon nanotubes (hereinafter sometimes referred to as "CNT") are materials having various properties, and their application in many fields is expected.
  • CNT is a single layer of a tubular body having a network structure of a hexagonal lattice, or a three-dimensional network structure composed of multiple layers arranged substantially coaxially, which is lightweight, conductive, and thermally conductive. Excellent in various properties such as elasticity, elasticity and mechanical strength. However, it is not easy to wire CNTs, and no technology has been proposed for utilizing CNTs as wires.
  • CNT as a substitute for metal which is a filling material of a via hole formed in a multilayer wiring structure.
  • CNT as a substitute for metal which is a filling material of a via hole formed in a multilayer wiring structure.
  • multilayer CNTs in which a plurality of incisions of the multilayer CNT concentrically extended to the end far from the growth origin of the multilayer CNT are brought into contact with the conductive layer The wiring structure used as an interlayer wiring of two or more conducting wire layers is proposed (patent document 1).
  • a carbon nanotube material in which a conductive deposit made of metal or the like is formed at the electrical junction of adjacent CNT wires, such carbon It is disclosed that nanotube materials can be applied to a wide range of applications (Patent Document 2). Moreover, the heater which has a heat conductive member made from the matrix of a carbon nanotube is proposed from the outstanding thermal conductivity which a CNT wire has (patent document 3).
  • the covered electric wire which consists of a core wire which consists of one or a plurality of wires, and an insulation coating which covers the core is used as electric power lines and signal lines in various fields, such as a car and industrial equipment.
  • a material of the wire which comprises a core wire although a copper or copper alloy is usually used from a viewpoint of an electrical property, aluminum or an aluminum alloy is proposed from a viewpoint of weight reduction in recent years.
  • the specific gravity of aluminum is about 1/3 of the specific gravity of copper
  • the conductivity of aluminum is about 2/3 of that of copper (based on 100% IACS for pure copper, about 66% IACS for pure aluminum)
  • An object of the present invention is to provide a carbon nanotube coated electric wire which is excellent in heat radiation characteristics, shape retention, and workability.
  • the aspect of the present invention comprises a carbon nanotube wire comprising one or more carbon nanotube aggregates composed of a plurality of carbon nanotubes, and an insulating covering layer covering the carbon nanotube wire, and the insulating covering layer is constituted
  • the material has a Rockwell hardness of greater than 22, and a ratio of the thickness of the insulating covering layer to the equivalent circle diameter of the carbon nanotube wire of greater than 0.05.
  • the Rockwell hardness of the material is 25 or more and 120 or less, and the ratio of the thickness of the insulating covering layer to the equivalent circle diameter of the carbon nanotube wire is 0.060 or more and 0.600. It is a carbon nanotube coated electric wire which is the following.
  • the aspect of this invention is a carbon nanotube coated electric wire whose circle equivalent diameter of the single wire which comprises the said carbon nanotube wire is 0.090 mm or more and 10 mm or less.
  • the aspect of this invention is a carbon nanotube coated electric wire whose circle equivalent diameter of the single wire which comprises the said carbon nanotube wire is 0.180 mm or more and 0.5 mm or less.
  • the carbon nanotube wire comprises a plurality of the aggregate of carbon nanotubes, and the half width ⁇ of an azimuth angle in an azimuth plot by small angle X-ray scattering showing the orientation of the plurality of aggregate of carbon nanotubes is 60 It is a carbon nanotube coated electric wire which is less than °°.
  • the q value of the peak top at the (10) peak of the scattering intensity by X-ray scattering indicating the density of the plurality of carbon nanotubes is 2.0 nm ⁇ 1 or more and 5.0 nm ⁇ 1 or less
  • width ⁇ q is a carbon nanotube covered electric wire is 0.1 nm -1 or 2.0 nm -1 or less.
  • a carbon nanotube wire using a carbon nanotube as a core wire is anisotropic in thermal conduction, and heat is preferentially conducted in the longitudinal direction as compared with the radial direction. That is, since the carbon nanotube wire has anisotropic heat dissipation characteristics, it has excellent heat dissipation characteristics as compared to metal core wires. Therefore, the design of the insulating covering layer for covering the core wire using carbon nanotubes needs to be designed differently from the insulating covering layer of the metal core wire.
  • the carbon nanotube wire has a Rockwell hardness of greater than 22 of the material forming the insulation covering layer, and the ratio of the thickness of the insulation covering layer to the equivalent circle diameter of the carbon nanotube wire is By being larger than 0.05, it is possible to obtain a carbon nanotube coated electric wire which is excellent in heat radiation characteristics, shape retention, and workability.
  • the Rockwell hardness of the material is 25 or more and 120 or less, and the ratio of the thickness of the insulating covering layer to the equivalent circle diameter of the carbon nanotube wire is 0.060 or more and 0.600 or less As a result, the shape of the carbon nanotube coated wire can be more easily maintained.
  • the carbon nanotube wire when the equivalent circle diameter of the single wire constituting the carbon nanotube wire is 0.090 mm or more and 10 mm or less, the carbon nanotube wire is excellent in the carbon nanotube coated wire while fully utilizing the strength of the carbon nanotube wire. Heat dissipation characteristics can be imparted. Furthermore, when the equivalent circle diameter of a single wire constituting the carbon nanotube wire is 0.180 mm or more and 0.5 mm or less, shape retentivity and workability can be improved even if the insulating coating layer is relatively thin. The heat dissipation characteristics can also be improved.
  • the carbon nanotube or carbon nanotube in the carbon nanotube wire has the half width ⁇ of the azimuth angle in the azimuth plot by small angle X-ray scattering of the carbon nanotube aggregate in the carbon nanotube wire being 60 ° or less. Since the aggregates can be present at high density, the carbon nanotube wire exhibits excellent heat dissipation characteristics.
  • q values of the peak top in (10) the peak of scattering intensity by X-ray scattering of aligned carbon nanotubes is at 2.0 nm -1 or 5.0 nm -1 or less, and the half width ⁇ q There 0.1nm by -1 to 2.0 nm -1 or less, because it has a carbon nanotube has high orientation, exhibits excellent heat dissipation properties of carbon nanotube wires.
  • FIG. 1 is a figure showing an example of the two-dimensional scattering image of the scattering vector q of a plurality of carbon nanotube aggregates by SAXS
  • the figure (b) is the position of transmission X-ray in the azimuth plot two-dimensional scattering image.
  • Is a graph showing an example of azimuth angle-scattering intensity of an arbitrary scattering vector q having an origin of.
  • 15 is a graph showing the relationship between q value and strength by WAXS of a plurality of carbon nanotubes constituting a carbon nanotube aggregate.
  • a carbon nanotube coated electric wire (hereinafter sometimes referred to as “CNT coated electric wire") 1 according to an embodiment of the present invention may be referred to as a carbon nanotube wire (hereinafter referred to as "CNT wire") 2.
  • the outer circumferential surface of the insulating coating layer 21 is coated on the outer circumferential surface 10. That is, the insulating coating layer 21 is coated along the longitudinal direction of the CNT wire 10. In the CNT-coated electric wire 1, the entire outer peripheral surface of the CNT wire 10 is covered with the insulating covering layer 21. Further, in the CNT-coated electric wire 1, the insulating covering layer 21 is in an aspect in direct contact with the outer peripheral surface of the CNT wire 10. In FIG.
  • the CNT wire 10 is a strand (single wire) formed of one CNT wire 10.
  • the CNT wire 10 may be in the form of a stranded wire obtained by twisting a plurality of CNT wires 10.
  • the equivalent circle diameter and the cross-sectional area of the CNT wire 10 can be appropriately adjusted.
  • the strength of the CNT wire 10 is higher than that of a single wire, and disconnection of the CNT wire 10 caused by the deformation of the CNT wire 10 can be suppressed more reliably.
  • the CNT wire 10 is sometimes referred to as a carbon nanotube assembly (hereinafter referred to as "CNT assembly") composed of a plurality of CNTs 11a, 11a, ... having a layer structure of one or more layers. 11) It is formed by bundling one or more of eleven.
  • the CNT wire means a CNT wire having a ratio of CNT of 90% by mass or more.
  • plating and a dopant are excluded in calculation of the CNT ratio in a CNT wire.
  • the CNT wire 10 has a configuration in which a plurality of CNT assemblies 11 are bundled.
  • the longitudinal direction of the CNT assembly 11 forms the longitudinal direction of the CNT wire 10. Therefore, the CNT assembly 11 is linear.
  • the plurality of CNT aggregates 11, 11,... In the CNT wire 10 are arranged substantially in the same longitudinal direction. Therefore, the plurality of CNT aggregates 11, 11, ... in the CNT wire 10 are oriented.
  • the equivalent circle diameter of the single wire (wire) constituting the CNT wire 10 is preferably 0.090 mm or more and 10 mm or less.
  • the equivalent circle diameter of the single wire constituting the CNT wire 10 is preferably 0.090 mm, more preferably 0.180 mm, from the viewpoint of making full use of the strength.
  • the rigidity of the CNT wire 10 itself is enhanced. Therefore, even if the insulating covering layer 21 is relatively thin, the shape retentivity and the workability can be improved.
  • the upper limit value of the circle equivalent diameter of the single wire constituting the CNT wire 10 is preferably 10 mm, more preferably 3 mm, still more preferably 1 mm, and particularly preferably 0.5 mm from the viewpoint of imparting excellent heat dissipation characteristics.
  • the equivalent circle diameter of the single wire constituting the CNT wire 10 is 0.5 mm or less, it is possible to suppress the surface area relative to the volume of the single wire from being reduced excessively, and to improve the heat dissipation characteristics.
  • the equivalent circle diameter of the CNT wire 10 as the stranded wire is preferably 0.090 mm or more and 15 mm or less.
  • the lower limit is preferably 0.090 mm, more preferably 0.400 mm, from the viewpoint of making full use of the strength of the CNT wire 10 as a stranded wire, and on the other hand, the excellent heat dissipation characteristics of the CNT wire 10 as a single wire
  • the upper limit thereof is preferably 15 mm, more preferably 3 mm, and still more preferably 1 mm, from the viewpoint of not impairing
  • the CNT assembly 11 is a bundle of CNTs 11 a having a layer structure of one or more layers.
  • the longitudinal direction of the CNTs 11 a forms the longitudinal direction of the CNT assembly 11.
  • the plurality of CNTs 11a, 11a,... In the CNT assembly 11 are arranged substantially in the same longitudinal direction. Therefore, the plurality of CNTs 11a, 11a,... In the CNT assembly 11 are oriented.
  • the equivalent circle diameter of the CNT assembly 11 is, for example, 20 nm or more and 1000 nm or less, and more typically 20 nm or more and 80 nm or less.
  • the width dimension of the outermost layer of the CNTs 11 a is, for example, 1.0 nm or more and 5.0 nm or less.
  • the CNTs 11 a constituting the CNT assembly 11 are cylindrical bodies having a single-layer structure or a multi-layer structure, and are respectively referred to as SWNT (single-walled nanotubes) and MWNT (multi-walled nanotubes).
  • SWNT single-walled nanotubes
  • MWNT multi-walled nanotubes
  • FIG. 2 for convenience, only the CNTs 11 a having a two-layer structure are described, but the CNT aggregate 11 includes CNTs having a three-layer structure or more and a CNT having a single-layer structure. It may be formed of CNT having a layer structure of three or more layer structure or CNT having a layer structure of single layer structure.
  • the CNT 11a having a two-layer structure is a three-dimensional network structure in which two cylindrical bodies T1 and T2 having a network structure of a hexagonal lattice are arranged substantially coaxially, and is called DWNT (Double-walled nanotube) .
  • the hexagonal lattice which is a structural unit, is a six-membered ring having a carbon atom at its apex, and adjacent to another six-membered ring, these are continuously bonded.
  • the properties of the CNTs 11a depend on the chirality of the above-mentioned cylindrical body.
  • the chirality is roughly classified into an armchair type, a zigzag type, and a chiral type.
  • the armchair type is metallic
  • the zigzag type is semiconductive and semimetallic
  • the chiral type is semiconductive and semimetallic. Therefore, the conductivity of the CNTs 11a largely differs depending on which chirality the tubular body has.
  • chiral CNTs 11a exhibit metallic behavior by doping chiral CNTs 11a exhibiting semiconducting behavior with substances having different electron donating properties or electron accepting properties (different elements). .
  • the doping of different elements causes scattering of conduction electrons inside the metal to lower the conductivity, but similar to this, the CNT 11a showing metallic behavior is doped with different elements. If it does, it causes a decrease in conductivity.
  • the doping effects on the CNTs 11a showing the behavior of the metal and the CNTs 11a showing the behavior of the semiconductivity are in a trade-off relationship from the viewpoint of the conductivity, and thus the behavior of the metal theoretically appears. It is desirable that the CNTs 11a and the CNTs 11a exhibiting the behavior of the semiconductor property are separately manufactured, and the doping process is performed only on the CNTs 11a exhibiting the behavior of the semiconductor property, and then these are combined. In the case where the CNTs 11a exhibiting metallic behavior and the CNTs 11a exhibiting semiconductive behavior are produced in a mixed state, it is preferable to select the layer structure of the CNTs 11a in which the doping process with different elements or molecules is effective. Thereby, the conductivity of the CNT wire 10 formed of a mixture of the CNTs 11a exhibiting metallic behavior and the CNTs 11a exhibiting semiconductive behavior can be further improved.
  • a CNT having a smaller number of layers such as a two-layer structure or a three-layer structure
  • a CNT having a larger number of layers is relatively more conductive than a CNT having a larger number of layers, and when doped, the two-layer structure or three layers
  • the doping effect in the structured CNT is the highest. Therefore, in order to further improve the conductivity of the CNT wire 10, it is preferable to increase the proportion of CNTs having a two-layer structure or a three-layer structure.
  • the ratio of CNTs having a two-layer structure or a three-layer structure to the entire CNTs is preferably 50 number% or more, and more preferably 75 number% or more.
  • the proportion of CNTs having a two-layer structure or a three-layer structure can be determined by observing and analyzing the cross section of the CNT assembly 11 with a transmission electron microscope (TEM) and measuring the number of layers of 50 to 200, preferably 100 CNTs. It can be calculated by measuring.
  • TEM transmission electron microscope
  • Fig.3 (a) is a figure which shows an example of the two-dimensional scattering image of the scattering vector q of several CNT assembly 11,11, ... by small angle X ray scattering (SAXS), and FIG.3 (b) is shown.
  • 6 is a graph showing an example of an azimuth plot showing the relationship between azimuth angle and scattering intensity of an arbitrary scattering vector q whose origin is the position of transmitted X-ray in a two-dimensional scattering image.
  • SAXS is suitable for evaluating structures of several nm to several tens of nm in size.
  • the orientation of the CNT 11a having an outer diameter of several nm and the orientation of the CNT aggregate 11 having an outer diameter of several tens nm by analyzing the information of the X-ray scattering image by the following method using SAXS Can be evaluated.
  • the x component of the scattering vector q (q 2 ⁇ / d: d is lattice spacing) of the CNT assembly 11
  • the y component q y is relatively narrowly distributed rather than q x .
  • half value width (DELTA) (theta) of the azimuth angle in the azimuth plot shown in FIG.3 (b) is 48 degrees. From these analysis results, in the CNT wire 10, it can be said that the plurality of CNTs 11a, 11a,... And the plurality of CNT aggregates 11, 11,. As described above, since the plurality of CNTs 11a, 11a,... And the plurality of CNT aggregates 11, 11,. It is easy to be dissipated while transmitting smoothly along the longitudinal direction of the.
  • the CNT wire 10 can adjust the heat radiation route in the longitudinal direction and the cross-sectional direction of the diameter by adjusting the orientation of the CNTs 11 a and the CNT aggregate 11, and therefore, the heat radiation characteristics superior to the metal core wire. Demonstrate.
  • orientation refers to the angle difference of the vector of the CNT and the CNT assembly inside with respect to the vector V in the longitudinal direction of the stranded wire produced by twist-collecting CNTs.
  • the CNT wire 10 is obtained by obtaining an orientation of a certain value or more indicated by the half width ⁇ of the azimuth angle in an azimuth plot of small angle X-ray scattering (SAXS) indicating the orientation of a plurality of CNT aggregates 11, 11,.
  • SAXS small angle X-ray scattering
  • the half value width ⁇ of the azimuth angle is preferably 60 ° or less, and particularly preferably 50 ° or less.
  • FIG. 4 is a graph showing the q value-intensity relationship by WAXS (wide-angle X-ray scattering) of the plurality of CNTs 11a, 11a,.
  • the CNTs 11a, 11a,... Form a hexagonal close-packed structure in plan view. can do. Therefore, the diameter distribution of the plurality of CNT aggregates is narrow in the CNT wire 10, and the plurality of CNTs 11a, 11a,... Form a hexagonal close-packed structure by having a regular arrangement, ie, a high density. It can be said that it exists in high density.
  • the plurality of CNT aggregates 11, 11... Have good orientation, and further, the plurality of CNTs 11a, 11a,. Because they are arranged at high density, the heat of the CNT wire 10 is easily dissipated while being smoothly transmitted along the longitudinal direction of the CNT aggregate 11. Therefore, the CNT wire rod 10 can adjust the heat dissipation route in the longitudinal direction and the cross-sectional direction of the diameter by adjusting the arrangement structure and density of the CNT aggregate 11 and the CNTs 11a, so it is superior to a metal core wire. Demonstrates heat dissipation characteristics.
  • multiple CNT11a, 11a, of intensity by X-ray scattering shows a density of ⁇ (10) q value of the peak top in the peak 2.0 nm - 1 or 5.0 nm -1 or less, and is preferably a half-value width [Delta] q (FWHM) is 0.1 nm -1 or 2.0 nm -1 or less.
  • the orientation of the CNT aggregate 11 and the CNTs 11 and the alignment structure and density of the CNTs 11a are adjusted by appropriately selecting the spinning method such as dry spinning, wet spinning, liquid crystal spinning, and spinning conditions of the spinning method described later. be able to.
  • thermoplastic resin As a material of the insulation coating layer 21, a thermoplastic resin can be mentioned, for example.
  • a thermoplastic resin for example, polypropylene (Young's modulus: 1.1 to 1.4, Rockwell hardness: 85 to 110), cellulose acetate (Young's modulus: 0.46 to 2.8, Rockwell hardness: 34 to 125), polyamide (Young's modulus: 1.1 to 4.2, Rockwell hardness: 103 to 118), trifluorochloroethylene resin (PCTFE) (Young's modulus :, Rockwell height: 75 to 95), tetrafluorinated And ethylene hexafluoride / propylene copolymer (FEP) (Young's modulus: 0.35, Rockwell hardness: 25) and the like can be mentioned. These may be used alone or in combination of two or more.
  • the thickness of the insulating covering layer 21 is not particularly limited, but is preferably 0.002 mm or more and 1.0 mm or less.
  • the lower limit of the thickness of the insulating covering layer 21 is 0.006 mm because the insulating covering layer 21 covered with the CNT 10 wire does not deteriorate even if the shape of the CNT 10 wire is deformed while sufficiently protecting the CNT 10 wire.
  • Preferably, 0.08 mm is particularly preferred.
  • the upper limit value of the thickness of the C insulating covering layer 21 is that the insulating covering layer 21 can correspond to the deformation as the shape of the CNT 10 wire deforms while the strength of the insulating covering layer 21 is sufficiently maintained. 0 mm is preferable and 0.8 mm is more preferable
  • the insulating covering layer 21 may be a single layer as shown in FIG. 1, or alternatively, may be two or more layers. When the insulating covering layer 21 is composed of a plurality of layers, the thickness of the insulating covering layer 21 is calculated by the sum of the layer thicknesses of the respective insulating covering layers 21. In addition, a layer of a thermosetting resin may be further provided between the outer surface of the CNT wire 10 and the insulating coating layer 21 as necessary.
  • the Rockwell hardness of the material constituting the insulating covering layer 21 is larger than 22 and the ratio of the thickness of the insulating covering layer 21 to the equivalent circle diameter of the CNT wire 10 is larger than 0.05 .
  • the Rockwell hardness of the material is greater than 22 and the ratio is greater than 0.05, the hardness of the insulating covering layer 21 is large, and the insulating covering layer 21 is also relatively thick, so the shape of the CNT wire 10 Even if it deform
  • the CNT-coated wire 1 exhibits excellent shape retention, and the CNT-coated wire 1 can be provided with excellent workability.
  • the Rockwell hardness of the material is 25 or more and 120 or less, and the ratio of the thickness of the insulating covering layer 21 to the equivalent circle diameter of the CNT wire 10 is 0.060 or more and 0.600 or less preferable.
  • the edge covering layer 21 can be controlled in a well-balanced manner within a range that is neither too hard nor too thick, and the shape of the CNT-coated wire 1 can be more easily maintained.
  • the excellent shape retentivity of the CNT-coated electric wire 1 can be maintained, and stable workability can be imparted.
  • the thickness of the insulating covering layer 21 it is possible to obtain the CNT-coated electric wire 1 having excellent heat dissipation characteristics without deteriorating the insulation reliability. Furthermore, the ratio of the thickness of the insulating covering layer 21 to the equivalent circle diameter of the CNT wire 10 is more preferably 0.015 or more. Thereby, the insulation reliability of the CNT-coated wire 1 can be improved.
  • the Rockwell hardness means a measured value of R scale, and can be measured based on JIS 7202-2. If the Rockwell hardness is 22 or less, the hardness of the insulating covering layer 21 is insufficient, and it is difficult to maintain the shape of the CNT-coated wire 1.
  • the thickness ratio of the insulating covering layer 21 to the equivalent circle diameter of the CNT wire 10 is 0.05 or less, the hardness of the insulating covering layer 21 is likewise insufficient, and the shape of the CNT covered electric wire 1 Hard to hold
  • the CNT covered electric wire 1 is excellent It is possible to exhibit the heat radiation characteristics and the shape retentivity, and to provide the CNT-coated electric wire 1 with excellent workability.
  • the ratio of the cross-sectional area in the radial direction of the insulating covering layer 21 to the cross-sectional area in the radial direction of the CNT wire 10 is preferably in the range of 0.05 or more and 0.7 or less.
  • the core wire is the CNT wire 10 which is lighter compared to copper, aluminum, etc., and the thickness of the insulating covering layer 21 is thinned. Since it can do, the outstanding thermal radiation characteristic to the heat of CNT wire material 10 can be acquired, without spoiling insulation reliability. Moreover, weight reduction of the electric wire coat
  • the CNT-covered electric wire 1 can be obtained by covering the outer surface of the CNT wire 10 with the insulating covering layer 21 at the ratio of the cross sectional area.
  • the shape in the longitudinal direction can be maintained, and deformation such as bending is easy. Therefore, the CNT-coated wire 1 can be formed in a shape along a desired wiring path.
  • adhesion between the CNT wire 10 and the insulating coating layer 21 is improved as compared to a coated wire using a core wire of aluminum or copper. It can improve and it can control exfoliation between CNT wire 10 and insulating covering layer 21.
  • the cross-sectional area in the radial direction of the CNT wire 10 is not particularly limited, but for example, 0.005 mm 2 or more and 80 mm 2 or less is preferable, 0 .01Mm 2 or 10 mm 2 and more preferably less, 0.03 mm 2 or more 6.0 mm 2 or less is particularly preferred.
  • the cross-sectional area in the radial direction of the insulating cover layer 21 is not particularly limited, from the viewpoint of further improving the insulation reliability, for example, preferably 0.00025Mm 2 or 56 mm 2 or less, 0.0005 mm 2 or more 7.0mm 2 or less is especially preferable.
  • the cross-sectional area can be measured, for example, from an image of a scanning electron microscope (SEM) observation. Specifically, after obtaining an SEM image (100 times to 10,000 times) of a radial cross section of the CNT-coated wire 1, the CNT wire 10 was penetrated from the area of the portion surrounded by the outer periphery of the CNT wire 10.
  • SEM scanning electron microscope
  • the sum of the area obtained by subtracting the area of the material of the insulating covering layer 21, the area of the portion of the insulating covering layer 21 covering the outer periphery of the CNT wire 10 and the area of the material of the insulating covering layer 21 intruding inside the CNT wire 10 is
  • the cross-sectional area in the radial direction of the CNT wire 10 and the cross-sectional area in the radial direction of the insulating coating layer 21 are respectively used.
  • the radial cross-sectional area of the insulating covering layer 21 also includes the resin that has entered between the CNT wires 10.
  • Young's modulus of CNT is higher than that of aluminum and copper used as conventional core wires. While the Young's modulus of aluminum is 70.3 GPa and the Young's modulus of copper is 129.8 GPa, the Young's modulus of CNT has a value of 300 to 1500 GPa, which is more than double. Therefore, in the CNT-coated electric wire 1, a material having a high Young's modulus (a thermoplastic resin having a high Young's modulus) can be used as the material of the insulating covering layer 21 as compared to a coated electric wire using aluminum and copper as core wires. Therefore, excellent wear resistance can be imparted to the insulating coating layer 21 of the CNT-coated electric wire 1, and the CNT-coated electric wire 1 exhibits excellent durability.
  • a material having a high Young's modulus a thermoplastic resin having a high Young's modulus
  • the Young's modulus of CNT is higher than that of aluminum and copper used as conventional core wires. Therefore, in the CNT-coated electric wire 1, the ratio of the Young's modulus of the material constituting the insulating coating layer to the Young's modulus of the core is smaller than the ratio of the Young's modulus of the coated electric wire using aluminum and copper as the core. Therefore, in the CNT-coated electric wire 1, peeling of the CNT wire 10 and the insulating covering layer 21 and cracking of the insulating covering layer 21 can be suppressed even when being repeatedly bent as compared with the covered electric wire using aluminum or copper as the core wire.
  • the ratio of the Young's modulus of the material constituting the insulating coating layer 21 to the Young's modulus of the CNT wire 10 is not particularly limited, but the lower limit of the ratio of the Young's modulus is the CNT wire even if the CNT-coated wire 1 is repeatedly bent. Since the insulating covering layer 21 follows 10 to prevent the insulating covering layer 21 from peeling off from the CNT wire 10, 0.0001 is preferable, and even if the CNT coated electric wire 1 is bent for a long period of time, from the CNT wire 10 In order to prevent the insulation coating layer 21 from peeling, 0.01 is more preferable, and 0.05 is particularly preferable.
  • the upper limit value of the ratio of Young's modulus is preferably 3.0 from the viewpoint of preventing the occurrence of cracks in the insulating covering layer 21 even if the CNT-coated wire 1 is repeatedly bent, and the CNT-coated wire 1 for a long time 1.0 is more preferable, and 0.7 is particularly preferable, from the viewpoint of preventing the occurrence of cracks in the insulating covering layer 21 even when the B is bent.
  • the thickness in the direction orthogonal to the longitudinal direction of the insulating covering layer 21 is preferably uniform from the viewpoint of improving the mechanical strength such as the abrasion resistance of the CNT-coated electric wire 1.
  • the uneven thickness ratio of the insulating coating layer 21 is preferably, for example, 50% or more from the point of imparting excellent abrasion resistance, and particularly preferably 80% or more from the point of further improving the abrasion resistance.
  • the minimum value / the maximum value of the thickness of the insulation coating layer 21) ⁇ 100 is calculated, and the value obtained by averaging the ⁇ values calculated in each cross section is meant.
  • the thickness of the insulating covering layer 21 can be measured, for example, from an image of SEM observation by circular approximation of the CNT wire 10.
  • the longitudinal center side refers to a region located at the center as viewed from the longitudinal direction of the line.
  • the uneven thickness ratio of the insulating covering layer 21 is, for example, when the insulating covering layer 21 is formed on the outer peripheral surface of the CNT wire 10 by extrusion coating, the tension in the longitudinal direction of the CNT wire 10 passing through the die during the extrusion process is increased. Can improve it.
  • the CNT-coated electric wire 1 can be manufactured by first manufacturing the CNTs 11 a, forming the CNT wire 10 from the obtained plurality of CNTs 11 a, and coating the outer circumferential surface of the CNT wire 10 with the insulating covering layer 21.
  • the CNTs 11a can be manufactured by a method such as a floating catalyst method (Japanese Patent No. 5819888), a substrate method (Japanese Patent No. 5590603), or the like.
  • the strands of the CNT wire 10 can be manufactured by dry spinning (Japanese Patent No. 5819888, Patent No. 5990202, Japanese Patent No. 5350635), wet spinning (Japanese Patent No. 5135620, Japanese Patent No. 5131571, Japanese Patent No. 5288359) Table 2014-530964) etc. can be produced.
  • a method of covering an insulating covering layer on a core wire of aluminum or copper can be used.
  • raw materials of the insulating covering layer 21 And a method of melting and extruding around the CNT wire 10 and coating it.
  • the CNT-coated electric wire 1 according to the embodiment of the present invention can be used as a general electric wire such as a wire harness, and a cable may be produced from the general electric wire using the CNT-coated electric wire 1.
  • Polypropylene (Sumitomo Chemical Corporation Sumitomo Nobren, Rockwell hardness: 92) Cellulose Acetate (Acetyl, Daicel Finechem, Rockwell Hardness: 65) Polyamide (Toray Industries Amilan, Rockwell hardness: 100) FEP (Daikin's Neoflon FEP, Rockwell hardness: 25) PTFE (tetrafluoroethylene resin) (manufactured by Asahi Kasei Corp. Fluon, Rockwell hardness: 20)
  • the same measurement is repeated every 10 cm at an arbitrary 1.0 m on the longitudinal center side of the CNT coated wire, and the circle (CNT wire equivalent circle) having the same area as the radial cross section of the CNT wire and the diameter of the CNT coated wire Circles with the same area as the directional cross-sectional area (CNT-coated wire equivalent circles) were obtained respectively, and the difference from the radius of the CNT wire equivalent circle was determined from the radius of the CNT-coated wire equivalent circle, and the thickness of the insulating covering layer was determined. .
  • Heat dissipation characteristics Four terminals were connected to both ends of a 100 cm CNT-coated wire, and resistance measurement was performed by the four-terminal method. At this time, the applied current was set to 2000 A / cm 2 and the time change of the resistance value was recorded. The rate of increase was calculated by comparing the resistance value at the start of measurement and after 10 minutes. Since the resistance of the CNT wire increases in proportion to the temperature, it can be judged that the smaller the rate of increase in resistance, the better the heat dissipation characteristics.
  • the increase rate of resistance is less than 5%, it will be " ⁇ ", if the increase rate of resistance is 5% or more and less than 15%, “ ⁇ ", if the increase rate of resistance is 15% or more and less than 30% If it was "O" or more, it was evaluated that it was excellent in the heat dissipation characteristic.
  • the Rockwell hardness of the material constituting the insulating coating layer is greater than 22, and the ratio of the thickness of the insulating coating layer to the equivalent circle diameter of the carbon nanotube wire is greater than 0.05.
  • a carbon nanotube-coated electric wire was obtained in which the heat radiation characteristics, the shape retention, and the workability were all excellent even when the resin type was any of polypropylene, cellulose acetate, polyamide, and FEP.
  • a CNT-coated wire excellent in insulation reliability was obtained.
  • Examples 2 to 3, 4 to 5, 8 to 14, and 17 to 19 a CNT-coated electric wire having more excellent shape retention and workability was obtained.
  • Example 7 From the comparison between Example 7 and Examples 8 to 9, it is possible to obtain a CNT-coated electric wire in which the shape retention and the workability are further improved as the circle equivalent diameter of the single wire is thicker. Furthermore, from the comparison between Example 16 and Example 17, a CNT-coated electric wire with improved shape retention and workability was obtained as the insulating covering layer is thicker.
  • the half value width ⁇ of the azimuth angle was 60 ° or less. Therefore, in the CNT wire of each of Examples 1 to 12, the CNT aggregate had excellent orientation.
  • q values of the peak top in (10) peak intensity are both at 2.0 nm -1 or 5.0 nm -1 or less, the half width ⁇ q are all 0.1nm -1 or more and 2.0 nm -1 or less. Therefore, in the CNT wires of Examples 1 to 19, the CNTs also had excellent orientation.
  • Comparative Examples 1 and 2 in which the Rockwell hardness of the material constituting the insulating coating layer is 22 or less, the shape retention can not be obtained, and the workability is also inferior. Furthermore, in Comparative Example 1 in which the ratio of the thickness of the insulating covering layer to the equivalent circle diameter of the CNT wire is 0.05 or less, the insulation reliability is also inferior.
  • Comparative Examples 3 to 5 in which the ratio of the thickness of the insulating covering layer to the equivalent circle diameter of the CNT wire is 0.05 or less, although the Rockwell hardness of the material constituting the insulating covering layer exceeds 22.
  • the insulation reliability, the shape retention, and the workability were all inferior or the heat dissipation characteristics were inferior.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
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Abstract

La présente invention concerne un fil électrique revêtu de nanotubes de carbone (1) ayant d'excellentes caractéristiques de dissipation de chaleur, propriétés de rétention de forme et aptitude au façonnage. Le fil électrique revêtu de nanotubes de carbone (1) comprend : un matériau (10) de fil de nanotubes de carbone comprenant au moins un agrégat (11) de nanotubes de carbone comprenant une pluralité de nanotubes de carbone (11a) ; et une couche de revêtement isolant (21) qui recouvre le matériau (10) de fil de nanotubes de carbone. Le matériau constituant la couche de revêtement isolant (21) a une dureté Rockwell supérieure à 22. Le rapport entre l'épaisseur de la couche de revêtement isolant (21) et le diamètre de cercle équivalent du matériau (10) de fil de nanotubes de carbone est supérieur à 0,05.
PCT/JP2018/039971 2017-10-26 2018-10-26 Fil électrique revêtu de nanotubes de carbone WO2019083029A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114341262A (zh) * 2019-09-03 2022-04-12 住友电气工业株式会社 碳纳米管-树脂复合体以及碳纳米管-树脂复合体的制造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003303516A (ja) * 2002-04-09 2003-10-24 Toyobo Co Ltd 細径電線コード
JP2015079671A (ja) * 2013-10-17 2015-04-23 株式会社 Ｍｇコーポレーション 導電線、導電線の製造方法およびコイル

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003303516A (ja) * 2002-04-09 2003-10-24 Toyobo Co Ltd 細径電線コード
JP2015079671A (ja) * 2013-10-17 2015-04-23 株式会社 Ｍｇコーポレーション 導電線、導電線の製造方法およびコイル

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114341262A (zh) * 2019-09-03 2022-04-12 住友电气工业株式会社 碳纳米管-树脂复合体以及碳纳米管-树脂复合体的制造方法

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