[go: up one dir, main page]

WO2018042783A1 - Organe conducteur, corps moulé conducteur, organe électrique/électronique, composition conductrice et procédé de production d'organe conducteur - Google Patents

Organe conducteur, corps moulé conducteur, organe électrique/électronique, composition conductrice et procédé de production d'organe conducteur Download PDF

Info

Publication number
WO2018042783A1
WO2018042783A1 PCT/JP2017/019885 JP2017019885W WO2018042783A1 WO 2018042783 A1 WO2018042783 A1 WO 2018042783A1 JP 2017019885 W JP2017019885 W JP 2017019885W WO 2018042783 A1 WO2018042783 A1 WO 2018042783A1
Authority
WO
WIPO (PCT)
Prior art keywords
conductive member
conductive
member according
sheet
carbon nanotube
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/019885
Other languages
English (en)
Japanese (ja)
Inventor
翼 井上
鉄春 三輪
宏一 長岡
松本　俊寛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shizuoka University NUC
JNC Corp
Original Assignee
Shizuoka University NUC
JNC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shizuoka University NUC, JNC Corp filed Critical Shizuoka University NUC
Priority to JP2018536942A priority Critical patent/JPWO2018042783A1/ja
Publication of WO2018042783A1 publication Critical patent/WO2018042783A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising 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
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber

Definitions

  • the present invention relates to a conductive member including a carbon nanotube array (CNT array), a conductive molded body, an electrical / electronic related member including the conductive member or the conductive molded body, a conductive composition, and the conductive member. It relates to the manufacturing method.
  • CNT array carbon nanotube array
  • a conductive molded body an electrical / electronic related member including the conductive member or the conductive molded body, a conductive composition, and the conductive member. It relates to the manufacturing method.
  • CNT carbon nanotubes
  • SPM scanning probe microscope
  • FED field emission display
  • conductive members high-strength resins, corrosion-resistant resins, wear-resistant resins, advanced Lubricating resins, secondary battery and fuel cell electrodes, LSI interlayer wiring materials, biosensors, and the like are considered.
  • Non-Patent Document 1 discloses a composite member of CNT and epoxy resin as an example of such a conductive member.
  • the upper limit of the conductivity of the composite member described in Non-Patent Document 1 when DC voltage is applied is about 10 ⁇ 2 Scm ⁇ 1 , and the upper limit of the volume content of CNT at that time is 3% by volume. However, it cannot be said that this level of conductivity has good conductivity.
  • An object of the present invention is to provide a conductive member having CNT as a conductive material and having good conductivity. Another object of the present invention is to provide an electric / electronic related member provided with the above conductive member or a molded body of the above conductive member. Furthermore, an object of this invention is to provide the electrically conductive composition which can form said electrically conductive member, and the manufacturing method of said electrically conductive member.
  • a conductive member comprising a conductive material including an array of carbon nanotubes and an insulating material, wherein at least a part of the carbon nanotube array is covered with the insulating material.
  • Two end portions in a direction along the arrangement direction of the carbon nanotube array in the sheet-like shape are a first exposed end portion and a second exposed end portion where the carbon nanotube array body is exposed,
  • the conductive member according to [12] above, wherein the direct current conductivity between the first exposed end and the second exposed end is 1 Scm ⁇ 1 or more.
  • a conductive molded body comprising a molded body of the conductive member described in [18] or [19].
  • An electric / electronic member comprising the conductive member according to any one of [1] to [19] or the conductive molded body according to [20].
  • [23] A method for producing a conductive member according to any one of [14] to [17], wherein the first raw material sheet includes the carbon nanotube array, and the raw material composition that provides the insulating material.
  • the second raw material sheet is stacked in the thickness direction, and the first raw material sheet and the second raw material sheet are brought into pressure contact while being heated in the thickness direction, and the raw material composition contained in the second raw material sheet A part of the object is moved to a gap between the carbon nanotubes in the carbon nanotube array included in the first raw material sheet, and has the sheet-like shape and forms the inclined region,
  • a method for manufacturing a conductive member A method for manufacturing a conductive member.
  • the volume content of the carbon nanotube array is 5% by volume or more, and the thermal conductivity between two points spaced in the arrangement direction of the carbon nanotube array is 10 W / mK or more.
  • Another aspect of the present invention is a heat transfer member including a conductive material including a carbon nanotube array and a heat shield material, wherein at least a part of the carbon nanotube array is covered with the heat shield material. And a heat transfer member having a volume content of 5% by volume of the carbon nanotube array in the heat transfer member.
  • the heat shielding material included in the heat transfer member may be an insulating material of the conductive member, may contain a resin, or is a matrix material that supports the carbon nanotube array. Also good.
  • a conductive member having CNT as a conductive material and having good conductivity is provided.
  • an electric / electronic related member provided with the said electrically conductive member or the molded object of said electrically conductive member is also provided.
  • the electrically conductive composition which can form said electrically conductive member, and the manufacturing method of said electrically conductive member are also provided.
  • FIG. 1 is a conceptual cross-sectional view of an example of a conductive sheet according to an embodiment of the present invention, in which a plane including the arrangement direction of a CNT array is a cut surface.
  • It is a flowchart which shows the manufacturing method of the electroconductive sheet which concerns on one Embodiment of this invention. It is a figure for demonstrating the manufacturing method of the electroconductive sheet which concerns on one Embodiment of this invention. It is a figure for demonstrating the manufacturing method of the electroconductive sheet which concerns on one Embodiment of this invention. It is a figure for demonstrating the manufacturing method of the electroconductive sheet which concerns on one Embodiment of this invention.
  • a conductive member according to an embodiment of the present invention includes a conductive material including a carbon nanotube array (CNT array) and an insulating material, and at least a part of the CNT array is covered with an insulating material.
  • CNT array carbon nanotube array
  • a “carbon nanotube array (CNT array)” is an aggregate of CNTs, and a structure in which a group of CNTs constituting this is aligned in a direction along the long axis of the CNTs.
  • the CNT array is provided with a conductive material including the CNT array.
  • the conductive member according to one embodiment has high conductivity in the direction along the arrangement direction.
  • the conductive member according to an embodiment of the present invention has a portion whose DC conductivity in the direction along the arrangement direction is 1 Scm ⁇ 1 or more.
  • the conductive member according to an embodiment of the present invention has a portion that is 10 Scm ⁇ 1 or more. In a more preferred example, the conductive member according to an embodiment of the present invention has a portion that is 50 Scm ⁇ 1 or more. In a more preferred example, the conductive member according to an embodiment of the present invention has a portion that is 100 Scm ⁇ 1 or more.
  • the CNT constituting the CNT array may be either single-walled CNT (SWCNT), double-walled CNT (DWCNT), or multilayered CNT (MWCNT), or a mixture of two or more of these. Good.
  • the surface of the CNT constituting the CNT array may be subjected to a treatment for improving the interaction with the insulating material.
  • the conductivity of each CNT constituting the CNT array is preferably high.
  • the overall shape of the CNT array is not limited. When it is particularly thin in one direction (thickness direction) like a cloth, it may be referred to as a CNT web based on the external similarity to the cloth.
  • the CNT array may include a carbon nanotube bundle (CNT bundle).
  • CNT bundle is an aggregate of CNTs, and a plurality of CNTs are positioned so that their major axis directions are substantially aligned, close to the minor axis direction, and bundles of CNTs.
  • the structure has a shape.
  • the CNT forest is a composite structure of a plurality of CNTs (hereinafter, each shape of the CNT that gives such a composite structure is referred to as a “primary structure”, and the above-described composite structure is also referred to as a “secondary structure”).
  • a plurality of CNTs are oriented in a certain direction (at least as a specific example, a direction substantially parallel to one normal line of a surface included in the substrate) with respect to at least a part of the long axis direction. It means an aggregate of CNTs grown as described above.
  • the length (height) of the CNT forest grown from the substrate in the direction parallel to the normal line of the substrate in a state of adhering to the substrate is referred to as “growth height”.
  • a CNT entangled body can be formed by picking a part of the CNTs in the CNT forest and pulling the CNTs away from the CNT array, that is, by continuously pulling out a plurality of CNTs from the CNT forest.
  • FIG. 1 is an image showing an example of a state in which a CNT entangled body is drawn and formed from such a CNT forest. 1 is a CNT forest. In FIG. 1, CNTs are pulled out in the left direction to form a thin cloth-like CNT entangled body.
  • FIG. 2 is a partially enlarged view showing the structure of the CNT entangled body thus obtained.
  • the plurality of CNTs constituting the CNT entangled body are arranged substantially in one direction (in the horizontal direction in FIG. 2).
  • the CNT entangled body may constitute the CNT array as it is, or the CNT array may be formed by stacking a plurality of CNT entangled bodies.
  • the thickness of the obtained CNT array increases as the number of CNT entanglements increases.
  • the conductivity in the arrangement direction of the CNT array composed of the array is increased. Therefore, the conductivity of the conductive member provided with this CNT array is also increased.
  • the major axis direction is almost aligned and adjacent to the minor axis direction. It is possible to increase the rate at which a plurality of positioned CNTs form a CNT bundle.
  • the CNT array may have a structure in which a plurality of CNTs are in contact with each other at or near the end.
  • electrical conduction between CNTs in contact with the major axis direction is facilitated, and as a result, electrical conductivity in the arrangement direction of the CNT array is increased.
  • Such a structure is easily seen in the CNT array formed from the CNT forest described above.
  • the volume content of the CNT array in the conductive member is not limited. As described above, the volume content is preferably such that the conductive member has a portion having a direct current conductivity in the direction along the arrangement direction of 1 Scm ⁇ 1 or more. From the viewpoint of satisfying such conditions more stably, the volume content of the CNT array in the conductive member may be preferably 4% by volume or more. From the viewpoint of more stably realizing a portion in which the direct current conductivity in the direction along the arrangement direction in the conductive member is 100 Scm ⁇ 1 or more, the volume content of the CNT array in the conductive member is 10% by volume or more. May be preferred.
  • the volume content of the CNT array in the conductive member may be preferably less than 30% by volume, and may be 25% by volume or less. May be more preferred.
  • any material can be used as long as it has moderate insulating properties, for example, a material having a DC conductivity of 10 ⁇ 9 Scm ⁇ 1 or less.
  • the insulating material include organic materials such as organic resins and silicone resins; inorganic materials such as oxides, carbides and hydroxides; and composite materials thereof.
  • organic materials include polyolefins such as polyethylene, polypropylene, and copolymers containing cyclic olefins; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon 66; polyvinyl chloride; polycarbonates; poly (meth) acrylic An acrylic resin such as methyl acid; a fluorine resin such as polytetrafluoroethylene; a polyimide; a polyurethane; a silicone resin; a phenol resin; and an epoxy resin.
  • the inorganic material include water glass and alumina.
  • the insulating material has a property of changing from a low viscosity state to a high state because it functions as a matrix material that covers and holds the conductive material.
  • the insulating material is preferably a thermoplastic material or a cured product of a curable material.
  • the conductive member according to an embodiment of the present invention may contain a material other than the CNT array and the insulating material.
  • examples of such materials include inorganic insulating materials such as silica filler and talc; inorganic conductive materials such as silver wire, copper powder and carbon powder; organic insulating materials such as melamine resin powder; poly (3,4 -Organic conductive materials such as ethylene dioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS) are exemplified.
  • PEDOT ethylene dioxythiophene
  • PSS polystyrene sulfonic acid
  • a flame retardant, a coloring material, a lubricant, a surfactant, a coupling agent and the like may be contained.
  • the content of such an additive material is appropriately set within a range that does not significantly affect the conductivity obtained by the conductive member according to one embodiment of the present invention containing the CNT array and the insulating material.
  • the arrangement of the CNT array in the conductive member according to an embodiment of the present invention is not limited.
  • the entire CNT array may be disposed (embedded) inside the conductive member, or a part of the CNT array may be exposed on the surface of the conductive member.
  • the end of the CNT array When a part of the CNT array is exposed on the surface of the conductive member, the end of the CNT array may be exposed or the end of the CNT array may be exposed. Good. If both ends in the arrangement direction of the CNT array are exposed, providing two or more electrical contacts so as to be in contact with these ends can particularly enhance the conductivity between them. it can.
  • the CNT array functions as a member element that imparts conductivity to the conductive member
  • the insulating material is a member that imparts insulation to the conductive member. Acts as an element. Therefore, at least a part of the surface of the conductive member may be made of an insulating material. In this way, the conductive member can have an insulating surface. If it demonstrates from another viewpoint, 100 M ⁇ / ⁇ or more of surface resistance may be sufficient as the at least one part surface in a conductive member. If the surface resistance is about this level, the surface is substantially insulative.
  • the CNT array has high conductivity along the arrangement direction of the CNT array, and a direction different from the arrangement direction, specifically, a direction along the direction orthogonal to the arrangement direction is normal. With respect to the surface, a member having high insulation can be obtained.
  • At least a part of the surface of the conductive member according to the embodiment of the present invention may have an arithmetic average roughness Ra defined by JIS B0601-1994 of 1 ⁇ m or less.
  • the relationship between the CNT array and the insulating material inside the conductive member according to an embodiment of the present invention is not limited. It may be preferable to provide an inclined region in which the content of the insulating material changes from the surface side toward the inner side in the direction orthogonal to the arrangement direction of the CNT array in the conductive member.
  • an inclined region By providing such an inclined region, a conductive region in which the CNT array body mainly exists and an insulating region in which the insulating material mainly exists can continuously exist in the conductive member. Since the mechanical properties may be different between the conductive region and the insulating region, there is a concern that problems such as easy peeling between the regions occur when these regions are in contact with each other without an inclined region. The presence of the inclined region can reduce the possibility of such a peeling problem.
  • the specific structure of the inclined area is not limited.
  • a specific example of the inclined region is a region having a portion where the content of the insulating material is reduced from the surface side to the inner side of the conductive member.
  • an insulating region exists on the surface side of the conductive member, and a conductive region exists on the inner side of the conductive member.
  • the conductive member can be used as a coated wiring or a coated wiring substrate.
  • the specific shape of the conductive member according to an embodiment of the present invention is not limited. It may have a sheet shape, may have a lump shape, or may have a ring shape or a cylindrical shape, for example.
  • the conductive member has a sheet-like shape, that is, the case where the conductive member is a conductive sheet will be described as an example.
  • sheet refers to a member having two main surfaces that are sufficiently larger than the other surfaces as two opposing surfaces.
  • the case where the main surface is a plane is included.
  • a curved surface may be formed, or local unevenness or a bent portion may be provided.
  • the concept of sheet includes the concept of film and the concept of tape.
  • the relationship between the in-plane direction of the conductive sheet and the arrangement direction of the CNT array is not limited.
  • the conductive sheet may have conductivity in the in-plane direction, may have conductivity in the thickness direction, or may have conductivity in both directions.
  • FIG. 3 is a conceptual cross-sectional view of an example of the conductive sheet according to an embodiment of the present invention, in which a plane including the arrangement direction of the CNT array is a cut surface.
  • the conductive sheet 10 includes a CNT array 11 and an insulating material 12.
  • the CNT array 11 includes a CNT array obtained by stacking a plurality of cloth-like CNT entanglements obtained by pulling out from a CNT forest.
  • the insulating material 12 is made of resin.
  • the arrangement direction D1 of the CNT array 11 is a direction along the in-plane direction of the conductive sheet 10.
  • the normals 10a and 10b of the main surfaces 10A and 10B of the conductive sheet 10 are located in a direction along the direction orthogonal to the arrangement direction D1 of the CNT array 11.
  • Two ends of the conductive sheet 10 in the direction along the arrangement direction D1 of the CNT array 11 are a first exposed end 131 and a second exposed end 132 where the CNT array 11 is exposed.
  • the direct current conductivity between the first exposed end portion 131 and the second exposed end portion 132 is 1 Scm ⁇ 1 or more.
  • one main surface 10 ⁇ / b> A and the other main surface 10 ⁇ / b> B of the conductive sheet 10 are both made of an insulating material 12. That is, the insulating regions R1A and R1B are located on both main surfaces 10A and 10B side of the conductive sheet 10.
  • a conductive region R ⁇ b> 2 which is a region substantially consisting only of the CNT array 11, exists at the center in the thickness direction of the conductive sheet 10.
  • the CNT array 11 is embedded in the conductive sheet 10 on both main surfaces 10A and 10B side. Therefore, the conductive sheet 10 is an anisotropic conductive member having conductivity in the arrangement direction D1 of the CNT array but having insulation in the thickness direction.
  • CNTs are difficult to drop off from the main surfaces 10A and 10B.
  • the conductive sheet 10 has two regions (insulating regions R1A and R1B and a conductive region R2) that are greatly different in electrical properties, but these regions are continuously connected. Therefore, the conductive sheet 10 is unlikely to peel off between these two regions (insulating regions R1A, R1B and conductive region R2). Note that the thicknesses of the insulating regions R1A and R1B may be different.
  • the conductive member according to one embodiment of the present invention may be moldable.
  • molding means a shape creation process performed by pressurization, heating, irradiation of ionizing radiation, and the like. Specific examples of the molding process include rolling, press molding, and extrusion molding. When the conductive member can be molded, it is easy to impart a predetermined shape by performing the molding process on the conductive member. In this specification, the conductive member that has been subjected to the molding process is also referred to as a “conductive molded body”.
  • the composition of the conductive member before the molding process and the conductive molded body may be the same or different.
  • a compositional change hardly occurs in the conductive member before and after the forming process.
  • the obtained conductive molded body has the same composition as the conductive member before the molding process.
  • the conductive member made of a thermosetting resin in a semi-cured state of the insulating material was subjected to a molding process including a hot pressing process, and the curing reaction of the thermosetting resin was advanced during the hot pressing process.
  • the obtained conductive molded body has a composition different from that of the conductive member before molding.
  • the conductive member is soft and contains an insulating material made of a polymer capable of crosslinking reaction and a crosslinking agent
  • the crosslinking agent is reacted by heat application or ultraviolet irradiation while molding or after molding.
  • the conductive member can be cured in a predetermined shape to obtain a conductive molded body.
  • a conductive member is manufactured using a raw material composition that provides an insulating material and a CNT array.
  • the composition of the raw material may be the same as or different from the composition of the insulating material.
  • the raw material composition has a composition different from that of the insulating material.
  • a specific example of a method for producing a conductive member is to prepare a conductive composition including a raw material composition that provides an insulating material and a CNT array, and perform molding on the conductive composition to obtain a conductive member. It is a method of forming.
  • the conductive composition according to one embodiment of the present invention includes the raw material composition that provides the insulating material and the CNT array, and a conductive member can be formed from the conductive composition.
  • FIG. 4 is a flowchart showing a method for manufacturing a conductive sheet according to an embodiment of the present invention.
  • 5 and 6 are views for explaining a method for manufacturing a conductive sheet according to an embodiment of the present invention.
  • a first raw material sheet 21 containing a CNT array and a second raw material sheet 22 made of a raw material composition that provides an insulating material are prepared, These sheets are stacked in the thickness direction (first step). From the viewpoint of improving the subsequent workability, this stack is preferably sandwiched between plates having excellent peelability, such as polytetrafluoroethylene (PTFE) plates 31 and 32.
  • the stack 40 shown in FIG. 5 includes a PTFE plate 31 / first raw material sheet 21 / second raw material sheet 22 / PTFE plate 32.
  • the stack 40 is set in a press device, the first raw material sheet 21 and the second raw material sheet 22 are brought into contact with each other in the thickness direction, and a part of the raw material composition contained in the second raw material sheet 22 is placed. Then, the first raw material sheet 21 is moved to the gap between the CNTs in the CNT array (second step). At this time, when the raw material composition is different from the insulating material, the reaction necessary for the raw material composition may be advanced to form the insulating material. In FIG. 6, heat and pressure are applied.
  • insulating region By controlling the contact pressure in the thickness direction of the stack (pressing pressure applied by a press), a region made of an insulating material (insulating region) and a region made of a CNT array (conductive region)
  • the insulating material is formed in the thickness direction, and further, the insulating material content decreases between these regions from the first raw material sheet 21 side to the second raw material sheet 22 side. And an inclined region in which the CNT array is present.
  • the raw material composition may be made of a material whose viscosity is lowered by heating. In this case, when the viscosity is lowered, the raw material composition easily moves to the gap between the group of CNTs constituting the CNT array, and the inclined region is easily formed. As a specific example of such a case, the raw material composition has thermoplasticity.
  • the raw material composition may contain a curable substance and be made of a material whose viscosity increases due to a curing reaction of the curable substance. In this case, with the progress of the curing reaction, the ease of movement of the group of CNTs constituting the CNT array into the gap decreases, and the inclined region is easily formed.
  • the curable substance is made of a compound having one or a plurality of epoxy groups or isocyanate groups.
  • the raw material composition may further contain a curing agent that reacts with the curable substance (for example, a compound having one or more hydroxyl groups or amino groups).
  • the curable substance is a substance having an unpaired electron (for example, a compound having one or a plurality of hydroxyl groups or amino groups), and further a polyvalent ion such as calcium ion.
  • a conductive sheet having an inclined region can be obtained.
  • the conductive sheet 10 shown in FIG. 3 has a structure in which both main surfaces 10A and 10B are made of an insulating material, but one of the main surfaces has a structure in which the CNTs of the CNT array are exposed. May be.
  • the stack of PTFE plate 31 / first raw material sheet 21 / second raw material sheet 22 / PTFE plate 32 is set in the press device. A stack of 2 raw material sheets / first raw material sheet / second raw material sheet / PTFE plate may be set. In this case, the conductive sheet 10 shown in FIG. 3 can be obtained.
  • heat is also applied during pressurization, but the present invention is not limited to this.
  • the second raw material sheet is made of a material that is cured by ultraviolet light
  • the insulating material is formed by performing ultraviolet light irradiation during or after pressurization.
  • the conductive member according to one embodiment of the present invention can also function as a heat transfer member. That is, since the CNT array that is a conductive material has a high thermal conductivity, even if the thermal conductivity of the insulating material is low, the structure composed of the CNT array and the insulating material as a whole has a high thermal conductivity. Can have. For example, when the insulating material is made of a resin, the thermal conductivity is generally 1 W / mK or less. Thus, when the insulating material is made of a heat shielding material having a low thermal conductivity in comparison with the CNT array, the heat transfer member (conductive member) includes the CNT array and the heat transfer member (conductive member). Prepare.
  • the thermal conductivity between points is 10 W / mK or more.
  • the thermal conductivity can be adjusted almost linearly by changing the volume content of the CNT array in the heat transfer member (conductive member).
  • the material constituting the heat shielding material insulating material
  • the kind of resin will be arbitrary.
  • the heat shielding material may have conductivity.
  • the relationship between the CNT array inside the heat transfer member and the heat shielding material is not limited, as is the case between the CNT array inside the conductive member and the conductive material.
  • the CNT array is positioned as a functional material and the heat shielding material as a structural material.
  • the heat shielding material may be preferably used as a matrix material for supporting the flexible CNT array and maintaining the shape of the heat transfer member.
  • Example 1 A CNT forest (CNT array) was produced by the manufacturing method described in Japanese Patent No. 5664832. Drawing out from the obtained CNT forest, a thin cloth-like CNT entangled body was obtained. By winding the CNT entangled body around a roll, the CNT entangled body was laminated to obtain CNT arrays having different numbers of layers.
  • FIG. 7 is a diagram showing a state in which a CNT entangled body is drawn from a CNT forest and wound around a roll to obtain a CNT array.
  • a plurality of types of CNT arrays having a stacking number of 2 to 400 thus obtained are immersed in ethanol, and then the ethanol is volatilized to increase the proportion of CNT bundles in the CNT array, thereby An array was obtained.
  • the arrangement direction of the CNT array was a direction along the direction perpendicular to the thickness direction of the CNT array. Using the first raw material sheet made of this CNT array, a conductive sheet having an inclined region was produced.
  • Example 1-1 An epoxy resin film was prepared and used as the second raw material sheet.
  • the 1st raw material sheet and the 2nd raw material sheet were piled up, these were pinched
  • This stack was molded by a hot press method to obtain a conductive member in which CNT arrays were arranged along a direction orthogonal to the thickness direction.
  • the conditions of the hot press method were as follows. Atmosphere: Air Pressure condition: 10 MPa Heating condition: 3 minutes at 90 ° C. and then 80 minutes at 130 ° C.
  • the volume content Vf (unit: volume%) of the CNT array in the conductive member obtained was determined by thermogravimetric analysis.
  • the DC conductivity ⁇ (unit: Scm ⁇ 1 ) between the first exposed end and the second exposed end, which are the ends along the arrangement direction of the CNT array, was measured. These results are shown in Table 1.
  • Example 1-2 A first raw material sheet of 30 mm ⁇ 20 mm ⁇ 10 ⁇ m was prepared.
  • LPDE low density polyethylene
  • the DC conductivity between both end portions along the arrangement direction of the CNT array in the conductive member was measured and found to be 45 Scm ⁇ 1 . Any of the following DC conductivity measurements were performed between both end portions along the arrangement direction of the CNT array.
  • the obtained conductive member was cut and molded into a size of 5 mm ⁇ 30 mm to obtain a test conductive member.
  • the conductive member for testing is a direction in which the major axis direction (direction having a length of 30 mm) is along the arrangement direction of the CNT array, and the end portions in the direction along the arrangement direction of the CNT array are all CNT arrays. My body was exposed. The direct current conductivity of this molded body was 51 Scm ⁇ 1 .
  • the test conductive member was stretched to a size of 101% of the initial length along the arrangement direction of the CNT array.
  • the direct current conductivity of the conductive molded body obtained by stretching was 63 Scm ⁇ 1 .
  • the test conductive member was stretched to 120% of the initial length along the in-plane direction perpendicular to the arrangement direction of the CNT array.
  • the direct current conductivity of the conductive molded body obtained by stretching was 56 Scm ⁇ 1 .
  • Example 1-3 A first raw material sheet of 30 mm ⁇ 20 mm ⁇ 5 ⁇ m was prepared. A toluene-containing gel (polystyrene concentration: 41% by mass) of polystyrene (PS) was prepared and applied on the first raw material sheet. The obtained coating film was dried at 120 ° C. for 30 minutes to obtain a conductive member. The surface resistance of the obtained conductive member was measured. It was 9 ⁇ / ⁇ on the first raw material sheet side, and was 100 M ⁇ / ⁇ or more on the opposite side (polystyrene gel coating film side) from the first raw material sheet.
  • PS polystyrene concentration
  • the obtained conductive molded body had a DC conductivity of 24 Scm ⁇ 1 .
  • the obtained conductive member was cut and molded into a size of 5 mm ⁇ 30 mm to obtain a test conductive member.
  • the conductive member for testing is a direction in which the major axis direction (direction having a length of 30 mm) is along the arrangement direction of the CNT array, and the end portions in the direction along the arrangement direction of the CNT array are all CNT arrays. My body was exposed.
  • the direct current conductivity of this molded body was 26 Scm ⁇ 1 .
  • the test conductive member was stretched to a size of 102% of the initial length along the arrangement direction of the CNT array.
  • the direct current conductivity of the conductive molded body obtained by stretching was 33 Scm ⁇ 1 .
  • the test conductive member was stretched to a size of 110% of the initial length along the in-plane direction orthogonal to the arrangement direction of the CNT array.
  • the direct current conductivity of the conductive molded body obtained by stretching was 36 Scm ⁇ 1 .
  • Example 1-4 A first raw material sheet of 30 mm ⁇ 20 mm ⁇ 5 ⁇ m was prepared. A gel-like 30 mm ⁇ 20 mm ⁇ 10 ⁇ m epoxy sheet was prepared as a second raw material sheet. The first raw material sheet and the second raw material sheet were stacked and further sandwiched between PTFE plates to obtain a stack. This stack was compressed from 130 ° C. and 3 MPa for 90 minutes in the thickness direction to obtain a conductive member in which CNT arrays were arranged in a direction perpendicular to the thickness direction. The surface resistance of the obtained conductive member was measured. It was 1 k ⁇ / ⁇ on the first raw material sheet side and 100 M ⁇ / ⁇ or higher on the second raw material sheet side.
  • the DC conductivity between both end portions along the arrangement direction of the CNT array in the conductive member was measured and found to be 26 Scm ⁇ 1 .
  • the surface roughness of the obtained conductive member was measured.
  • the arithmetic average roughness Ra defined in JIS B0601-1994 was measured on the surface opposite to the first raw material sheet (the coating film side of the epoxy sheet), it was 0.4 ⁇ m.
  • the obtained conductive member was cut and molded into a size of 5 mm ⁇ 30 mm to obtain a test conductive member.
  • the conductive member for testing is a direction in which the major axis direction (direction having a length of 30 mm) is along the arrangement direction of the CNT array, and the end portions in the direction along the arrangement direction of the CNT array are all CNT arrays.
  • My body was exposed.
  • the direct current conductivity of this molded body was 26 Scm ⁇ 1 .
  • An electrode was attached to the end portion (first exposed end portion, second exposed end portion) along the arrangement direction of the CNT array in the conductive member for test, and the current was supplied.
  • the current was 1.3 A when the applied voltage was 13 VDC.
  • the surface temperature of the main surface of the test conductive member was 90 ° C.
  • Example 1-5 A first raw material sheet of 30 mm ⁇ 20 mm ⁇ 30 ⁇ m was prepared. A gel-like 30 mm ⁇ 20 mm ⁇ 20 ⁇ m epoxy sheet was prepared as a second raw material sheet. The first raw material sheet and the second raw material sheet were stacked and further sandwiched between PTFE plates to obtain a stack. This stack was compressed from 130 ° C. and 3 MPa for 90 minutes in the thickness direction to obtain a conductive member in which CNT arrays were arranged in a direction perpendicular to the thickness direction. The DC conductivity of this conductive member was 200 Scm ⁇ 1 . An electrode was attached to the end of the conductive member along the arrangement direction of the CNT array, and the current was applied. The current was 900 mA when the applied voltage was DC 1.8V. The surface temperature of the main surface of the conductive member at this time was 90 ° C. The response time constant when the applied voltage was changed was 3 seconds.
  • Example 2 In the same manufacturing method as in Example 1, the range of the number of stacked CNT entangled bodies was increased from that in Example 1 (2 to 400) to obtain a plurality of first raw material sheets made of CNT arrays.
  • Example 2-1 An epoxy resin film (bisphenol A type, 130 ° C. curing type) was prepared and used as the second raw material sheet.
  • the 1st raw material sheet and the 2nd raw material sheet were piled up, these were pinched
  • This stack was molded by a hot press method to obtain a conductive member in which CNT arrays were arranged along a direction orthogonal to the thickness direction.
  • the conditions of the hot press method were as follows. Atmosphere: Air Pressure condition: 2 MPa Heating conditions: 90 ° C for 5 minutes, then 130 ° C for 90 minutes
  • the obtained conductive member has CNTs in the entire thickness direction of the conductive member, and the epoxy resin derived from the second raw material sheet enters the CNT array as a matrix material. It was a structure.
  • the volume content Vf (unit: volume%) of the CNT array in the conductive member was determined by thermogravimetric analysis.
  • DC conductivity sigma // (Unit: Scm -1) between the first exposed end and a second exposed end is an end portion along the arrangement direction of the CNT array was measured.
  • the measurement results are shown in Table 2.
  • the measurement direction of the DC conductivity ⁇ // is referred to as “in-plane orientation direction”.
  • DC conductivity ⁇ ⁇ between two ends in a direction orthogonal to the thickness direction of the conductive member (that is, a direction in the main surface of the conductive member) and also orthogonal to the arrangement direction of the CNT array (Unit: Scm ⁇ 1 ) was measured.
  • Table 3 shows the measurement results.
  • the measurement direction of the DC conductivity sigma ⁇ as "plane orthogonal direction”.
  • the thermal conductivity in the in-plane orientation direction lambda // (Unit: W / mK) and in-plane direction perpendicular thermal conductivity lambda ⁇ was measured.
  • the thermal diffusivity in each direction was measured by the optical alternating current method, and the thermal conductivity in each direction was calculated based on the weight density obtained from mass and dimension measurement and the specific heat capacity obtained from differential scanning calorimetry. The calculation results are shown in Table 4 (thermal conductivity ⁇ // ) and Table 5 (thermal conductivity ⁇ ⁇ ).
  • Example 2-2 A polyamide resin film (xylylene sebacamide-based, “LEXTER 8500” manufactured by Mitsubishi Gas Chemical Company, Inc.) was prepared and used as the second raw material sheet. The 1st raw material sheet and the 2nd raw material sheet were piled up, these were pinched
  • the obtained conductive member has CNTs in the entire thickness direction of the conductive member, and the polyamide resin derived from the second raw material sheet enters the CNT array as a matrix material. It was a structure.
  • the rate ⁇ // and the thermal conductivity ⁇ ⁇ in the in-plane orthogonal direction were measured.
  • the measurement results of the DC conductivity ⁇ are shown in Table 6, and the calculation results of the thermal conductivity ⁇ are shown in Table 7.
  • FIG. 10 is a graph showing the dependence of the direct current conductivity ⁇ // in the in-plane orientation direction on the volume content Vf of the CNT array, prepared based on Tables 2 and 6.
  • DC conductivity sigma // The more volume content Vf tends to have confirmed increased. This tendency is confirmed both when the material constituting the second raw material sheet is an epoxy resin (“ ⁇ ” in FIG. 10) and when it is a polyamide resin (“ ⁇ ” in FIG. 10).
  • the results are numerically equivalent. Therefore, it can be said that the resin type has little influence on the tendency that the DC conductivity ⁇ // increases as the volume content Vf increases.
  • the volume content Vf of the CNT array is 40% by volume or more
  • the effect of increasing the volume content Vf of the CNT array on the DC conductivity ⁇ // is difficult to confirm. It was.
  • This result may indicate that there is a limit to increasing the orientation and aggregation density of the electric conduction path in the CNT array only by increasing the volume content Vf. Therefore, the bulk density of the CNT array is increased by further increasing the tensile strength imparted along the orientation direction when making the CNT array, and further reducing the diameter of the CNTs constituting the CNT array. If possible, the direct current conductivity ⁇ // in the in-plane orientation direction may further increase.
  • FIG. 11 is a graph showing the dependence of the thermal conductivity ⁇ // in the in-plane orientation direction on the volume content Vf of the CNT array, prepared based on Tables 4 and 7.
  • the thermal conductivity ⁇ // in the in-plane orientation direction tends to increase almost linearly, and even if the volume content Vf is about 5% by volume, the in-plane orientation is increased.
  • the thermal conductivity ⁇ // in the direction could be increased to about 10 W / mK.
  • the single thermal conductivity ⁇ of the epoxy resin or polyamide resin constituting the second raw material sheet is about 0.3 W / mK or less, it can be said that the thermal conductivity ⁇ is extremely high.
  • the thermal conductivity ⁇ of the conductive member can be increased to about 80 W / mK by setting the volume content Vf to about 50% by volume.
  • the thermal conductivity ⁇ the effect of the type of resin constituting the second raw material sheet on the thermal conductivity ⁇ of the conductive member was slight.
  • the conductive member and conductive molded body according to the present invention are suitably used as an anisotropic conductive sheet, a wiring member, a magnetic shield, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un organe conducteur (feuille conductrice (10)) qui comprend un matériau conducteur contenant un ensemble de nanotubes de carbone alignés (ensemble de CNT alignés) (11) et un matériau isolant (12), et qui a une structure dans laquelle au moins une partie de l'ensemble de CNT alignés (11) est recouverte du matériau isolant (12). Il est préférable que l'organe conducteur (feuille conductrice (10)) ait une partie dont la conductivité en courant continu soit supérieure ou égale à 1 Scm-1 dans une direction longeant la direction d'alignement D1 de l'ensemble de CNT alignés (11).
PCT/JP2017/019885 2016-08-31 2017-05-29 Organe conducteur, corps moulé conducteur, organe électrique/électronique, composition conductrice et procédé de production d'organe conducteur Ceased WO2018042783A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018536942A JPWO2018042783A1 (ja) 2016-08-31 2017-05-29 導電部材、導電性成形体、電気・電子関連部材、導電性組成物、および導電部材の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-169065 2016-08-31
JP2016169065 2016-08-31

Publications (1)

Publication Number Publication Date
WO2018042783A1 true WO2018042783A1 (fr) 2018-03-08

Family

ID=61301765

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/019885 Ceased WO2018042783A1 (fr) 2016-08-31 2017-05-29 Organe conducteur, corps moulé conducteur, organe électrique/électronique, composition conductrice et procédé de production d'organe conducteur

Country Status (2)

Country Link
JP (1) JPWO2018042783A1 (fr)
WO (1) WO2018042783A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022065967A (ja) * 2020-10-16 2022-04-28 国立大学法人静岡大学 電磁遮蔽シート
JP2023117181A (ja) * 2022-02-10 2023-08-23 高圧ガス工業株式会社 Ｃｎｔ樹脂複合体

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005007861A (ja) * 2003-05-27 2005-01-13 Mitsubishi Gas Chem Co Inc 三層構造の配向性カーボンナノチューブ膜複合シート、および該配向性カーボンナノチューブ膜の固定化方法
JP2005520889A (ja) * 2002-03-18 2005-07-14 アトフイナ・リサーチ 良好な機械的特性を有する伝導性ポリオレフィン
WO2006011655A1 (fr) * 2004-07-27 2006-02-02 National Institute Of Advanced Industrial Scienceand Technology Nano tube de carbone à couche unique et structure globale de nano tube de carbone à couche unique, leur processus de production, appareil de production et utilisation
JP2008523254A (ja) * 2004-11-09 2008-07-03 ボード オブ リージェンツ， ザ ユニバーシティ オブ テキサス システム ナノファイバーのリボンおよびシートならびにナノファイバーの撚り糸および無撚り糸の製造および適用
JP2010285344A (ja) * 2009-06-09 2010-12-24 Qinghua Univ 保護構造体を有するカーボンナノチューブ構造体及びその製造方法
JP2011116637A (ja) * 2009-12-03 2011-06-16 Beijing Funate Innovation Technology Co Ltd 異なる密度を有するカーボンナノチューブフィルム及びその製造方法
JP2013082595A (ja) * 2011-10-12 2013-05-09 National Institute Of Advanced Industrial Science & Technology カーボンナノチューブ複合材料および導電材料
JP2015138718A (ja) * 2014-01-24 2015-07-30 日立造船株式会社 導電性カーボンナノチューブ複合材料
WO2016136686A1 (fr) * 2015-02-23 2016-09-01 リンテック オブ アメリカ インク Feuille adhésive
JP2017057246A (ja) * 2015-09-14 2017-03-23 リンテック株式会社 柔軟性シート、熱伝導部材、導電性部材、帯電防止部材、発熱体、電磁波遮蔽体、及び柔軟性シートの製造方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005520889A (ja) * 2002-03-18 2005-07-14 アトフイナ・リサーチ 良好な機械的特性を有する伝導性ポリオレフィン
JP2005007861A (ja) * 2003-05-27 2005-01-13 Mitsubishi Gas Chem Co Inc 三層構造の配向性カーボンナノチューブ膜複合シート、および該配向性カーボンナノチューブ膜の固定化方法
WO2006011655A1 (fr) * 2004-07-27 2006-02-02 National Institute Of Advanced Industrial Scienceand Technology Nano tube de carbone à couche unique et structure globale de nano tube de carbone à couche unique, leur processus de production, appareil de production et utilisation
JP2008523254A (ja) * 2004-11-09 2008-07-03 ボード オブ リージェンツ， ザ ユニバーシティ オブ テキサス システム ナノファイバーのリボンおよびシートならびにナノファイバーの撚り糸および無撚り糸の製造および適用
JP2010285344A (ja) * 2009-06-09 2010-12-24 Qinghua Univ 保護構造体を有するカーボンナノチューブ構造体及びその製造方法
JP2011116637A (ja) * 2009-12-03 2011-06-16 Beijing Funate Innovation Technology Co Ltd 異なる密度を有するカーボンナノチューブフィルム及びその製造方法
JP2013082595A (ja) * 2011-10-12 2013-05-09 National Institute Of Advanced Industrial Science & Technology カーボンナノチューブ複合材料および導電材料
JP2015138718A (ja) * 2014-01-24 2015-07-30 日立造船株式会社 導電性カーボンナノチューブ複合材料
WO2016136686A1 (fr) * 2015-02-23 2016-09-01 リンテック オブ アメリカ インク Feuille adhésive
JP2017057246A (ja) * 2015-09-14 2017-03-23 リンテック株式会社 柔軟性シート、熱伝導部材、導電性部材、帯電防止部材、発熱体、電磁波遮蔽体、及び柔軟性シートの製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022065967A (ja) * 2020-10-16 2022-04-28 国立大学法人静岡大学 電磁遮蔽シート
JP7613717B2 (ja) 2020-10-16 2025-01-15 国立大学法人静岡大学 電磁遮蔽シート
JP2023117181A (ja) * 2022-02-10 2023-08-23 高圧ガス工業株式会社 Ｃｎｔ樹脂複合体

Also Published As

Publication number Publication date
JPWO2018042783A1 (ja) 2019-07-11

Similar Documents

Publication Publication Date Title
Liang et al. Multifunctional flexible electromagnetic interference shielding silver nanowires/cellulose films with excellent thermal management and joule heating performances
Hu et al. A low-cost, printable, and stretchable strain sensor based on highly conductive elastic composites with tunable sensitivity for human motion monitoring
US10937598B2 (en) Flexible electrode and sensor element
Luo et al. Graphite nanoplatelet enabled embeddable fiber sensor for in situ curing monitoring and structural health monitoring of polymeric composites
CN108349014B (zh) 柔性片材、导热、导电、防静电部件、加热元件、电磁波屏蔽件以及产生柔性片材的方法
Xu et al. Wavy ribbons of carbon nanotubes for stretchable conductors
Yan et al. Stretchable graphene thermistor with tunable thermal index
KR101238667B1 (ko) 그래핀 탄소섬유발열지를 이용한 양면 함침형 면상발열체의 제조방법
Han et al. High‐performance stretchable strain sensor based on Ag nanoparticles sandwiched between two 3D‐printed polyurethane fibrous textiles
CN103426941A (zh) 透明电极及包括其的电子材料
JP6205333B2 (ja) 熱電変換モジュール
KR101521694B1 (ko) 플렉서블/스트레처블 투명도전성 필름 및 그 제조방법
US20160153762A1 (en) Strain sensors and methods of manufacture and use
JP2020516494A (ja) 熱収縮性ポリマー及びナノファイバーシートを含む多層複合材
Gong et al. Trunk-inspired SWCNT-based wrinkled films for highly-stretchable electromagnetic interference shielding and wearable thermotherapy
KR100723298B1 (ko) 카본소재가 함침된 프리프레그를 이용한 방열구조체
KR20150002972A (ko) 탄소나노튜브(cnt) 네트워크 필름을 구비하는 양극성 변형 센서
Jang et al. Stretchability of PMMA-supported CVD graphene and of its electrical contacts
WO2018042783A1 (fr) Organe conducteur, corps moulé conducteur, organe électrique/électronique, composition conductrice et procédé de production d'organe conducteur
KR101434565B1 (ko) 전도성 페이스트 조성물을 포함하는 후막형 ptc 발열체
Shin et al. Evaluation of dispersion of MWCNT/cellulose composites sheet using electrical resistance 3D-mapping for strain sensing
KR20200142287A (ko) 발열기능을 구비한 그래핀 코팅 탄소섬유 방석
KR102763728B1 (ko) 전기 절연 및 급속 발열이 가능한 탄소 나노튜브-섬유 복합시트 및 이의 제조방법
Lv et al. Three-dimensional conducting elastomeric composites based on buckling carbon nanotube sheets for interconnects and temperature sensor
Miao et al. On finding of high piezoresistive response of carbon nanotube films without surfactants for in-plane strain detection

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17845794

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018536942

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17845794

Country of ref document: EP

Kind code of ref document: A1