WO2021200518A1 - Film électroconducteur étirable, capteur, absorbeur d'ondes radio et réflecteur - Google Patents

Film électroconducteur étirable, capteur, absorbeur d'ondes radio et réflecteur Download PDF

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Publication number
WO2021200518A1
WO2021200518A1 PCT/JP2021/012436 JP2021012436W WO2021200518A1 WO 2021200518 A1 WO2021200518 A1 WO 2021200518A1 JP 2021012436 W JP2021012436 W JP 2021012436W WO 2021200518 A1 WO2021200518 A1 WO 2021200518A1
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Prior art keywords
film
conductive film
base material
metal film
stretchable conductive
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PCT/JP2021/012436
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English (en)
Japanese (ja)
Inventor
陽介 中西
直樹 永岡
梨恵 林内
真郷 葛田
広宣 待永
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日東電工株式会社
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Publication of WO2021200518A1 publication Critical patent/WO2021200518A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/84—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by variation of applied mechanical force, e.g. of pressure
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields

Definitions

  • the present invention relates to a stretchable conductive film, a sensor using the film, a radio wave absorber, and a reflector.
  • Patent Document 1 describes a tire pressure sensor in which a piezoelectric thin film is formed on a flexible film-like substrate.
  • Patent Document 2 describes an electronic device capable of detecting strain and temperature, which comprises an electrode made of a metal nitride film on an insulating film base material such as polyimide.
  • An object of the present invention is to provide a stretchable conductive film having excellent elasticity and flexibility in addition to conductivity.
  • the present invention relates to the following stretchable conductive films and the like.
  • a film-like base material and a metal film formed on at least one main surface of the base material are provided, and the base material has a stress of 10 N / mm 2 or less when strained by 10% at room temperature.
  • ⁇ 3> The stretchable conductive film according to ⁇ 1> or ⁇ 2>, wherein the metal film has a thickness of 10 to 500 nm.
  • the metal film is a film containing at least one selected from gold, silver, copper, iron, aluminum, nickel, manganese, cobalt, and an alloy containing at least one of these, ⁇ 1> to ⁇ 3>.
  • the stretchable conductive film according to any one of. ⁇ 5> The stretchable conductive film according to any one of ⁇ 1> to ⁇ 4>, wherein the strain resistance increase rate A 20 represented by the following formula is 30% or less.
  • a 20 100 ⁇ (R 20- R 0 ) / R 0 R 0 [ ⁇ ]: Electrical resistance when the stretchable conductive film is distorted by 0% at room temperature
  • a sensor provided with the stretchable conductive film according to any one of ⁇ 5>.
  • ⁇ 7> A radio wave absorber or reflector provided with the stretchable conductive film according to any one of ⁇ 1> to ⁇ 4>.
  • a stretchable conductive film having excellent elasticity, flexibility, and conductivity is provided.
  • FIG. 1 is a cross-sectional view showing an embodiment of the stretchable conductive film of the present invention.
  • FIG. 2 is a diagram illustrating a method for measuring the strain resistance increase rate.
  • the stretchable conductive film of the present invention includes a film-like base material and a metal film formed on at least one main surface of the base material.
  • FIG. 1 is a cross-sectional view showing an embodiment of the stretchable conductive film 1.
  • the metal film 20 may be formed on only one side of the base material 10, or may be formed on both sides, although not shown. Further, as shown in FIG. 1, the metal film 20 may be formed on the entire main surface of the base material 10, or may be formed at least partially, although not shown. Further, the metal film may be formed in the shape of various circuit patterns according to the use of the stretchable conductive film.
  • the base material has a stress of 10 N / mm 2 or less when strained by 10% at room temperature.
  • the stress is preferably 7 N / mm 2 or less, more preferably 5 N / mm 2 or less.
  • the stress is preferably 0.1 N / mm 2 or more, more preferably 0.5 N / mm 2 or more, and further preferably 1 N / mm 2 or more.
  • room temperature means 21 ° C to 25 ° C.
  • the stress when strained by 10% is measured in accordance with JIS7161-1: 2014.
  • the base material in the present invention is in the form of a film.
  • the thickness of the base material is preferably 10 to 500 ⁇ m, more preferably 20 to 300 ⁇ m. When the thickness of the base material is 500 ⁇ m or less, the load does not become too large and the followability is good, and when it is 10 ⁇ m or more, the handleability is good.
  • the base material is not particularly limited as long as it is a material that satisfies the above specific stress and has flexibility and elasticity, and examples thereof include elastomers and fibers. Elastomers are preferred from the standpoint of flexibility.
  • elastomer for example, urethane rubber, silicone rubber, fluororubber, nitrile rubber, acrylic rubber, styrene rubber, chloroprene rubber, butyl rubber, ethylene rubber, propylene rubber, ethylene propylene rubber, natural rubber, and two or more of these are combined. Examples include a complex and the like.
  • the stretchable conductive film of the present invention includes a metal film formed on at least one main surface of the base material.
  • a ductile metal film is preferable because it easily follows the deformation of the base material.
  • the ductile metal at least one selected from gold, silver, copper, iron, aluminum, nickel, manganese, cobalt and an alloy containing at least one of these is preferable.
  • the oxygen atom concentration in the metal film is preferably 5.0 ⁇ 10 20 atom / cm 3 or less.
  • the oxygen atom concentration in the metal film is more preferably 3.0 ⁇ 10 20 atom / cm 3 or less, and further preferably 1.0 ⁇ 10 20 atom / cm 3 or less.
  • the lower limit is preferably 0 atom / cm 3 .
  • the oxygen atom concentration in the metal film is measured at a depth (T 0.5 ) of 1/2 the thickness (T) of the metal film from the outermost surface of the metal film.
  • the metal film can be formed by, for example, sputtering as described later.
  • oxygen-containing substances are volatilized from water, oxygen, carbon dioxide, unreacted monomers and the like existing in the base material and the chamber, and are taken into the metal film. Therefore, in order to keep the oxygen atom concentration in the metal film within the above range, for example, the base material is heated before sputtering, and the inside of the chamber is degassed by degassing or the like, so that the water content and oxygen in the base material and the chamber are degassed.
  • Carbon dioxide, unreacted monomer and the like can be mentioned.
  • the thickness of the metal film is preferably 10 to 500 nm, more preferably 20 to 300 nm. It is preferable that the thickness of the metal film is within the range, because the stress difference with the base material is small and the followability is good. Further, the metal film may be a single-layer film or a multilayer film in which different metal layers are laminated. In the case of a multilayer film, it is preferable to satisfy the above thickness as a whole.
  • the strain resistance increase rate A 20 represented by the following formula is preferably 30% or less, more preferably 20% or less.
  • a 20 100 ⁇ (R 20- R 0 ) / R 0 R 0 [ ⁇ ]: Electrical resistance when the stretchable conductive film is distorted by 0% at room temperature
  • strain resistance increase rate A 20 The smaller the strain resistance increase rate A 20 is, the more preferable it is because it means that the stretchable conductive film is excellent in elasticity and conductivity.
  • the stretchable conductive film of the present invention can be produced by forming a metal film on at least one main surface of a film-like base material.
  • a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method (CVD) such as plasma CVD, optical CVD, laser CVD, electrolytic plating, chemical plating, etc.
  • CVD chemical vapor deposition method
  • a physical vapor deposition method is preferable, and a sputtering method is more preferable.
  • the sputtering method is preferable from the viewpoint that the degree of vacuum is high, a large area can be formed, and the film thickness can be easily controlled.
  • the target and the adherend are placed facing each other in the chamber of the vacuum device, and gas ions are accelerated by applying a voltage while supplying gas to irradiate the target material, and the target material is ejected from the target surface.
  • the target material is laminated on the surface of the adherend.
  • the target material contains a substance constituting a metal film.
  • Examples of the sputtering method include a bipolar sputtering method, an ECR (electron cyclotron resonance) sputtering method, a magnetron sputtering method, and an ion beam sputtering method.
  • the electrode used in the sputtering method may be a direct current (DC) power supply, an alternating current medium frequency (AC / MF) power supply, a high frequency (RF) power supply, or a high frequency power supply in which a direct current power supply is superimposed.
  • DC direct current
  • AC / MF alternating current medium frequency
  • RF high frequency
  • the temperature for heating the base material is preferably 50 to 200 ° C., preferably 80 to 180 ° C., more preferably 100 to 150 ° C., and the time for heating the base material is preferable. Is 1 to 100 minutes, more preferably 5 to 60 minutes, and more preferably 10 to 50 minutes. From the viewpoint of removing outgas, the pressure inside the chamber is preferably 1.0 ⁇ 10 -4 [Pa] or less, more preferably 5.0 ⁇ 10 -5 [Pa] or less.
  • the stretchable conductive film of the present invention can be suitably used as various sensors such as a strain sensor, a temperature sensor, a heat flow sensor, and a magnetic sensor. Further, since the stretchable conductive film of the present invention is excellent in flexibility and elasticity, it can be applied to a portion accompanied by deformation. Therefore, it can be attached to curved surfaces such as pipes, electric wires, and living organisms with good followability, and the sensor sensitivity is stable. Therefore, for example, it is suitably used for various sensors installed inside tires, wearable sensors, etc., whose demand is expected to increase with the spread of automatic driving systems.
  • the strain sensor of the present invention includes, for example, the stretchable conductive film of the present invention.
  • the metal films themselves function as electrodes.
  • the metal film is preferably an Al film.
  • the strain sensor can measure the amount of strain by measuring the capacitance that changes with the deformation of the film.
  • the temperature sensor of the present invention includes, for example, a Ni film as a metal film (conductive layer) of the stretchable conductive film of the present invention.
  • the metal film itself functions as a sensor.
  • the temperature sensor can measure the temperature by measuring the electrical resistance of the metal film that changes with the temperature change of the film.
  • the heat flow sensor of the present invention includes, for example, an Fe-Pt alloy film as a metal film (conductive layer) of the stretchable conductive film of the present invention.
  • the metal film itself functions as a sensor.
  • the heat flow sensor can measure the heat flow by measuring the electromotive force of the metal film that changes with the temperature gradient of the film.
  • the magnetic sensor of the present invention includes, for example, a magnetic thin film as a metal film (conductive layer) of the stretchable conductive film of the present invention.
  • the magnetic thin film preferably contains at least one selected from the group consisting of Mn, Fe, Ni and Co.
  • the metal film itself functions as a sensor.
  • the magnetic sensor can measure the magnetic field strength by measuring the electrical signal that changes with the environmental magnetic field. Electrical signals include voltage, Hall voltage, current, resistance, and the like.
  • the stretchable conductive film of the present invention has conductivity, it can be used as a member of a radio wave absorber or a reflector. Further, since the stretchable conductive film of the present invention is excellent in flexibility and elasticity, the radio wave absorber or reflector using the stretchable conductive film has high flexibility. Therefore, the workability is excellent, and roll molding becomes possible at the time of manufacturing.
  • the radio wave absorber of the present invention is, for example, a ⁇ / 4 type radio wave absorber, in which a reflective layer, a dielectric layer, and an impedance matching layer are laminated in this order, and a stretcher of the present invention is applied to at least one of the reflective layer and the impedance matching layer.
  • a bull conductive film can be used.
  • the impedance matching layer may be applied to a support film such as polyethylene terephthalate by, for example, sputtering, vapor deposition, ion plating or coating (for example, bar coating). It can be produced by forming a non-porous film on one main surface of a base material by a film forming method.
  • the material of the impedance matching layer may be a metal such as indium tin oxide (ITO), an alloy, an inorganic material such as a metal oxide, or an organic material such as a conductive polymer and carbon nanotubes. ..
  • the impedance matching layer is preferably set to a sheet resistance in the range of 220 to 600 ⁇ / ⁇ .
  • the dielectric layer in the radio wave absorber preferably has a relative permittivity of 2.0 to 20.0. With such a relative permittivity, the thickness of the dielectric layer can be easily adjusted, and the radio wave absorption performance of the radio wave absorber can be easily adjusted.
  • the relative permittivity of the dielectric layer is, for example, the relative permittivity at 10 GHz measured according to the cavity resonance method.
  • the dielectric layer is made of, for example, ethylene vinyl acetate copolymer, vinyl chloride resin, urethane resin, acrylic resin, acrylic urethane resin, polyethylene, polypropylene, silicone, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, and cycloolefin polymer. It is preferable to contain at least one polymer selected from the above group. Further, the dielectric layer may be formed as a single layer, or may be formed by a plurality of layers made of the same or different materials.
  • the reflector of the present invention is used, for example, for controlling the reflection angle of a millimeter wave.
  • a reflective layer, a dielectric layer, and a conductive pattern layer are laminated in this order, and the stretcher of the present invention is applied to at least one of the reflective layer and the conductive pattern layer.
  • a bull conductive film can be used.
  • the conductive pattern layer is formed on a support film such as polyethylene terephthalate by, for example, sputtering, vapor deposition, ion plating or coating (for example, bar coating). It can be produced by forming a non-porous film on one main surface of the base material by the method, and further forming a pattern on the non-porous film by laser processing, etching or the like.
  • the material of the conductive pattern layer may be a metal such as indium tin oxide (ITO), an alloy, an inorganic material such as a metal oxide, or an organic material such as a conductive polymer and carbon nanotubes. ..
  • the dielectric layer in the reflector preferably has a relative permittivity of 2.0 to 20.0. With such a relative permittivity, the thickness of the dielectric layer can be easily adjusted, and the radio wave absorption performance of the reflector can be easily adjusted.
  • the relative permittivity of the dielectric layer is, for example, the relative permittivity at 10 GHz measured according to the cavity resonance method.
  • the dielectric layer is made of, for example, ethylene vinyl acetate copolymer, vinyl chloride resin, urethane resin, acrylic resin, acrylic urethane resin, polyethylene, polypropylene, silicone, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, and cycloolefin polymer. It is preferable to contain at least one polymer selected from the above group. Further, the dielectric layer may be formed as a single layer, or may be formed by a plurality of layers made of the same or different materials.
  • Example 1 ⁇ Manufacturing of stretchable conductive film (base material with metal film)>
  • a base material a urethane rubber film (manufactured by Nihon Matai Co., Ltd., product number: Esmer PX98, thickness: 150 ⁇ m) having a stress of 2.9 N / mm 2 (elastic modulus 29 MPa) when strained by 10% at room temperature is used. board. After heat-treating the substrate at 140 ° C. for 30 minutes before film formation, the ultimate vacuum in the apparatus was increased to 1.5 ⁇ 10-5 [Pa]. Then, using a 3-inch Al target, DC sputtering was performed at an output of 200 W under an Ar atmosphere and a back pressure of 0.3 Pa to form a 100 nm metal film (Al layer) on the surface of the substrate.
  • Example 2 As the base material, the same as in Example 1 except that a urethane rubber film (thickness: 30 ⁇ m) having a stress of 4.4 N / mm 2 (elastic modulus 44 MPa) when strained by 10% at room temperature was used. A metal film was formed on the surface of the substrate.
  • Example 3 Except for using a urethane rubber film (manufactured by Kurabo Co., Ltd., product number: Cranzir, thickness: 50 ⁇ m) having a stress of 2.8 N / mm 2 (elastic modulus 28 MPa) when strained by 10% at room temperature as the base material. Made a metal film on the surface of the base material in the same manner as in Example 1.
  • Example 4 A metal film was formed on the surface of the base material in the same manner as in Example 1 except that the ultimate vacuum degree in the apparatus was set to 5.0 ⁇ 10 -4 [Pa] without heat treatment of the base material.
  • Example 5 A metal film was formed on the surface of the base material in the same manner as in Example 2 except that the ultimate vacuum degree in the apparatus was set to 5.0 ⁇ 10 -4 [Pa] without heat treatment of the base material.
  • Example 6 A metal film was formed on the surface of the base material in the same manner as in Example 3 except that the ultimate vacuum degree in the apparatus was set to 5.0 ⁇ 10 -4 [Pa] without heat treatment of the base material.
  • Example 7 A metal film was formed on the surface of the base material in the same manner as in Example 1 except that the Ni target was used instead of the Al target.
  • Example 8 A metal film was formed on the surface of the base material in the same manner as in Example 1 except that the Cu target was used instead of the Al target.
  • Example 1 A metal film was formed on the surface of the base material in the same manner as in Example 1 except that a polyethylene terephthalate film (thickness: 50 ⁇ m) having an elastic modulus of 3.0 GPa was used as the base material.
  • the oxygen atom concentration in the metal film was measured by the following method. Using ADEPT-1010 manufactured by Albac Phi Co., Ltd., the concentration distribution of oxygen atoms in the metal film in the depth direction was investigated under the conditions of primary ion species Cs + and primary acceleration voltage of 3.0 kV. The depth was set to half the film thickness of the metal film, that is, a depth of 50 nm. The results are shown in Table 1 below.
  • a x (%) 100 x (R x -R 0 ) / R 0 (Ro [ ⁇ ]: resistance value between terminals before stretching (at 0% strain), R x [ ⁇ ]: resistance value between terminals at X% strain)
  • Table 1 below shows the resistance increase rates (A 20 , A 50 , A 100 ) when the strain is 20%, 50%, and 100%.
  • the strain resistance increase rate (A 20 ) when the strain was 20% was evaluated based on the following criteria, and if it was 50% or less, it was passed. A: 30% or less B: 50% or less C: More than 50% D: Break
  • the films of the examples are all excellent in flexibility, elasticity, and conductivity.
  • the films of the examples are all excellent in flexibility, elasticity, and conductivity.
  • the resistance increase due to strain is suppressed, and the flexibility, elasticity, and conductivity are further excellent. I understand.
  • a reflective layer, a dielectric layer, and an impedance matching layer were laminated in this order, and a radio wave absorber using a base material with a metal film produced in Examples or Comparative Examples was produced as the reflective layer.
  • Example 9 A dielectric layer having a relative permittivity of 2.6 composed of an acrylic resin layer having a thickness of 560 ⁇ m was laminated on the metal film side of the base material with a metal film produced in Example 3, and an impedance matching layer was further laminated. A ⁇ / 4 type radio wave absorber was created. The impedance matching layer was formed by forming an ITO layer on one side of a polyethylene terephthalate base material so that the sheet resistance was 377 ⁇ .
  • the stretchable conductive film of the present invention can be used as a member of a radio wave absorber and is excellent in flexibility and elasticity, so that it can be installed on a curved surface.
  • Example 10 A dielectric layer having a relative permittivity of 2.6 composed of an acrylic resin layer having a thickness of 500 ⁇ m was laminated on the metal film side of the base material with a metal film produced in Example 3, and a conductive pattern layer was further laminated. I created a reflector.
  • the conductive pattern layer was prepared by patterning an Al film on one side of a polyethylene terephthalate base material.
  • Example 3 A reflector was prepared in the same manner as in Example 10 except that the base material with a metal film prepared in Comparative Example 1 was used as the reflective layer.
  • the stretchable conductive film of the present invention can be used as a member of a reflector, and also has excellent flexibility and elasticity, so that it can be installed on a curved surface.
  • the stretchable conductive film of the present invention can be used as a member of various sensors such as a strain sensor, a temperature sensor, a heat flow sensor, and a magnetic sensor, and a radio wave absorber or a reflector. Further, since the stretchable conductive film of the present invention is excellent in flexibility and elasticity, it can be installed on a curved surface and can be applied to a place accompanied by deformation.
  • Stretchable conductive film 10 ... Base material, 20 ... Metal film

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention se rapporte à un film électroconducteur étirable comprenant un substrat de type film et un film métallique formé sur au moins l'une des surfaces principales du substrat, la contrainte dans le substrat sous une déformation de 10 % à température ambiante étant égale ou inférieure à 10 N/mm2.
PCT/JP2021/012436 2020-03-31 2021-03-24 Film électroconducteur étirable, capteur, absorbeur d'ondes radio et réflecteur WO2021200518A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04131233A (ja) * 1990-09-25 1992-05-01 Bridgestone Corp 可撓性部材のガスバリア性低下防止方法
JPH10223003A (ja) * 1997-02-12 1998-08-21 Ichikoh Ind Ltd 車両用灯具
JP2001284880A (ja) * 2000-03-31 2001-10-12 Furuya Kinzoku:Kk 電磁波遮蔽体
JP2003042296A (ja) * 2001-07-27 2003-02-13 Suzutora:Kk 帯電防止パッキン材
JP2004095782A (ja) * 2002-08-30 2004-03-25 Emf:Kk 電波吸収体及びその製造方法
JP2015055615A (ja) * 2013-09-13 2015-03-23 藤倉ゴム工業株式会社 エラスティックフレキシブルセンサ
KR20170105987A (ko) * 2016-03-11 2017-09-20 (주)알킨스 신축성을 갖는 전기전도성 필름 및 그 제조방법
WO2020067052A1 (fr) * 2018-09-25 2020-04-02 積水化学工業株式会社 Corps perméable aux ondes radio

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04131233A (ja) * 1990-09-25 1992-05-01 Bridgestone Corp 可撓性部材のガスバリア性低下防止方法
JPH10223003A (ja) * 1997-02-12 1998-08-21 Ichikoh Ind Ltd 車両用灯具
JP2001284880A (ja) * 2000-03-31 2001-10-12 Furuya Kinzoku:Kk 電磁波遮蔽体
JP2003042296A (ja) * 2001-07-27 2003-02-13 Suzutora:Kk 帯電防止パッキン材
JP2004095782A (ja) * 2002-08-30 2004-03-25 Emf:Kk 電波吸収体及びその製造方法
JP2015055615A (ja) * 2013-09-13 2015-03-23 藤倉ゴム工業株式会社 エラスティックフレキシブルセンサ
KR20170105987A (ko) * 2016-03-11 2017-09-20 (주)알킨스 신축성을 갖는 전기전도성 필름 및 그 제조방법
WO2020067052A1 (fr) * 2018-09-25 2020-04-02 積水化学工業株式会社 Corps perméable aux ondes radio

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