WO2022131298A1 - 誘電体層の製造方法、樹脂組成物、及び誘電体層を含む積層体 - Google Patents

誘電体層の製造方法、樹脂組成物、及び誘電体層を含む積層体 Download PDF

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Publication number
WO2022131298A1
WO2022131298A1 PCT/JP2021/046304 JP2021046304W WO2022131298A1 WO 2022131298 A1 WO2022131298 A1 WO 2022131298A1 JP 2021046304 W JP2021046304 W JP 2021046304W WO 2022131298 A1 WO2022131298 A1 WO 2022131298A1
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Prior art keywords
dielectric layer
resin composition
ghz
electromagnetic wave
layer
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PCT/JP2021/046304
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English (en)
French (fr)
Japanese (ja)
Inventor
碩芳 西山
亮 正田
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Toppan Inc
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Toppan Inc
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Priority to CN202180084206.5A priority Critical patent/CN116600990A/zh
Priority to EP21906659.4A priority patent/EP4266850A4/en
Priority to KR1020237014972A priority patent/KR20230121722A/ko
Priority to JP2022514217A priority patent/JP7323708B2/ja
Publication of WO2022131298A1 publication Critical patent/WO2022131298A1/ja
Priority to JP2022179132A priority patent/JP2023016814A/ja
Priority to US18/208,068 priority patent/US20230420156A1/en
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/002—Inhomogeneous material in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors (thin- or thick-film circuits; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor)
    • 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
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/20—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06
    • H01G4/206—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06 inorganic and synthetic material
    • 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
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/14—Organic dielectrics
    • H01G4/145—Organic dielectrics vapour deposited
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/20—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06

Definitions

  • the present disclosure relates to a method for manufacturing a dielectric layer included in a reflective electromagnetic wave absorber, a resin composition used for forming the dielectric layer, and a laminate containing the dielectric layer.
  • Patent Document 1 discloses a radio wave absorber having a dielectric layer between a resistance film containing ultrafine conductive fibers and a radio wave reflector.
  • Patent Document 2 includes a first layer which is a dielectric layer or a magnetic material layer, and a conductive layer provided on at least one side of the first layer, and the relative permittivity of the first layer is 1 to 10. The electromagnetic wave absorber is disclosed.
  • the dielectric layer of the reflective electromagnetic wave absorber is a layer for interfering the incident electromagnetic wave with the reflected electromagnetic wave.
  • ⁇ indicates the wavelength of the electromagnetic wave to be reduced (unit: m)
  • ⁇ r indicates the relative permittivity of the material constituting the dielectric layer
  • d indicates the thickness of the dielectric layer (unit: m).
  • Reflection attenuation is obtained by shifting the phase of the incident electromagnetic wave and the phase of the reflected electromagnetic wave by ⁇ .
  • the dielectric layer has to be thickened. Therefore, there is still room for improvement in terms of manufacturing efficiency of the dielectric layer and space saving.
  • the present disclosure provides a method for efficiently manufacturing a dielectric layer used for a reflective electromagnetic wave absorber, which can realize an excellent reflection attenuation amount.
  • the present disclosure also provides a resin composition used for forming such a dielectric layer and a laminate containing the dielectric layer.
  • One aspect of the present disclosure relates to a method for manufacturing a dielectric layer included in a reflective electromagnetic wave absorber.
  • This production method comprises a step of preparing a resin composition containing at least one kind of dielectric compound and a resin component and having a relative permittivity of more than 10.0 at a frequency of 3.7 GHz or 90 GHz, and the resin composition. It includes a step of forming a dielectric layer having a thickness of 20 to 7000 ⁇ m.
  • the relative permittivity of the first layer is set in the range of 1 to 10 in order to exhibit good electromagnetic wave absorption performance in a bandwidth of 50 to 100 GHz and a bandwidth of 2 GHz or more. It is accepted (see paragraph [0016] of Patent Document 2).
  • the relative permittivity of the dielectric layer is set to a value higher than 10.0. This is based on the following technical ideas. That is, for example, considering a 76 GHz in-vehicle millimeter-wave radar that is expected to be put into practical use, the allowable value of the occupied frequency bandwidth is limited to the range of 500 MHz (Japan) to 1 GHz (foreign countries).
  • sufficient absorption performance may be satisfied in this frequency band of about 1 GHz.
  • the relative permittivity of the dielectric layer tends to decrease as the frequency increases. If the relative permittivity at a frequency of 3.7 GHz or 90 GHz is higher than 10.0, the dielectric layer according to the present disclosure can be used as an electromagnetic wave absorber for 5 G (28 GHz) or millimeter wave radar (76 GHz) first. It can be fully effective for the problems mentioned.
  • One aspect of the present disclosure relates to a resin composition used for forming a dielectric layer included in a reflective electromagnetic wave absorber.
  • This resin composition contains at least one kind of dielectric compound and a resin component, and has a relative permittivity higher than 10.0 at a frequency of 3.7 GHz or 90 GHz.
  • the embodiment of the dielectric compound is, for example, powdery, and its relative permittivity is preferably higher than the relative permittivity of the resin component.
  • Specific examples of the dielectric compound include metal compounds such as titanium oxide and barium titanate.
  • the relative permittivity of the resin component at a frequency of 3.7 GHz or 90 GHz is preferably 2.5 to 9.5, for example.
  • the resin composition itself has adhesiveness.
  • the dielectric layer By forming the dielectric layer with the adhesive resin composition, the dielectric layer can be efficiently attached to the target member.
  • the adhesive strength of the resin composition to the stainless 304 steel sheet is preferably 1.0 N / 25 mm or more.
  • One aspect of the present disclosure relates to a laminate including a dielectric layer.
  • This laminate includes a dielectric layer made of the above resin composition and an adhesive layer provided on at least one surface of the dielectric layer. According to such a configuration, the dielectric layer can be efficiently attached to the target member via the adhesive layer.
  • a method for efficiently manufacturing a dielectric layer used for a reflection type electromagnetic wave absorber which can realize an excellent reflection attenuation amount. Further, according to the present disclosure, there is provided a resin composition used for forming such a dielectric layer and a laminate containing the dielectric layer.
  • FIG. 1 is a cross-sectional view schematically showing a first embodiment of the laminated body according to the present disclosure.
  • FIG. 2 is a cross-sectional view schematically showing a second embodiment of the laminated body according to the present disclosure.
  • FIG. 1 is a cross-sectional view schematically showing a reflective electromagnetic wave absorber according to the first embodiment.
  • the electromagnetic wave absorber 10 shown in this figure is in the form of a film or a sheet, and has a laminated structure including an electromagnetic wave transmitting layer 1, a dielectric layer 3, and a reflecting layer 4 in this order.
  • the film-shaped electromagnetic wave absorber has, for example, a total thickness of 24 to 250 ⁇ m.
  • the sheet-shaped electromagnetic wave absorber has, for example, an overall thickness of 0.25 to 7.1 mm.
  • the electromagnetic wave transmitting layer 1 is a layer for allowing electromagnetic waves incident from the outside to reach the dielectric layer 3. That is, the electromagnetic wave transmitting layer 1 is a layer for impedance matching according to the environment and layer structure in which the electromagnetic wave absorber 10 is used, whereby the electromagnetic wave absorber 10 having a large reflection attenuation amount can be obtained.
  • the sheet resistance of the electromagnetic wave transmitting layer 1 may be set according to the relative permittivity of the dielectric layer 3, for example, at 3.7 GHz.
  • the sheet resistance of the electromagnetic wave transmitting layer 1 may be set in the range of 200 to 800 ⁇ / ⁇ , or may be set in the range of 350 to 400 ⁇ / ⁇ .
  • the sheet resistance of the electromagnetic wave transmitting layer 1 may be set in the range of 200 to 800 ⁇ / ⁇ , and may be set in the range of 350 to 400 ⁇ / ⁇ . ..
  • the electromagnetic wave transmitting layer 1 contains an inorganic material or an organic material having conductivity.
  • the conductive inorganic material include indium tin oxide (ITO), zinc oxide (IZO), aluminum zinc oxide (AZO), carbon nanotubes, graphene, Ag, Al, Au, Pt, Pd, Cu, and Co. , Cr, In, Ag-Cu, Cu-Au, and nanoparticles containing one or more selected from the group consisting of Ni nanoparticles, or nanoparticles, and examples of the organic material having conductivity include polythiophene derivatives. , Polyacetylene derivatives, polyaniline derivatives, polypyrrole derivatives.
  • the electromagnetic wave transmitting layer 1 may contain a mixture (PEDOT / PSS) of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PPS).
  • PEDOT polyethylene dioxythiophene
  • PPS polystyrene sulfonic acid
  • the thickness (film thickness) of the electromagnetic wave transmitting layer 1 is preferably in the range of 0.1 nm to 100 nm, and preferably in the range of 1 nm to 50 nm. More preferred.
  • the film thickness is 0.1 nm or more, it is easy to form a uniform film, and there is a tendency that the function as the electromagnetic wave transmitting layer 1 can be more sufficiently fulfilled.
  • the film thickness is 100 nm or less, sufficient flexibility can be maintained, and it is possible to more reliably prevent cracks in the thin film due to external factors such as bending and tension after film formation. It tends to suppress heat damage and shrinkage to the substrate.
  • the thickness (thickness) of the electromagnetic wave transmitting layer 1 is preferably in the range of 0.1 to 2.0 ⁇ m, preferably 0.1 to 0.4 ⁇ m. It is more preferable to keep it within the range.
  • the film thickness is 0.1 ⁇ m or more, it is easy to form a uniform film, and there is a tendency that the function as the electromagnetic wave transmitting layer 1 can be more sufficiently fulfilled.
  • the film thickness is 2.0 ⁇ m or less, sufficient flexibility can be maintained, and it is possible to more reliably prevent cracks in the thin film due to external factors such as bending and pulling after film formation. There is a tendency to be able to do it.
  • Examples of the film forming method include a dry coating method and a wet coating method.
  • Examples of the dry coating method include resistance heating, induction heating, a vacuum deposition method using an ion beam (EB), a sputtering method, and the like.
  • the resistance heating method the material is placed in a ceramic crucible, a voltage is applied to the heater surrounding the crucible to pass an electric current, and the crucible is heated in a vacuum to evaporate the inorganic material from the opening and use it as a base material.
  • a film is formed by adhering.
  • the film formation speed is adjusted by controlling the distance between the material and the base material, the voltage applied to the heater, and the current. By controlling, the film thickness is controlled.
  • the ion beam emits electrons by passing an electric current through the filament in a vacuum, and by directly hitting the material with the electrons emitted by the electromagnetic lens, it heats and evaporates the inorganic material and attaches it to the substrate to form a film. do. It is used when an inorganic material that requires a large amount of heat or a large film formation rate is required for evaporation.
  • the distance between the material and the base material, the amount of electrons generated from the filament by the electric current, and the irradiation position and range (squeezing) of the material are controlled by the electromagnetic lens, the film formation speed is adjusted, and the shutter opening / closing time and line speed are used as described above.
  • the film time is controlled and the film thickness is controlled.
  • a rare gas such as Ar is mainly introduced onto a target made of an inorganic material, Ar is turned into plasma by applying a voltage, and the plasmaized Ar is accelerated by the voltage and collides with the target. , The material is physically blown off (sputtering) and adhered to the base material to form a film. Inorganic materials that cannot be formed by the air vapor deposition method may be able to be formed by the sputtering method.
  • the film formation speed is adjusted by controlling the distance between the target and the base material, the power applied to the target, and the Ar gas pressure, and the film formation time is controlled by the shutter opening / closing time and line speed as described above to control the film thickness. do. It is mainly used when forming a film of an inorganic material.
  • the wet coating method is a method in which a material is mainly applied to a base material.
  • a solid material under normal temperature and pressure is appropriately dissolved in a solvent or inked by dispersion, coated, and then dried to remove the solvent to form a film. do.
  • Examples of the coating method include a die coat, a micro gravure coat, a rod gravure coat, and a gravure coat.
  • the rotation ratio is controlled, ink is applied to the substrate, and the substrate is dried to control the film thickness. It is mainly used when forming films of organic materials and some inorganic dispersion materials.
  • the sheet resistance value of the electromagnetic wave transmitting layer 1 can be measured using, for example, Lorester GP MCP-T610 (trade name, manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
  • the dielectric layer 3 is a layer for interfering an incident electromagnetic wave with a reflected electromagnetic wave.
  • ⁇ indicates the wavelength of the electromagnetic wave to be suppressed (unit: m)
  • ⁇ r indicates the relative permittivity of the material constituting the dielectric layer 3
  • d indicates the thickness of the dielectric layer 3 (unit: m). show. Reflection attenuation is obtained by shifting the phase of the incident electromagnetic wave and the phase of the reflected electromagnetic wave by ⁇ .
  • the dielectric layer 3 is composed of a resin composition having a relative permittivity higher than 10.0 at a frequency of 3.7 GHz. Since the relative permittivity of the dielectric layer 3 is higher than 10.0, excellent absorption performance (preferably ⁇ 15 dB, more preferably ⁇ 20 dB) can be realized in a specific frequency band as described above. In addition to this, since the dielectric layer 3 can be made thin, both productivity improvement and space saving of the dielectric layer 3 can be achieved to a high level.
  • the relative permittivity of the dielectric layer 3 at a frequency of 3.7 GHz is preferably higher than 10.0 and 30.0 or less, and more preferably higher than 10.0 and 20.0 or less.
  • the dielectric layer 3 When the relative permittivity of the dielectric layer 3 at a frequency of 3.7 GHz or less is 30.0 or less, the dielectric layer 3 having sufficient strength tends to be formed. For example, if an excessive amount of a dielectric compound is added to the dielectric layer 3 in order to increase the relative permittivity of the dielectric layer 3, the dielectric layer 3 tends to become brittle.
  • the thickness of the dielectric layer 3 may be appropriately set according to the frequency band and the relative permittivity. For example, assuming use in a 60 GHz, 76 GHz or 90 GHz band such as a millimeter wave radar, the thickness of the dielectric layer 3 is preferably 100 to 400 ⁇ m, more preferably 250 to 400 ⁇ m.
  • the thickness of the dielectric layer 3 is preferably 450 to 7000 ⁇ m, more preferably 650 to 6500 ⁇ m. Further, the thickness of the dielectric layer 3 is preferable when it is assumed that the terahertz wave, for example, 300 GHz or 350 GHz band, which has been attracting attention in the fields of next-generation communication standards, measurement / analysis technology, medical treatment, etc., is used in recent years. Is 20 to 80 ⁇ m, more preferably 50 to 80 ⁇ m.
  • the resin composition constituting the dielectric layer 3 contains at least one kind of dielectric compound and a resin component.
  • the relative permittivity of the dielectric layer 3 can be adjusted according to the selection of the dielectric compound in the resin composition and its content.
  • the content of the dielectric compound is preferably 10 to 300 parts by volume, and more preferably 25 to 100 parts by volume with respect to 100 parts by volume of the resin composition.
  • the content of the dielectric compound is preferably 10 to 900 parts by mass, more preferably 25 to 100 parts by mass with respect to 100 parts by mass of the resin composition.
  • the relative permittivity of the dielectric layer 3 tends to be sufficiently large, while when it is not more than the upper limit value, the wet coating method or There is a tendency to efficiently manufacture the dielectric layer 3 by extrusion molding.
  • dielectric compounds barium titanate, titanium oxide and zinc oxide, aluminum oxide, magnesium oxide, niobium oxide, tantalum oxide, vanadium oxide, forsterite (Mg 2 SiO 4 ), barium magnesium niobate (Ba (Mg 1 / )).
  • metal compounds such as 3 Nb 2/3 ) O 3
  • barium neodymate titanate Ba 3 Nd 9.3 Ti 18 O 54
  • gallium nitride and aluminum nitride.
  • the aspect of the dielectric compound is preferably a powder (eg, nanoparticles).
  • the relative permittivity of the dielectric compound is preferably higher than the relative permittivity of the resin component.
  • the relative permittivity of the dielectric compound at a frequency of 3.7 GHz or 90 GHz is preferably higher than 10 and 5000 or less, more preferably 100 to 5000, and even more preferably 1000 to 5000.
  • the resin component examples include acrylic resin, methacrylic resin, silicone resin, polycarbonate, epoxy resin, glyptal resin, polyvinyl chloride, polyvinylformal, phenol resin, urea resin and polychloroprene resin.
  • the relative permittivity of the resin component at a frequency of 3.7 GHz or 90 GHz is preferably 2.5 to 9.5, more preferably 3.5 to 9.5, still more preferably 5.0 to 9.5. Is.
  • the resin composition preferably has adhesiveness.
  • the dielectric layer 3 can be efficiently attached to the surface 4F of the reflective layer 4.
  • examples of such materials include silicone pressure-sensitive adhesives, acrylic pressure-sensitive adhesives and urethane pressure-sensitive adhesives. These materials may be used as the resin component, or an adhesive layer composed of these materials may be formed on at least one surface of the dielectric layer 3.
  • the adhesive strength of the resin composition itself or the adhesive layer to the stainless 304 steel sheet is preferably 1.0 N / 25 mm or more, even if it is 3.0 to 10.0 N / 25 mm or 10.0 to 15.0 N / 25 mm. good.
  • the complex permittivity of the dielectric layer 3 is expressed by the following equation.
  • i is the imaginary unit
  • ⁇ ' is the real part of the complex permittivity
  • Complex permittivity ⁇ ⁇ '-i ⁇ ”
  • the real part of the complex permittivity is the relative permittivity (ratio to the permittivity ⁇ 0 of vacuum).
  • the relative permittivity and the dielectric loss tangent can be determined using a permittivity measuring device.
  • the real part of the complex dielectric constant of the dielectric layer 3 at 3.7 GHz or 90 GHz is preferably larger than 10, more preferably 10.5 to 30, and even more preferably 12 to 20. When this value is larger than 10, it tends to be possible to achieve excellent absorption performance in a specific frequency band. On the other hand, when this value is 30 or less, the dielectric layer 3 having sufficient strength tends to be formed.
  • the imaginary portion of the complex dielectric constant of the dielectric layer 3 at 3.7 GHz or 90 GHz is preferably 5 or less, more preferably 0 to 3.5, and even more preferably 0 to 3.
  • the reflective layer 4 is a layer for reflecting electromagnetic waves incident from the dielectric layer 3 and reaching the dielectric layer 3.
  • the thickness of the reflective layer 4 is, for example, 4 to 250 ⁇ m, and may be 4 to 12 ⁇ m or 50 to 100 ⁇ m.
  • the reflective layer 4 is made of a conductive material, and it is preferable that the sheet resistance value is 100 ⁇ / ⁇ or less because electromagnetic waves can be reflected.
  • a material may be an inorganic material or an organic material.
  • the conductive inorganic material include zinc oxide tin (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), carbon nanotubes, graphene, Ag, Al, Au, Pt, Pd, Cu, Co, Cr. , In, Ag-Cu, Cu-Au and nanoparticles containing one or more selected from the group consisting of Ni nanoparticles, or nanoparticles.
  • Examples of the organic material having conductivity include a polythiophene derivative, a polyacetylene derivative, a polyaniline derivative, and a polypyrrole derivative.
  • a conductive inorganic material or organic material may be formed on a substrate with a thickness such that the sheet resistance is 100 ⁇ / ⁇ or less. From the viewpoints of flexibility, film forming property, stability, sheet resistance value and low cost, it is possible to use a laminated film (Al-deposited PET film) including a PET film and an aluminum layer deposited on the surface thereof as a reflective layer. preferable.
  • the electromagnetic wave absorber 10 is manufactured, for example, through the following steps. First, a roll-shaped dielectric layer is produced, and then a roll-shaped laminated body including the dielectric layer is produced by a roll-to-roll method. The electromagnetic wave absorber 10 is obtained by cutting this laminated body into a predetermined size.
  • the roll-shaped dielectric layer is manufactured through (A) a step of preparing the above resin composition and (B) a step of forming a dielectric layer composed of this resin composition by a roll-to-roll method.
  • the thickness of the dielectric layer is sufficiently thin, so that the electromagnetic wave absorber 10 can be manufactured by the roll-to-roll method.
  • the frequency band to be applied is low (for example, less than 28 GHz)
  • the dielectric layer can be formed by extrusion molding. That is, the manufacturing method may be appropriately selected according to the frequency band to be applied (in other words, the thickness of the dielectric layer).
  • the method for producing the dielectric layer and the laminated body is not particularly limited, and the dielectric layer and the laminated body can be produced by using conventionally known methods such as a dry laminating method and a melt-extruded laminating method.
  • the dielectric layer can be produced by comma coating, die coating, extrusion film formation, or calendar film formation.
  • comma coating an appropriate gap is created between the comma roll and the coating roll, the base material runs between them, a certain amount of coating liquid is applied to the film from the gap, and the film is dried to form a film. ..
  • a dielectric layer having an arbitrary film thickness can be obtained by adjusting the gap.
  • a dielectric layer can be produced by applying a coating liquid from a die slot to a base material conveyed on a backup roll with a gap called a coating gap and drying it.
  • a dielectric layer having an arbitrary film thickness can be obtained by adjusting the supply liquid flow rate, coating gap, substrate transfer speed, and the like.
  • a release-treated PET, an electromagnetic wave transmission layer, or a reflection layer can be used as before.
  • the resin composition for forming the dielectric layer is supplied to a melt extruder heated to a temperature of about Tm + 100 ° C. or higher than the melting point of the resin composition to form the dielectric layer.
  • the resin composition for this purpose is melted, extruded into a sheet from a die head such as a T-die, the extruded sheet is rapidly cooled and solidified by a rotating cooling drum or the like, and the dielectric layer is formed by winding. can do.
  • the thickness of the dielectric layer can be controlled by the degree of opening of the "lip" that discharges the resin.
  • a dielectric layer can be produced by melting a resin using a mixing roll, inserting a resin composition between two or more calendar rolls, rotating the resin, rolling, cooling, and winding the resin. The thickness of the dielectric layer can be controlled by adjusting the clearance between the calendar rolls. If the base material can be attached, it is the same as before.
  • a laminated body can be produced by laminating the electromagnetic wave transmitting layer or the reflecting layer with a laminator. If the resin composition itself has no adhesiveness or the adhesive strength is small, an adhesive layer is separately prepared by using a dry laminate or the like, and the adhesive layer is applied to the resin composition itself by laminating and bonding. An adhesive layer can be imparted by laminating with an electromagnetic wave transmitting layer or a reflective layer used when the laminate is dried and made into a laminated body. Further, a laminated body can be produced by applying an adhesive to an electromagnetic wave transmitting layer or a reflective layer, drying the layer, and dry laminating the dielectric layer.
  • FIG. 2 is a cross-sectional view schematically showing a reflective electromagnetic wave absorber according to the second embodiment.
  • the reflective electromagnetic wave absorber 20 shown in this figure is in the form of a film or a sheet, and has a laminated structure including an electromagnetic wave transmitting layer 1, a resistance layer 5, a dielectric layer 3, and a reflecting layer 4 in this order.
  • the electromagnetic wave absorber 20 has the same configuration as the electromagnetic wave absorber 10 according to the first embodiment, except that the resistance layer 5 is provided between the electromagnetic wave transmitting layer 1 and the dielectric layer 3.
  • the resistance layer 5 will be described.
  • the resistance layer 5 is a layer for bringing the electromagnetic wave incident from the electromagnetic wave transmitting layer 1 to the dielectric layer 3. That is, the resistance layer 5 is a layer for impedance matching according to the environment in which the electromagnetic wave absorber 20 is used and the characteristics of the electromagnetic wave transmitting layer 1. For example, when the electromagnetic wave absorber 20 is used in air (impedance: 377 ⁇ / ⁇ ), the real part (relative permittivity) of the complex dielectric constant of the dielectric layer 3 is 2.9, and the thickness is 50 ⁇ m. When the sheet resistance value of the resistance layer 5 is set in the range of 270 to 500 ⁇ / ⁇ , high reflection attenuation can be obtained.
  • the resistance layer 5 is made of a conductive material.
  • a material may be an inorganic material or an organic material.
  • the conductive inorganic material include indium tin oxide (ITO), zinc oxide (IZO), aluminum zinc oxide (AZO), carbon nanotubes, graphene, Ag, Al, Au, Pt, Pd, Cu, and Co. , Cr, In, Ag-Cu, Cu-Au and nanoparticles containing one or more selected from the group consisting of Ni nanoparticles, or nanoparticles.
  • the organic material having conductivity include a polythiophene derivative, a polyacetylene derivative, a polyaniline derivative, and a polypyrrole derivative.
  • the resistance layer 5 is made of a conductive polymer containing polyethylene dioxythiophene (PEDOT) from the viewpoints of flexibility, film forming suitability of wet coating, sheet resistance stability in the atmosphere after film formation, and sheet resistance value. Is preferable.
  • the resistance layer 5 may be formed of a mixture (PEDOT / PSS) of polyethylene dioxythiophene (PEDOT) and polystyrene sulfonic acid (PPS).
  • the sheet resistance value of the resistance layer 5 can be appropriately set by, for example, selecting a material having conductivity and adjusting the thickness of the resistance layer 5.
  • the thickness of the resistance layer 5 is preferably in the range of 0.1 to 2.0 ⁇ m, more preferably in the range of 0.1 to 0.4 ⁇ m.
  • the sheet resistance value can be measured using, for example, Lorester GP MCP-T610 (trade name, manufactured by Mitsubishi Chemical Analytec Co., Ltd.).
  • the relative permittivity of the dielectric layer 3 at a frequency of 3.7 GHz or 90 GHz is higher than 10.0, so that the dielectric layer 3 can be made sufficiently thin. can.
  • both productivity improvement and space saving of the dielectric layer 3 can be achieved to a high level.
  • a large reflection attenuation of 15 dB or more (more preferably 20 dB or more) can be achieved.
  • the present invention is not limited to the above embodiments.
  • the film-shaped or sheet-shaped electromagnetic wave absorbers 10 and 20 are exemplified, but the shape of the electromagnetic wave absorber is not limited to this.
  • the reflective layer 4 shown in FIGS. 1 and 2 does not have to be layered.
  • Resin component-Acrylic resin OC-3405 (manufactured by Saiden Chemical Co., Ltd., relative permittivity at 3.7 GHz: 4.2) -Silicone resin: MHM-SI500 (manufactured by Niei Kako Co., Ltd., relative permittivity at 3.7 GHz: 3.2) -Urethane resin: C60A10WN (manufactured by BASF Japan, Relative permittivity at 3.7 GHz: 4.5)
  • Dielectric compound / barium titanate powder BT-01 (manufactured by Sakai Chemical Industry Co., Ltd.) -Titanium oxide powder: CR-60 (manufactured by Ishihara Sangyo Co., Ltd.)
  • Example 1 to 3 and Comparative Examples 1 and 2 The resin compositions having the compositions shown in Table 1 were prepared respectively. The following items were evaluated for the resin compositions according to Examples and Comparative Examples.
  • a dielectric layer having the thickness shown in Table 1 was formed by die coating.
  • the thicknesses shown in Table 1 assume 90 GHz mobile communication. Since the thickness of the dielectric layer that can be formed by one coating is about 200 ⁇ m, only two coatings are required in Examples 1 to 3, whereas three coatings are required in Comparative Examples 1 and 2. Painting is required.
  • Example 4 and comparative example 3 The resin compositions having the compositions shown in Table 2 were prepared respectively. These resin compositions were evaluated in the same manner as in Example 1 above (1) to (3) and (5). Since the urethane resin used as the resin component does not have adhesiveness, a sample in which an acrylic resin (OC-3405) to which a dielectric compound is not added is laminated on one side of a film made of a resin composition with a wire bar # 5. was prepared separately. The adhesive strength of the adhesive layer made of this acrylic resin was evaluated in the same manner as above. The evaluation of (4) was carried out as follows. (4) Evaluation of Thickness of Dielectric Layer A dielectric layer having the thickness shown in Table 2 was formed by a calendar film formation. The thickness shown in Table 2 assumes 3.7 GHz communication. The thickness of the dielectric layer that can be formed by one calendar film formation is about 800 ⁇ m.
  • Example 5 and Comparative Example 4 The resin compositions having the compositions shown in Table 3 were prepared respectively. These resin compositions were evaluated in the same manner as in Example 4 above (1) to (3) and (5). The evaluation of (4) was carried out as follows. (4) Evaluation of Thickness of Dielectric Layer A dielectric layer having the thickness shown in Table 3 was formed by a calendar film formation. The thicknesses shown in Table 3 assume 28 GHz communication. However, since there is no data on the relative permittivity of the dielectric layer at 28 GHz, the thickness of the dielectric layer was set based on the relative permittivity at 3.7 GHz.
  • Example 6 and Comparative Example 5 The resin compositions having the compositions shown in Table 4 were prepared respectively. These resin compositions were evaluated in the same manner as in Example 4 above (1) to (3) and (5). The evaluation of (4) was carried out as follows. (4) Evaluation of Thickness of Dielectric Layer A dielectric layer having the thickness shown in Table 4 was formed by a calendar film formation. The thicknesses shown in Table 4 assume 60 GHz communication. However, since there is no data on the relative permittivity of the dielectric layer at 60 GHz, the thickness of the dielectric layer was set based on the relative permittivity at 90 GHz.
  • Example 7 and Comparative Example 6 The resin compositions having the compositions shown in Table 5 were prepared respectively. These resin compositions were evaluated in the same manner as in Example 4 above (1) to (3) and (5). The evaluation of (4) was carried out as follows. (4) Evaluation of Thickness of Dielectric Layer A dielectric layer having the thickness shown in Table 5 was formed by a calendar film formation. The thicknesses shown in Table 5 assume 350 GHz communication. However, since there is no data on the relative permittivity of the dielectric layer at 350 GHz, the thickness of the dielectric layer was set based on the relative permittivity at 90 GHz.
  • Electromagnetic wave transmitting layer 3 ... Dielectric layer, 4 ... Reflecting layer, 4F ... Surface, 5 ... Resistance layer, 10, 20 ... Reflective electromagnetic wave absorber.

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PCT/JP2021/046304 2020-12-17 2021-12-15 誘電体層の製造方法、樹脂組成物、及び誘電体層を含む積層体 Ceased WO2022131298A1 (ja)

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