WO2023042799A1 - Suppresseur d'ondes électromagnétiques - Google Patents

Suppresseur d'ondes électromagnétiques Download PDF

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Publication number
WO2023042799A1
WO2023042799A1 PCT/JP2022/034072 JP2022034072W WO2023042799A1 WO 2023042799 A1 WO2023042799 A1 WO 2023042799A1 JP 2022034072 W JP2022034072 W JP 2022034072W WO 2023042799 A1 WO2023042799 A1 WO 2023042799A1
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electromagnetic wave
layer
sheet resistance
barrier
suppressor
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PCT/JP2022/034072
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English (en)
Japanese (ja)
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美穂 今井
亮 正田
碩芳 西山
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凸版印刷株式会社
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Priority to JP2023548459A priority Critical patent/JPWO2023042799A1/ja
Publication of WO2023042799A1 publication Critical patent/WO2023042799A1/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
    • 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
    • B32B7/023—Optical properties
    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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 disclosure relates to electromagnetic wave suppressors.
  • Patent Document 1 discloses a radio wave absorber having a dielectric layer between a resistive film containing ultrafine conductive fibers and a radio wave reflector.
  • Patent Document 2 includes a first layer that is a dielectric layer or a magnetic layer and a conductive layer provided on at least one side of the first layer, and the first layer has a relative dielectric constant of 1 to 10. An electromagnetic wave absorber is disclosed.
  • the surface resistivity of the resistive film in the electromagnetic wave absorber described in Patent Document 1 is adjusted to a predetermined value so as to match the radio wave characteristic impedance of free space. More specifically, in the invention described in Patent Document 1, the amount of carbon nanotubes contained in the resistive film and the thickness of the resistive film are adjusted so that the surface resistivity of the resistive film is in the range of 377 ⁇ 30 ⁇ / ⁇ . etc. is set.
  • an electromagnetic wave suppressor comprising an electromagnetic wave transmission layer for impedance matching and a dielectric layer
  • the present inventors discovered a phenomenon in which the performance of the electromagnetic wave suppressor drops rapidly (return loss is reduced). We encountered a phenomenon of a sharp decline).
  • the main cause was an increase in the sheet resistance value of the electromagnetic wave permeable layer.
  • the electromagnetic wave permeable layer was in direct contact with the dielectric layer, such a phenomenon was likely to occur. I got some insight.
  • the present disclosure has been made in view of the above problems, and provides an electromagnetic wave suppressor capable of maintaining sufficient return loss over a long period of time.
  • the electromagnetic wave suppressor includes, in this order, an electromagnetic wave transmission layer having conductivity, a barrier layer, a dielectric layer containing at least one dielectric compound and a resin component, and a reflector.
  • an electromagnetic wave transmission layer having conductivity
  • a barrier layer between the electromagnetic wave permeable layer and the dielectric layer, for example, the sheet resistance value of the electromagnetic wave permeable layer is prevented from fluctuating (particularly increasing) due to substances contained in the dielectric layer. can be done. Therefore, the electromagnetic wave suppressor can maintain sufficient return loss over a long period of time.
  • an electromagnetic wave suppressor capable of maintaining sufficient return loss over a long period of time.
  • FIG. 1 is a cross-sectional view schematically showing one embodiment of an electromagnetic wave suppressor according to the present disclosure.
  • FIG. 2 is a cross-sectional view schematically showing a modification of the electromagnetic wave suppressor shown in FIG. 3(a) and 3(b) are sectional views schematically showing modifications of the electromagnetic wave suppressor shown in FIGS. 1 and 2, respectively.
  • FIG. 4 is a cross-sectional view schematically showing a configuration including an adhesive layer, which is a modification of the electromagnetic wave suppressor shown in FIG.
  • FIG. 5 is a cross-sectional view schematically showing another embodiment of an electromagnetic wave suppressor according to the present disclosure.
  • FIG. 6 is a cross-sectional view schematically showing another embodiment of an electromagnetic wave suppressor according to the present disclosure.
  • FIG. 1 is a cross-sectional view schematically showing a reflective electromagnetic wave suppressor according to this embodiment.
  • the electromagnetic wave suppressor 10 shown in this figure is in the form of a film or a sheet, and includes a substrate layer 1, an electromagnetic wave transmission layer 2, a barrier layer 3, a dielectric layer 4, and a reflective layer 5 (reflector). It has a laminated structure with an order.
  • the film-like electromagnetic wave suppressor has a total thickness of, for example, 24 to 250 ⁇ m.
  • the sheet-like electromagnetic wave suppressor has a total thickness of 0.25 to 7.1 mm, for example.
  • the base material layer 1 is composed of, for example, a polymer film.
  • materials for the polymer film include polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides such as nylon; polyolefins such as polypropylene and cycloolefin; polycarbonates; is not limited to
  • the polymer film is preferably a polyester film, a polyamide film or a polyolefin film, more preferably a polyester film or a polyamide film, and even more preferably a polyethylene terephthalate film (PET film).
  • PET film is desirable from the viewpoint of transparency, workability and adhesion.
  • the PET film is preferably a biaxially stretched PET film from the viewpoint of transparency and gas barrier properties.
  • the thickness of the polymer film is not particularly limited, it is preferably 3 ⁇ m or more and 100 ⁇ m or less, more preferably 5 ⁇ m or more and 50 ⁇ m or less. When the thickness is 3 ⁇ m or more, processing is easy, and when the thickness is 100 ⁇ m or less, the total thickness of the electromagnetic wave suppressor can be reduced.
  • the polymer film may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer and a slipping agent, if necessary.
  • the surface of the polymer film may be subjected to surface treatments such as corona treatment, flame treatment and plasma treatment.
  • the surface of the substrate layer 1 (polymer film) is the surface to be coated when the electromagnetic wave transmission layer 2 is formed by coating. For example, when the electromagnetic wave permeable layer 2 is transferred to another layer after coating, or when the electromagnetic wave permeable layer 2 is formed by a method other than coating, the electromagnetic wave suppressor 10 does not have the base layer 1. good too.
  • the electromagnetic wave transmission layer 2 is a layer for allowing electromagnetic waves incident from the outside to reach the dielectric layer 4 . That is, the electromagnetic wave transmission layer 2 is a layer for impedance matching according to the environment in which the electromagnetic wave suppressor 10 is used.
  • the sheet resistance value of the electromagnetic wave transmission layer 2 is set in the range of 350 to 600 ⁇ / ⁇ , for example.
  • the electromagnetic wave permeable layer 2 contains a conductive inorganic material or organic material.
  • conductive inorganic materials include indium tin oxide (ITO), indium zinc oxide (IZO), zinc aluminum oxide (AZO), carbon nanotubes, graphene, Ag, Al, Au, Pt, Pd, Cu, Co , Cr, In, Ag—Cu, Cu—Au, and Ni nanoparticles, or nanowires.
  • conductive organic materials include polythiophene derivatives, polyacetylene derivatives, polyaniline derivatives, and polypyrrole derivatives.
  • a conductive polymer containing polyethylenedioxythiophene (PEDOT) is preferable from the viewpoint of flexibility, film formability, stability, and sheet resistance of 377 ⁇ / ⁇ .
  • the electromagnetic wave transmission layer 2 may contain a mixture (PEDOT/PSS) of polyethylenedioxythiophene (PEDOT) and polystyrene sulfonic acid (PPS).
  • the sheet resistance value of the electromagnetic wave permeable layer 2 can be appropriately set, for example, by selecting a conductive organic material and adjusting the film thickness.
  • the thickness (film thickness) of the electromagnetic wave permeable layer 2 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 film thickness is 0.1 ⁇ m or more, it tends to be easy to form a uniform film, and the function of the electromagnetic wave transmitting layer 2 can be more sufficiently achieved.
  • the film thickness is 2.0 ⁇ m or less, sufficient flexibility can be maintained, and cracks in the thin film due to external factors such as bending and pulling after film formation can be more reliably prevented. tend to be able to
  • the sheet resistance value of the electromagnetic wave permeable layer 2 can be measured using, for example, Loresta GP MCP-T610 (trade name, manufactured by Mitsubishi Chemical Analytic Tech Co., Ltd.).
  • the sheet resistance change rate C1 of the electromagnetic wave transmitting layer 2 calculated by the following formula is preferably 60% or less, more preferably 35% or less, and even more preferably 9% or less.
  • Sheet resistance change rate C 1 [%] (R 1 ⁇ R 0 )/R 0 ⁇ 100
  • R 1 indicates the sheet resistance value of the electromagnetic wave permeable layer 2 after exposing the electromagnetic wave suppressor 10 to an environment with a temperature of 85° C. and a relative humidity of 85% for 24 hours; The sheet resistance value of the electromagnetic wave permeable layer 2 before exposing the suppressor 10 is shown. ]
  • the sheet resistance change rate C2 of the electromagnetic wave permeable layer 2 calculated by the following formula is preferably 9% or less, more preferably 6% or less, and even more preferably 2.5% or less.
  • Sheet resistance change rate C 2 [%] (R 2 ⁇ R 0 )/R 0 ⁇ 100
  • R 2 represents the sheet resistance value of the electromagnetic wave permeable layer 2 after the electromagnetic wave suppressor 10 has been exposed to an environment with a temperature of 85° C. and a relative humidity of 85% for 500 hours
  • R 0 represents the The sheet resistance value of the electromagnetic wave permeable layer 2 before exposing the suppressor 10 is shown.
  • the barrier layer 3 is provided between the electromagnetic wave permeable layer 2 and the dielectric layer 4 .
  • the barrier layer 3 plays a role of suppressing a change in the sheet resistance value of the electromagnetic wave transmission layer 2 due to substances contained in the dielectric layer 4 . It is also presumed that it also plays a role in suppressing changes in the sheet resistance value of the electromagnetic wave permeable layer 2 due to gases (for example, carbon dioxide) that may be generated from the dielectric layer 4 .
  • the sheet resistance value of the barrier layer 3 is preferably sufficiently high, for example, 1.0 ⁇ 10 6 ⁇ / ⁇ or more. By setting the sheet resistance value of the barrier layer 3 to 1.0 ⁇ 10 6 ⁇ / ⁇ or more, it is possible to suppress reflection of the electromagnetic waves incident from the electromagnetic wave transmission layer 2 on the surface of the barrier layer 3 .
  • the oxygen permeability of the barrier layer 3 is preferably 4.0 ⁇ 10 2 cc/(m 2 ⁇ day ⁇ atm) or less, more preferably 1.0 ⁇ 10 1 cc/(m 2 ⁇ day ⁇ atm). or less, more preferably 1.0 ⁇ 10 ⁇ 1 cc/(m 2 ⁇ day ⁇ atm) or less.
  • Oxygen permeability means a value measured under conditions of temperature of 30° C. and relative humidity of 70% according to the method described in JIS K7126-2.
  • the water vapor permeability of the barrier layer 3 is preferably 1.0 ⁇ 10 2 g/m 2 /day or less, more preferably 1.0 ⁇ 10 1 g/m 2 /day or less, still more preferably 2 .0 ⁇ 10 ⁇ 1 g/m 2 /day or less.
  • the water vapor permeability means a value measured under conditions of a temperature of 40°C and a relative humidity of 90% according to the method described in JIS K7129B.
  • the barrier layer 3 of this embodiment has a laminated structure including a base film 3a and a vapor deposition layer 3b.
  • the vapor deposition layer 3b is provided on one surface of the base film 3a.
  • the electromagnetic wave permeable layer 2 the base film 3a, the deposited layer 3b and the dielectric layer 4 are arranged in this order.
  • a vapor deposition layer 3b may be formed on the surface of the base film 3a on the electromagnetic wave transmission layer 2 side.
  • the electromagnetic wave permeable layer 2, the deposited layer 3b, the substrate film 3a and the dielectric layer 4 may be arranged in this order.
  • the base film 3a is composed of a polymer film. Specific examples thereof include those exemplified in the description of the base material layer 1 .
  • a vacuum deposition method, a sputtering method, or a PECVD method can be used as a method for forming the deposition layer 3b.
  • the vacuum deposition method include a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, and an induction heating vacuum deposition method.
  • Examples of the sputtering method include a reactive sputtering method and a dual magnetron sputtering method.
  • the sputtering method is preferred from the viewpoint of film uniformity, and the vacuum deposition method is preferred from the viewpoint of cost, and can be selected according to the purpose and application.
  • the thickness of the base film 3a is, for example, 9-50 ⁇ m, preferably 12-30 ⁇ m. If the thickness is 9 ⁇ m or more, the strength of the base film 3a tends to be sufficiently secured. It tends to be possible to manufacture
  • vapor deposition layer 3b is preferably 5 nm or more and 100 nm or less. When the thickness of the deposited layer 3b is 5 nm or more, there is a tendency that better barrier properties can be obtained.
  • the thickness is 100 nm or less, the occurrence of cracks tends to be suppressed, and deterioration of the water vapor barrier properties and oxygen barrier properties due to cracks can be suppressed.
  • the cost can be reduced due to the reduction in the amount of material used and the shortening of the film formation time, which is preferable from an economic point of view.
  • the barrier layer 3 may have a laminated structure including a substrate film 3a, a vapor deposition layer 3b, and a barrier coating layer 3c in this order.
  • the barrier coating layer 3c is provided so as to cover the deposition layer 3b.
  • the barrier coating layer 3c is provided to prevent various secondary damages in the post-process and to impart high barrier properties.
  • the thickness of the barrier coating layer 3c is preferably 50-2000 nm, more preferably 100-1000 nm. When the thickness of the barrier coating layer 3c is 50 nm or more, film formation tends to be easier, while when it is 2000 nm or less, cracking or curling tends to be suppressed.
  • the barrier coating layer 3c may contain siloxane bonds.
  • a compound containing a siloxane bond is preferably formed, for example, by reacting a silanol group with a silane compound.
  • silane compounds include compounds represented by the following formula (1).
  • n represents an integer of 0 to 3
  • R 1 and R 2 each independently represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms.
  • Examples of the compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane. etc. Polysilazanes containing nitrogen may also be used.
  • Compounds containing Ti atoms include, for example, compounds represented by the following formula (2).
  • R 1 n (OR 2 ) 4-n Ti (2) [In the formula, n represents an integer of 0 to 3, R 1 and R 2 each independently represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ] Examples of the compound represented by formula (2) include tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, and the like.
  • Compounds containing Al atoms include, for example, compounds represented by the following formula (3).
  • R 1 m (OR 2 ) 3-m Al (3) [In the formula, m represents an integer of 0 to 2, R 1 and R 2 each independently represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ]
  • Examples of the compound represented by formula (3) include trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, and tributoxyaluminum.
  • Compounds containing Zr atoms include, for example, compounds represented by the following formula (4).
  • R 1 n (OR 2 ) 4-n Zr (4) [In the formula, n represents an integer of 0 to 3, R 1 and R 2 each independently represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms. ]
  • Examples of the compound represented by the formula (4) include tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, and tetrabutoxyzirconium.
  • the barrier coating layer 3c can also be formed in the air.
  • a polar compound such as polyvinyl alcohol, polyvinylpyrrolidone, or ethylene vinyl alcohol
  • a chlorine-containing compound such as polyvinylidene chloride, a Si atom-containing compound
  • It can be formed by applying a coating liquid containing a compound containing a Ti atom, a compound containing an Al atom, a compound containing a Zr atom, or the like on the vapor deposition layer 3b, followed by drying and curing.
  • the coating liquid When the barrier coating layer 3c is formed in the atmosphere, the coating liquid may be applied using, for example, a gravure coater, a dip coater, a reverse coater, a wire bar coater, or a die coater. After being applied, the coating liquid is cured.
  • the curing method is not particularly limited, but includes ultraviolet curing, heat curing, and the like. In the case of UV curing, the coating liquid may contain a polymerization initiator and a compound having a double bond. Moreover, heat aging may be performed as needed.
  • particles of inorganic oxides such as magnesium, calcium, zinc, aluminum, silicon, titanium, and zirconium are dehydrated via phosphorus atoms derived from phosphorus compounds.
  • a method of using a reaction product obtained by condensation as a barrier coating layer is exemplified.
  • the functional group e.g., hydroxyl group
  • the site of the phosphorus compound that can react with the inorganic oxide e.g., a halogen atom directly bonded to the phosphorus atom or a bonded oxygen atoms
  • the reaction product is obtained, for example, by applying a coating liquid containing an inorganic oxide and a phosphorus compound to the surface of the vapor deposition layer 3b and heat-treating the formed coating film, whereby the particles of the inorganic oxide are derived from the phosphorus compound. It is obtained by proceeding a reaction that bonds through the phosphorus atom.
  • the lower limit of the heat treatment temperature is 110° C. or higher, preferably 120° C. or higher, more preferably 140° C. or higher, and even more preferably 170° C. or higher. When the heat treatment temperature is low, it becomes difficult to obtain a sufficient reaction rate, which causes a decrease in productivity.
  • a preferable upper limit of the temperature of the heat treatment is 220° C. or less, and preferably 190° C. or less, though it varies depending on the type of substrate.
  • the heat treatment can be performed in air, under a nitrogen atmosphere, under an argon atmosphere, or the like.
  • the coating liquid may further contain a resin as long as it does not aggregate.
  • the resins include acrylic resins and polyester resins.
  • the coating liquid preferably contains a resin having high compatibility with other materials in the coating liquid.
  • the coating liquid may further contain a filler, a leveling agent, an antifoaming agent, an ultraviolet absorber, an antioxidant, a silane coupling agent, a titanium chelating agent, and the like, if necessary.
  • the dielectric layer 4 is a layer for causing interference between incident electromagnetic waves and reflected electromagnetic waves.
  • the thickness and the like of the dielectric layer 4 are set so as to satisfy the conditions represented by the following formula.
  • d ⁇ /(4( ⁇ r ) 1/2 )
  • ⁇ indicates the wavelength (unit: m) of the electromagnetic wave to be suppressed
  • ⁇ r is the dielectric constant of the material forming the dielectric layer 4
  • d is the thickness (unit: m) of the dielectric layer 4. 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 4 is made of a resin composition with a dielectric constant higher than 10.0 at a frequency of 3.7 GHz.
  • a dielectric constant of the dielectric layer 4 is higher than 10.0, as described above, excellent absorption performance (preferably -15 dB, more preferably -20 dB) can be achieved in a specific frequency band.
  • the relative dielectric constant of the dielectric layer 4 at a frequency of 3.7 GHz is preferably higher than 10.0 and 30.0 or less, more preferably higher than 10.0 and 20.0 or less.
  • Dielectric layer 4 having a dielectric constant of 30.0 or less at a frequency of 3.7 GHz tends to be able to form dielectric layer 4 having sufficient strength. For example, blending an excessive amount of a dielectric compound into the dielectric layer 4 in order to increase the dielectric constant of the dielectric layer 4 tends to make the dielectric layer 4 brittle.
  • the thickness of the dielectric layer 4 may be appropriately set depending on the frequency band and relative permittivity. For example, assuming use in the 60 GHz, 76 GHz or 90 GHz band of millimeter wave radar, the thickness of the dielectric layer 4 is preferably 100 to 400 ⁇ m, more preferably 250 to 400 ⁇ m.
  • the thickness of the dielectric layer 4 is preferably 450 to 7000 ⁇ m, more preferably 800 to 6500 ⁇ m.
  • the thickness of the dielectric layer 4 is preferably is 20-80 ⁇ m, more preferably 50-80 ⁇ m.
  • the resin composition that constitutes the dielectric layer 4 contains at least one kind of dielectric compound and a resin component.
  • the dielectric constant of the dielectric layer 4 can be adjusted according to the selection and content of the dielectric compound in the resin composition.
  • the content of the dielectric compound is preferably 10 to 300 parts by volume, 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, based on 100 parts by mass of the resin composition.
  • Dielectric compounds include metal compounds such as barium titanate, titanium oxide and zinc oxide. Preferred embodiments of the dielectric compound are powders (eg, nanoparticles).
  • the relative permittivity of the dielectric compound is preferably higher than that of the resin component.
  • the relative permittivity of the dielectric compound at a frequency of 3.7 GHz is preferably higher than 10 and 5,000 or less, more preferably 100 to 5,000, still more preferably 1,000 to 5,000.
  • resin components include acrylic resins, methacrylic resins, silicone resins, polycarbonates, epoxy resins, cribtal resins, polyvinyl chloride, polyvinyl formal, phenolic resins, urea resins, and polychloroprene resins.
  • the dielectric constant of the resin component at a frequency of 3.7 GHz is preferably 2.5 to 9.5, more preferably 3.5 to 9.5, still more preferably 5.0 to 9.5. .
  • the resin composition preferably has stickiness. Thereby, the dielectric layer 4 can be efficiently attached to the surface of the reflective layer 5 .
  • examples of such materials include silicone adhesives, acrylic adhesives, and urethane adhesives. These materials may be used as the resin component, or an adhesive layer made of these materials may be formed on at least one surface of the dielectric layer 4 .
  • the adhesive strength of the resin composition itself or the adhesive layer to a stainless steel 304 steel plate 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.
  • an adhesive layer 6 may be arranged between the electromagnetic wave transmission layer 2 and the barrier layer 3 as shown in FIG.
  • the thickness of the adhesive layer 6 is, for example, 1-120 ⁇ m, preferably 10-30 ⁇ m. When the thickness of the adhesive layer 6 is 10 ⁇ m or more, sufficient adhesion tends to be ensured.
  • the reflective layer 5 is a layer for reflecting electromagnetic waves incident from the dielectric layer 4 to reach the dielectric layer 4 .
  • the thickness of the reflective layer 5 is, for example, 4-250 ⁇ m, and may be 4-12 ⁇ m or 50-100 ⁇ m.
  • the reflective layer 5 is made of, for example, a conductive material with a sheet resistance of 100 ⁇ / ⁇ or less.
  • a conductive material with a sheet resistance of 100 ⁇ / ⁇ or less.
  • Such materials may be inorganic or organic.
  • Inorganic materials having conductivity include, for example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc aluminum oxide (AZO), carbon nanotubes, graphene, Ag, Al, Au, Pt, Pd, Cu, Co, Cr , In, Ag—Cu, Cu—Au, and Ni nanoparticles, or nanowires.
  • conductive organic materials include polythiophene derivatives, polyacetylene derivatives, polyaniline derivatives, and polypyrrole derivatives.
  • a conductive inorganic material or organic material may be formed on the substrate.
  • Al-deposited PET film comprising a PET film and an aluminum layer deposited on its surface (Al-deposited PET film) as a reflective layer.
  • the electromagnetic wave suppressor 10 is manufactured through the following steps, for example. First, a laminate of the substrate layer 1 and the electromagnetic wave permeable layer 2 is produced by roll-to-roll. Moreover, the barrier layer 3 or the laminated body containing this is produced by roll to roll. Furthermore, a laminate including the dielectric layer 4 is produced by roll-to-roll. After laminating these laminates on the reflective layer 5, the electromagnetic wave suppressor 10 is obtained by cutting into a predetermined size. A roll-shaped laminate including the dielectric layer 4 is produced through (A) the step of preparing the resin composition and (B) the step of forming the dielectric layer 4 from the resin composition by roll-to-roll. manufactured.
  • the electromagnetic wave suppressor 10 can be manufactured by roll-to-roll because the thickness of the dielectric layer 4 is sufficiently thin.
  • the frequency band to be applied is low (for example, less than 28 GHz)
  • the dielectric layer 4 can be formed, for example, by extrusion. 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 electromagnetic wave suppressor 10 by providing the barrier layer 3 between the electromagnetic wave transmitting layer 2 and the dielectric layer 4, the sheet resistance value of the electromagnetic wave transmitting layer 2 is reduced due to the substance contained in the dielectric layer 4. Fluctuation can be suppressed. Therefore, the electromagnetic wave suppressor 10 can maintain sufficient return loss over a long period of time.
  • the electromagnetic wave suppressor 20 shown in FIG. 5 includes a substrate layer 1, an electromagnetic wave transmitting layer 2, a single-layer barrier layer 13, a dielectric layer 4, and a reflective layer 5 in this order.
  • the barrier layer 13 is composed of, for example, a polymer film. Specific examples thereof include those exemplified in the description of the base material layer 1 .
  • polymer films it is preferable to use, as the barrier layer 13, those having excellent gas barrier properties (for example, PET film and polypropylene film).
  • the thickness of the polymer film is, for example, 5-50 ⁇ m, and may be 12-30 ⁇ m.
  • the barrier layer 13 may be composed of an adhesive.
  • the thickness of the adhesive layer is, for example, 10-50 ⁇ m, and may be 100-500 ⁇ m. From the viewpoint of maintaining the sheet resistance value of the electromagnetic wave permeable layer 2, it is preferable to use a silicone adhesive, an acrylic adhesive, or a urethane adhesive as the adhesive.
  • the single-layer barrier layer 13 does not necessarily have to have high gas barrier properties.
  • the water vapor permeability of the barrier layer 13 may be, for example, 4.0 ⁇ 10 2 g/m 2 /day or less.
  • the electromagnetic wave suppressor may have an adhesive layer.
  • the electromagnetic wave suppressor 30 shown in FIG. 6 includes a base layer 1, an electromagnetic wave transmission layer 2, an adhesive layer 6, a base film 3a, a vapor deposition layer 3b, a barrier coating layer 3c, an adhesive layer 7, A dielectric layer 4, an adhesive layer 8 and a reflective layer 5 are provided in this order.
  • the adhesive layer 7 bonds the barrier coating layer 3c and the dielectric layer 4 together.
  • the adhesive layer 8 bonds the dielectric layer 4 and the reflective layer 5 together.
  • Examples of adhesives constituting the adhesive layer include acrylic adhesives, silicone adhesives, polyolefin adhesives, urethane adhesives, polyvinyl ether adhesives, and the like.
  • the thickness of the adhesive layer is, for example, 0.5-50 ⁇ m, and may be 1-20 ⁇ m or 2-6 ⁇ m.
  • the adhesive constituting the adhesive layer may have oxygen barrier properties.
  • the oxygen permeability of the adhesive layer is, for example, 1000 cc/(m 2 ⁇ day ⁇ atm) or less in the thickness direction at a thickness of 5 ⁇ m.
  • the oxygen permeability is preferably 500 cc/(m 2 ⁇ day ⁇ atm) or less, more preferably 100 cc/(m 2 ⁇ day ⁇ atm) or less, and 50 cc/(m 2 ⁇ day ⁇ atm) or less. is more preferably 10 cc/(m 2 ⁇ day ⁇ atm) or less.
  • the adhesive layer has an oxygen barrier property, even if the barrier layer 3 has a defect, it can be compensated for.
  • the lower limit of oxygen permeability is not particularly limited, it is, for example, 0.1 cc/(m 2 ⁇ day ⁇ atm).
  • the film-like or sheet-like electromagnetic wave suppressor 10 and its modification were exemplified, but the shape of the electromagnetic wave suppressor is not limited to this.
  • the reflecting layer 5 is used as a structure (reflector) for reflecting electromagnetic waves, but the structure of the reflector may not be layered as long as it can reflect electromagnetic waves.
  • the electromagnetic wave suppressor may be sandwiched between films having gas barrier properties, or the electromagnetic wave suppressor may be housed and sealed in a packaging bag having gas barrier properties.
  • This disclosure relates to: [1] an electromagnetic wave transmission layer having electrical conductivity; a barrier layer; a dielectric layer containing at least one dielectric compound and a resin component; a reflector; in that order.
  • the electromagnetic wave transmission layer contains a conductive polymer, The electromagnetic wave suppressor according to [1], wherein the dielectric compound is at least one of titanium oxide and barium titanate.
  • the barrier layer includes a substrate film and an oxide deposition layer provided on one surface of the substrate film.
  • the barrier layer further includes a barrier coating layer provided to cover the vapor deposition layer.
  • the barrier layer includes at least one of a polymer film and an adhesive layer.
  • the barrier layer has a water vapor permeability of 4.0 ⁇ 10 2 g/m 2 /day or less.
  • the electromagnetic wave permeable layer has a sheet resistance change rate C1 calculated by the following formula of 60% or less.
  • Sheet resistance change rate C 1 [%] (R 1 ⁇ R 0 )/R 0 ⁇ 100
  • R 1 represents the sheet resistance value of the electromagnetic wave permeable layer after exposing the electromagnetic wave suppressor to an environment with a temperature of 85° C. and a relative humidity of 85% for 24 hours
  • R 0 represents the The sheet resistance value of the electromagnetic wave permeable layer before exposing the electromagnetic wave suppressor is shown.
  • [8] The electromagnetic wave suppressor according to any one of [1] to [7], wherein the electromagnetic wave permeable layer has a sheet resistance change rate C2 calculated by the following formula of 9% or less.
  • Sheet resistance change rate C 2 [%] (R 2 ⁇ R 0 )/R 0 ⁇ 100
  • R 2 represents the sheet resistance value of the electromagnetic wave permeable layer after exposing the electromagnetic wave suppressor to an environment of 85° C. and 85% relative humidity for 500 hours
  • R 0 represents the The sheet resistance value of the electromagnetic wave permeable layer before exposing the electromagnetic wave suppressor is shown.
  • Example 1 An electromagnetic wave transmitting layer (thickness: 440 nm) of (B1) PEDOT/PSS was formed by coating on the surface of the biaxially stretched PET film.
  • a barrier layer was prepared by forming (C2) a barrier coating layer (thickness: 400 nm) on the surface (alumina-deposited surface) of (C1) an alumina-deposited PET film.
  • C4 a silicone adhesive, (B1) the PEDOT/PSS electromagnetic wave transmission layer and (C1) the surface (PET surface) of alumina-deposited PET were laminated with a laminator.
  • the thickness of the silicone adhesive layer was 10 ⁇ m.
  • a composition having the following composition was prepared to form a dielectric layer.
  • Example 2 This experiment was carried out in the same manner as in Example 1, except that (C3) a biaxially stretched PET film (thickness: 12 ⁇ m) was used as the barrier layer instead of forming the barrier layer with (C1) and (C2). An electromagnetic wave suppressor (thickness: 429 ⁇ m) according to the example was produced (see FIG. 4).
  • Example 3 Instead of forming a barrier layer with (C1) and (C2), a layer (C4) of silicone pressure-sensitive adhesive (thickness: 10 ⁇ m) was formed as a barrier layer on the surface of (B1) PEDOT/PSS electromagnetic wave transmission layer. Thereafter, an electromagnetic wave suppressor (thickness: 427 ⁇ m) according to this example was produced in the same manner as in Example 1, except that the barrier layer and the dielectric layer were laminated by a laminator (see FIG. 5).
  • Example 4 An electromagnetic wave suppressor (thickness: 429 ⁇ m) according to this example was produced in the same manner as in Example 1, except that the direction of the barrier layer was reversed.
  • the layer structure of this electromagnetic wave suppressor is the same as that of the electromagnetic wave suppressor shown in FIG. 3(b) except that an adhesive layer is formed between the electromagnetic wave transmission layer and the barrier coating layer.
  • Example 5 (Example 5) (B1) Instead of forming an electromagnetic wave-transmitting layer of a mixture (PEDOT/PSS) of polyethylenedioxythiophene (PEDOT) and polystyrene sulfonic acid (PPS), (B2) forming an electromagnetic wave-transmitting layer of a polyaniline derivative.
  • An electromagnetic wave suppressor (thickness: 429 ⁇ m) according to this example was produced in the same manner as in Example 1 (see FIG. 3(a)).
  • Example 6 (Example 6)
  • a layer of (B3) indium tin oxide (ITO) is formed by a sputtering method.
  • An electromagnetic wave suppressor (thickness: 429 ⁇ m) according to this example was produced in the same manner as in Example 1, except that it was formed (see FIG. 3A).
  • Example 7 An electromagnetic wave transmitting layer (thickness: 440 nm) of (B1) PEDOT/PSS was formed by coating on the surface of the biaxially stretched PET film.
  • a barrier layer was prepared by forming (C2) a barrier coating layer (thickness: 400 nm) on the surface (alumina-deposited surface) of (C1) an alumina-deposited PET film.
  • C4 a silicone adhesive, (B1) the PEDOT/PSS electromagnetic wave transmission layer and (C1) the surface (PET surface) of alumina-deposited PET were laminated with a laminator.
  • the thickness of the silicone adhesive layer was 10 ⁇ m.
  • a composition having the following composition was mixed, melted, kneaded, extruded, cooled, and cut to prepare a masterbatch.
  • a dielectric layer (thickness: 325 ⁇ m) is formed through a process of rolling a masterbatch containing this composition with a calendar molding machine. bottom.
  • a composition having the following composition was prepared.
  • Example 8 A composition having the following composition was prepared to form a dielectric layer.
  • An electromagnetic wave suppressor (thickness: 429 ⁇ m) according to this example was produced in the same manner as in Example 1, except that a dielectric layer (thickness: 345 ⁇ m) was formed through a drying step (FIG. 3). (a)).
  • Example 9 A composition having the following composition was prepared to form a dielectric layer.
  • An electromagnetic wave suppressor (thickness: 464 ⁇ m) according to this example was produced in the same manner as in Example 1, except that a dielectric layer (thickness: 380 ⁇ m) was formed through a drying step (see FIG. 3 ( a) see).
  • Example 10 A composition having the following composition was prepared to form a dielectric layer.
  • D1 Zinc oxide powder: 69 parts by mass
  • D2 Acrylic resin: 31 parts by mass
  • An electromagnetic wave suppressor (thickness: 470 ⁇ m) according to this example was produced in the same manner as in Example 1, except that a dielectric layer (thickness: 350 ⁇ m) was formed through a drying step (see FIG. 3 ( a) see).
  • Example 11 An electromagnetic wave suppressor (thickness: 830 ⁇ m) according to this example was produced in the same manner as in Example 7, except that a dielectric layer (thickness: 710 ⁇ m) was formed (see FIG. 6).
  • Comparative example 1 Electromagnetic wave suppression according to Comparative Example 1 in the same manner as in Example 1, except that no barrier layer is arranged between the electromagnetic wave permeable layer and the dielectric layer, and the electromagnetic wave permeable layer is in direct contact with the dielectric layer. A body (thickness: 407 ⁇ m) was produced.
  • Comparative example 2 Electromagnetic wave suppression according to Comparative Example 2 in the same manner as in Example 5, except that no barrier layer was arranged between the electromagnetic wave permeable layer and the dielectric layer, and the electromagnetic wave permeable layer was in direct contact with the dielectric layer. A body (thickness: 407 ⁇ m) was produced.
  • Comparative Example 3 Electromagnetic wave suppression according to Comparative Example 3 in the same manner as in Example 6, except that no barrier layer was arranged between the electromagnetic wave permeable layer and the dielectric layer, and the electromagnetic wave permeable layer was in direct contact with the dielectric layer. A body (thickness: 407 ⁇ m) was produced.
  • Comparative Example 4 Electromagnetic wave suppression according to Comparative Example 4 in the same manner as in Example 8, except that no barrier layer was arranged between the electromagnetic wave permeable layer and the dielectric layer, and the electromagnetic wave permeable layer was in direct contact with the dielectric layer. A body (thickness: 407 ⁇ m) was produced.
  • Comparative Example 5 Electromagnetic wave suppression according to Comparative Example 5 in the same manner as in Example 9, except that no barrier layer was arranged between the electromagnetic wave permeable layer and the dielectric layer, and the electromagnetic wave permeable layer was in direct contact with the dielectric layer. A body (thickness: 407 ⁇ m) was produced.
  • Comparative Example 6 Electromagnetic wave suppression according to Comparative Example 6 in the same manner as in Example 10, except that no barrier layer was arranged between the electromagnetic wave permeable layer and the dielectric layer, and the electromagnetic wave permeable layer was in direct contact with the dielectric layer. A body (thickness: 407 ⁇ m) was produced.
  • the electromagnetic wave suppressors according to the examples and the comparative examples and the layers constituting the same were evaluated as follows. Results are shown in Tables 5-8.
  • OTR oxygen transmission rate of Barrier Layer
  • the oxygen transmission rate (OTR) of the barrier layer was measured using an oxygen transmission rate measuring device (manufactured by MOCON, trade name: OX-TRAN) at a temperature of 30° C. and a relative humidity of 70%. It was measured in accordance with JIS K-7126-2 under conditions.
  • the unit of oxygen permeability is [cc/(m 2 ⁇ day ⁇ atm)].
  • the water vapor transmission rate (WVTR) of the barrier layer was measured using a water vapor transmission rate measuring device (manufactured by MOCON, trade name: PERMATRAN 3/31) at a temperature of 40 ° C. and a relative humidity of 90%. It was measured in accordance with JIS K-7129 under conditions.
  • the unit of water vapor permeability is [g/m 2 /day].
  • the sheet resistance change rate was negative in some cases.
  • the main reason for this is presumed to be the additives contained in the mixture (B). That is, in addition to PEDOT/PSS, the mixture of (B) is added with an anti-deterioration agent and the like. drop) vector and present. It is presumed that in some examples, the action of the anti-deterioration agent became dominant, the vector of sheet resistance decrease became relatively large, and the rate of change became negative. According to studies by the present inventors, the reliability of the electromagnetic wave suppressor can be ensured unless the sheet resistance change rate is less than ⁇ 40% (absolute value is greater than 40%).
  • a return loss of the electromagnetic wave suppressor after being exposed to an environment with a temperature of 85° C. and a relative humidity of 85% for 24 hours was measured using the following equipment.
  • the electromagnetic wave suppressors according to Examples 1 and 4 were also measured for return loss after being exposed to an environment with a temperature of 85° C. and a relative humidity of 85% for 500 hours.
  • an electromagnetic wave suppressor capable of maintaining sufficient return loss over a long period of time.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)

Abstract

Un suppresseur d'ondes électromagnétiques selon la présente divulgation est équipé, dans cet ordre, d'une couche de transmission d'onde électromagnétique conductrice, d'une couche barrière, d'une couche diélectrique qui contient un ou plusieurs types de composé diélectrique et de composant de résine et d'un corps réfléchissant. Un composé métallique de celui-ci est, par exemple, de l'oxyde de titane et/ou du titanate de baryum. La couche barrière de celle-ci contient, par exemple, un film de substrat et une couche de dépôt d'oxyde disposée sur une surface du film de substrat, et peut également contenir une couche de revêtement de barrière disposée de façon à recouvrir la couche de dépôt.
PCT/JP2022/034072 2021-09-16 2022-09-12 Suppresseur d'ondes électromagnétiques WO2023042799A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018230026A1 (fr) * 2017-06-13 2018-12-20 日東電工株式会社 Absorbeur d'ondes électromagnétiques et article moulé ayant un absorbeur d'ondes électromagnétiques
JP2020168775A (ja) * 2019-04-02 2020-10-15 凸版印刷株式会社 透明導電性ガスバリア積層体及びその製造方法、並びにデバイス

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018230026A1 (fr) * 2017-06-13 2018-12-20 日東電工株式会社 Absorbeur d'ondes électromagnétiques et article moulé ayant un absorbeur d'ondes électromagnétiques
JP2020168775A (ja) * 2019-04-02 2020-10-15 凸版印刷株式会社 透明導電性ガスバリア積層体及びその製造方法、並びにデバイス

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