WO2022004670A1 - Élément de transmission d'ondes électromagnétiques à éclat métallique, et élément décoratif - Google Patents

Élément de transmission d'ondes électromagnétiques à éclat métallique, et élément décoratif Download PDF

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Publication number
WO2022004670A1
WO2022004670A1 PCT/JP2021/024389 JP2021024389W WO2022004670A1 WO 2022004670 A1 WO2022004670 A1 WO 2022004670A1 JP 2021024389 W JP2021024389 W JP 2021024389W WO 2022004670 A1 WO2022004670 A1 WO 2022004670A1
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Prior art keywords
metallic luster
electromagnetic wave
layer
substrate
transmitting
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PCT/JP2021/024389
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English (en)
Japanese (ja)
Inventor
孝洋 中井
遼太郎 横井
秀行 米澤
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日東電工株式会社
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Publication of WO2022004670A1 publication Critical patent/WO2022004670A1/fr

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Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon

Definitions

  • the present invention relates to an electromagnetic wave transmitting metallic luster member and a decorative member.
  • a member having electromagnetic wave transmission and metallic luster has both a high-class appearance derived from the metallic luster and electromagnetic wave transmission, and is therefore suitably used for an apparatus for transmitting and receiving electromagnetic waves.
  • metal is used for the metallic luster member, it is practically impossible or disturbed to transmit and receive electromagnetic waves. Therefore, an electromagnetic wave-transmitting metallic luster member having both metallic luster and electromagnetic wave transmission is required in order not to interfere with the transmission and reception of electromagnetic waves and not to impair the design.
  • Such an electromagnetic wave transmissive metal gloss member is used as a device for transmitting and receiving electromagnetic waves, and is used for various devices that require communication, for example, electronic devices such as automobile door handles provided with smart keys, in-vehicle communication devices, mobile phones, and personal computers. It is expected to be applied to devices and the like. Furthermore, in recent years, with the development of IoT technology, it is expected to be applied in a wide range of fields such as home appliances such as refrigerators and household appliances, which have not been conventionally used for communication and the like.
  • Patent Document 1 discloses a resin product containing a metal film made of chromium (Cr) or indium (In).
  • This resin product has a resin base material, an inorganic base film containing an inorganic compound formed on the resin base material, and a brilliant and discontinuous film formed on the inorganic base film by a physical vapor deposition method. It contains a metal film made of chromium (Cr) or indium (In) of the structure.
  • Patent Document 1 As the inorganic base film, in Patent Document 1, (a) a thin film of a metal compound, for example, a titanium compound such as titanium oxide (TIO, TiO 2 , Ti 3 O 5, etc.); silicon oxide (SiO, SiO 2, etc.), nitrided.
  • a metal compound for example, a titanium compound such as titanium oxide (TIO, TiO 2 , Ti 3 O 5, etc.); silicon oxide (SiO, SiO 2, etc.), nitrided.
  • Silicon compounds such as silicon (Si 3 N 4 etc.); Aluminum compounds such as aluminum oxide (Al 2 O 3 ); Iron compounds such as iron oxide (Fe 2 O 3 ); Selene compounds such as selenium oxide (CeO); Oxidation A zircon compound such as zircon (ZrO); a zinc compound such as zinc sulfide (ZnS), etc., (b) a coating film of an inorganic paint, for example, silicon, amorphous TIO z, etc. (other, the above-exemplified metal compound) as a main component. A coating film made of an inorganic paint is used.
  • the metallic luster member in the prior art generally has a metallic luster layer formed on a smooth surface. Further, as a conventional metallic luster member, a member having a metallic luster with a high degree of luster has been studied from the viewpoint of designability. In addition, the needs for designs of metallic luster members are diversifying, and when a metallic luster member is attached to an adherend member to form a decorative member, the surface shape and color of the adherent member can be visually recognized through the metallic luster member. A metallic luster member having transparency is also desired.
  • the present invention has been made in view of the above, and provides an electromagnetic wave-transmitting metallic luster member having electromagnetic wave permeability and having metallic luster and transparency with suppressed coloring, and a decorative member. The purpose.
  • the present invention is as follows.
  • a substrate and a metallic luster layer formed on the substrate are provided.
  • the metallic luster layer contains a plurality of portions that are discontinuous with each other at least in part.
  • the metallic luster layer contains aluminum or an aluminum alloy, and the metallic luster layer contains aluminum or an aluminum alloy.
  • An electromagnetic wave transmissive metallic luster member having a CIE-XYZ color system SCI system with a reflected Y value of 10 to 25% and a transmitted Y value of 30 to 65%.
  • the electromagnetic wave-transmitting metallic luster member according to [1] further comprising an inorganic oxide-containing layer between the substrate and the metallic luster layer.
  • the electromagnetic wave-transmitting metallic luster member according to any one of [2] to [5], wherein the thickness of the inorganic oxide-containing layer is 1 nm to 1000 nm.
  • Item 2 Electromagnetic wave transmission according to any one of [1] to [6], wherein a resin layer is provided on the surface of the metallic luster layer opposite to the surface on the substrate side, and the haze value of the resin layer is less than 20%.
  • Metallic luster member [8] The electromagnetic wave-transmitting metallic luster member according to any one of [1] to [7], wherein the metallic luster layer has a thickness of 3 nm to 10 nm.
  • Metallic luster member is any of a substrate film, a resin molded substrate, a glass substrate, or an article to which metallic luster should be imparted.
  • Metallic luster member is any of a substrate film, a resin molded substrate, a glass substrate, or an article to which metallic luster should be imparted.
  • Metallic luster member is any of a substrate film, a resin molded substrate, a glass substrate, or an article to which metallic luster should be imparted.
  • an electromagnetic wave-transmitting metallic luster member having excellent electromagnetic wave transparency and having both metallic luster and transparency with suppressed coloring, and a decorative member.
  • FIG. 1 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member according to an embodiment of the present invention.
  • FIG. 2 is a diagram showing an electron micrograph (SEM image) of the surface of an electromagnetic wave transmitting metallic luster member according to an embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view of a decorative member according to an embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member according to an embodiment of the present invention.
  • FIG. 5 is a diagram for explaining a method for measuring the thickness of the metallic luster layer of the electromagnetic wave transmitting metallic luster member according to the embodiment of the present invention.
  • FIG. 6 is a diagram showing an electron micrograph (TEM image) of a cross section of an electromagnetic wave transmitting metallic luster member according to an embodiment of the present invention.
  • FIG. 7 is a diagram showing the relationship between the a * value and the b * value of the transmitted light of the electromagnetic wave transmitting metallic luster members of Examples and Comparative Examples.
  • FIG. 8 is a diagram showing the relationship between the transmitted Y value and the a * value of the transmitted light of the electromagnetic wave transmitting metallic luster members of Examples and Comparative Examples.
  • FIG. 9 is a diagram showing the relationship between the transmitted Y value and the b * value of the transmitted light of the electromagnetic wave transmitting metallic luster members of Examples and Comparative Examples.
  • FIG. 10 is a diagram showing the relationship between the a * value and the b * value of the reflected light of the electromagnetic wave transmitting metallic luster members of Examples and Comparative Examples.
  • FIG. 11 is a diagram showing the relationship between the reflected Y value and the a * value of the reflected light of the electromagnetic wave transmitting metallic luster members of Examples and Comparative Examples.
  • FIG. 12 is a diagram showing the relationship between the reflected Y value and the b * value of the reflected light of the electromagnetic wave transmitting metallic luster members of Examples and Comparative Examples.
  • the electromagnetic wave-transmitting metallic luster member according to the embodiment of the present invention includes a substrate and a metallic luster layer formed on the substrate.
  • the metallic luster layer contains a plurality of portions that are discontinuous with each other at least in part.
  • the metallic luster layer contains aluminum or an aluminum alloy, and the metallic luster layer contains aluminum or an aluminum alloy.
  • the reflection Y value of the SCI method of the CIE-XYZ color system is 10 to 25%, and the transmission Y value is 30 to 65%.
  • FIG. 1 shows a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member 1 according to an embodiment of the present invention.
  • FIG. 2 shows an example of an electron micrograph (SEM image) of the surface of the electromagnetic wave transmitting metallic luster member 1 according to the embodiment of the present invention.
  • the electromagnetic wave transmitting metallic luster member 1 includes a substrate 10 and a metallic luster layer 12 formed on the substrate 10.
  • the electromagnetic wave transmitting metallic luster member 1 may further include an inorganic oxide-containing layer between the substrate 10 and the metallic luster layer 12, and the inorganic oxide-containing layer 11 may be an indium oxide-containing layer.
  • the metallic luster layer 12 is preferably formed on the indium oxide-containing layer.
  • the inorganic oxide-containing layer 11 is provided on the surface of the substrate 10.
  • the inorganic oxide-containing layer 11 may be provided directly on the surface of the substrate 10, or may be indirectly provided via a protective layer or the like provided on the surface of the substrate 10. It is preferable that the inorganic oxide-containing layer 11 is provided on the surface of the substrate 10 in a continuous state, in other words, without any gaps.
  • the smoothness and corrosion resistance of the electromagnetic wave-transmitting metallic luster member 1 can be improved, and the inorganic oxide-containing layer 11 is formed without variation in the plane. It also becomes easy to film.
  • the metallic luster layer 12 is laminated on the inorganic oxide-containing layer 11.
  • the metallic luster layer 12 includes a plurality of portions 12a. By being laminated on the inorganic oxide-containing layer 11, these portions 12a are separated from each other by a gap 12b at least in a discontinuous state, that is, in at least a part. Since they are separated by the gap 12b, the sheet resistance of these portions 12a becomes large and the interaction with the radio wave decreases, so that the radio wave can be transmitted.
  • Each of these portions 12a is an aggregate of sputtered particles formed by vapor deposition, sputtering, or the like of a metal. When the sputtered particles form a thin film on a substrate such as the substrate 10, the surface diffusivity of the particles on the substrate affects the shape of the thin film.
  • discontinuous state means a state in which they are separated from each other by a gap 12b, and as a result, they are electrically isolated from each other. By being electrically insulated, the sheet resistance becomes large, and the desired electromagnetic wave transmission can be obtained.
  • the discontinuous form is not particularly limited, and includes, for example, islands, cracks, and the like.
  • the "island-like” means particles that are aggregates of spattered particles, as shown in an electron micrograph (SEM image) of the surface of the metal gloss layer of the electromagnetic wave transmitting metal gloss member in FIG.
  • SEM image electron micrograph
  • the crack structure is a structure in which a metal thin film is divided by cracks.
  • the metallic luster layer 12 having a crack structure can be formed, for example, by providing a metal thin film layer on an inorganic oxide-containing layer formed on a substrate and bending and stretching the metal thin film layer to cause cracks in the metal thin film layer.
  • the metallic luster layer 12 having a crack structure is easily formed by providing a brittle layer made of a material having poor elasticity, that is, easily forming cracks by stretching, between the inorganic oxide-containing layer and the metal thin film layer. be able to.
  • the mode in which the metallic luster layer 12 is discontinuous is not particularly limited, but from the viewpoint of productivity, it is preferably "island-shaped".
  • the electromagnetic wave transmissive metallic luster member according to the embodiment of the present invention has a reflection Y value of 10 to 25% and a transmission Y value of 30 to 65% in the SCI method of the CIE-XYZ color system.
  • the reflected Y value of the electromagnetic wave transmissive metal gloss member 1 is based on JIS Z 8722 using a spectrophotometer and the transmitted Y value is based on an integrating sphere type spectrotransmittance measuring device. Can be measured. Specifically, it can be measured by the method described in the column of Examples. By setting the reflected Y value and the transmitted Y value in the electromagnetic wave transmissive metallic luster member within a specific range, a metallic luster having excellent electromagnetic wave transmission and suppressed coloring can be obtained, and good transparency can be obtained. I found that it was possible.
  • the surface shape and color of the adherend member can be visually recognized even through the electromagnetic wave-transmitting metallic luster member. ..
  • the reflected Y value and the transmitted Y value of the electromagnetic wave transmitting metallic luster member 1 can be adjusted by adjusting the film thickness of the metal layer.
  • the reflection Y value (visual reflectance) is measured by incident light on the surface of the electromagnetic wave transmissive metal gloss member on the metal gloss layer side (the surface opposite to the side having the substrate of the metal gloss layer).
  • the average reflectance loaded with the visibility in the wavelength range and the light intensity of the light source.
  • the reflection Y value is preferably 10% or more from the viewpoint of obtaining an appearance showing a metallic luster with suppressed coloring. Further, it is preferably 25% or less from the viewpoint of visibility of the design due to transmission.
  • the electromagnetic wave transmissive metallic luster member 1 has a CIE-L * a * b * color system of reflected light on the adherend member side. It is preferable that both the a * value and the b * value are close to 0.
  • the CIE-L * a * b * color system is the color system recommended by the CIE (International Commission on Illumination) in 1976.
  • L * indicates the brightness, and the larger the value from 0 to 100, the brighter the color system.
  • the chromaticity is represented by a * and b * , and a * is an index indicating the degree of red to green in the color tone, and when the value of a * is large in the positive direction, the color tone becomes red.
  • b * is an index indicating the degree of yellow to blue of the color tone, and when the value of b * is large in the positive direction, the color tone becomes yellow.
  • both a * and b * are 0, the color is achromatic.
  • the transmitted Y value (luminous efficiency) is measured by incident light on the surface of the electromagnetic wave transmitting metal gloss member on the substrate side (the surface opposite to the side of the substrate having the metallic gloss layer). Luminous efficiency in the wavelength range and average transmittance loaded with the light intensity of the light source.
  • the transmission Y value is preferably 30% or more from the viewpoint of visibility of the design due to transmission. Further, it is preferably 65% or less from the viewpoint of metallic luster appearance.
  • the transmission characteristics (transmitt Y value, a * value and b * value) of the electromagnetic wave transmissive metal gloss member according to the embodiment of the present invention are such that the electromagnetic wave transmissive metal gloss member is made of water-rimmed glass S200200 (Matsunami Glass Industry Co., Ltd.).
  • the a * value and the b * value of the transmitted light on the adherend member side are both close to 0 in the CIE-L * a * b * color system. preferable.
  • the electromagnetic wave transmittance of the electromagnetic wave transmitting metallic luster member 1 has a correlation with the sheet resistance.
  • the sheet resistance of the electromagnetic wave transmitting metallic luster member is preferably 100 ⁇ / ⁇ or more.
  • the electromagnetic wave transmission property is about 10 [ ⁇ dB] or less at a wavelength of 5 GHz.
  • the sheet resistance is more preferably 200 ⁇ / ⁇ or more, further preferably 600 ⁇ / ⁇ or more, still more preferably 1000 ⁇ / ⁇ or more.
  • the amount of radio wave transmission attenuation in the microwave band (5 GHz) is preferably less than 10 [ ⁇ dB], more preferably less than 5 [ ⁇ dB], and even more preferably less than 2 [ ⁇ dB]. .
  • the amount of radio wave transmission attenuation in the microwave band (5 GHz) is 10 [ ⁇ dB] or more, there is a problem that 90% or more of the radio waves are blocked.
  • the amount of radio wave transmission attenuation and sheet resistance of the electromagnetic wave transmissive metallic luster member 1 are affected by the material and thickness of the inorganic oxide-containing layer 11 and the metallic luster layer 12.
  • examples of the substrate 10 include resin, glass, ceramics, and the like from the viewpoint of electromagnetic wave transmission.
  • the substrate 10 may be a substrate film, a resin molded substrate, a glass substrate, or an article to which metallic luster should be imparted.
  • examples of the base film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, polycarbonate (PC), cycloolefin polymer (COP), and polystyrene.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PEN polybutylene terephthalate
  • polyamide polyvinyl chloride
  • PC polycarbonate
  • COP cycloolefin polymer
  • polystyrene Polypropylene
  • PP Polypropylene
  • the material can withstand high temperatures such as vapor deposition and spatter. Therefore, among the above materials, for example, polyethylene terephthalate and polyethylene na. Phthalates, acrylics, polycarbonates, cycloolefin polymers, ABS, polypropylene and polyurethane are preferred. Of these, polyethylene terephthalate, cycloolefin polymer, polycarbonate, and acrylic are preferable because they have a good balance between heat resistance and cost.
  • the base film may be a single-layer film or a laminated film. From the viewpoint of ease of processing and the like, the thickness is preferably, for example, about 6 ⁇ m to 250 ⁇ m. Plasma treatment or easy-adhesion treatment may be performed in order to strengthen the adhesive force with the inorganic oxide-containing layer 11 and the metallic luster layer 12.
  • the metallic luster layer 12 may be provided on at least a part of the base film, may be provided on only one side of the base film, or may be provided on both sides.
  • the base film may be formed with a smooth or antiglare hard coat layer, if necessary.
  • the hard coat layer By providing the hard coat layer, the scratch resistance of the metal thin film can be improved.
  • the smooth hard coat layer By providing the smooth hard coat layer, the metallic luster is increased, and conversely, the anti-glare hard coat layer can prevent glare.
  • the hard coat layer can be formed by applying a solution containing a curable resin.
  • the curable resin examples include thermosetting resins, ultraviolet curable resins, and electron beam curable resins.
  • the curable resin examples include various resins such as polyester-based, acrylic-based, urethane-based, acrylic-urethane-based, amide-based, silicone-based, silicate-based, epoxy-based, melamine-based, oxetane-based, and acrylic urethane-based resins.
  • these curable resins one kind or two or more kinds can be appropriately selected and used.
  • acrylic resins, acrylic urethane resins, and epoxy resins are preferable because they have high hardness, can be cured by ultraviolet rays, and are excellent in productivity.
  • the base film is only an example of an object (base 10) on which the metallic luster layer 12 can be formed.
  • the substrate 10 includes a resin molded substrate, a glass substrate, and the article itself to which metallic luster should be imparted, in addition to the substrate film as described above.
  • the resin molded base material and the articles to be imparted with metallic luster include structural parts for vehicles, vehicle-mounted products, housings for electronic devices, housings for home appliances, structural parts, mechanical parts, and various automobiles. Examples include parts for household appliances such as parts for electronic equipment, furniture, kitchen goods, medical equipment, parts for building materials, other structural parts and exterior parts.
  • the metallic luster layer 12 can be formed on all of these substrates, and may be formed on a part of the surface of the substrate or on the entire surface of the substrate.
  • the substrate 10 to which the metallic luster layer 12 is to be provided preferably satisfies the same materials and conditions as the above-mentioned substrate film.
  • the electromagnetic wave-transmitting metallic luster member 1 may further include an inorganic oxide-containing layer 11 between the substrate 10 and the metallic luster layer 12.
  • the inorganic oxide-containing layer 11 may be provided directly on the surface of the substrate 10, or may be indirectly provided via a protective film or the like provided on the surface of the substrate 10.
  • the inorganic oxide-containing layer 11 is preferably provided continuously on the surface of the substrate 10 to be imparted metallic luster, in other words, without gaps.
  • the smoothness and corrosion resistance of the inorganic oxide-containing layer 11, the metallic luster layer 12, and the electromagnetic wave-permeable metallic luster member 1 can be improved, and the inorganic oxide-containing layer 11 can be provided. It also facilitates film formation without in-plane variation.
  • the inorganic oxide-containing layer 11 is further provided between the substrate 10 and the metallic luster layer 12, that is, the inorganic oxide-containing layer 11 is formed on the substrate 10, and the metallic luster layer 12 is formed on the inorganic oxide-containing layer 11.
  • the inorganic oxide-containing layer 11 is formed on the substrate 10
  • the metallic luster layer 12 is formed on the inorganic oxide-containing layer 11. Is preferable because it facilitates the formation of the metallic luster layer 12 in a discontinuous state.
  • the details of the mechanism are not always clear, but when sputtered particles due to metal deposition or sputtering form a thin film on the substrate, the surface diffusivity of the particles on the substrate affects the shape of the thin film, and the substrate.
  • the inorganic oxide-containing layer 11 is preferably an indium oxide-containing layer.
  • indium oxide-containing layer indium oxide (In 2 O 3 ) itself can be used, or a metal-containing substance such as indium tin oxide (ITO) or indium zinc oxide (IZO) is used. You can also do it.
  • the indium oxide-containing layer preferably contains either indium oxide (In 2 O 3 ), indium tin oxide (ITO), or indium zinc oxide (IZO).
  • ITO and IZO containing a second metal are more preferable because they have high discharge stability in the sputtering process.
  • a continuous film can be formed along the surface of the substrate, and in this case, the metallic luster laminated on the inorganic oxide-containing layer. It is preferable because the layer tends to have an island-like discontinuous structure, for example. Further, as will be described later, in this case, not only chromium (Cr) or indium (In) but also aluminum or aluminum or aluminum or indium (In), which is usually difficult to have a discontinuous structure, is difficult to be applied to the metallic luster layer. It becomes easier to include aluminum alloy.
  • the thickness of the inorganic oxide-containing layer 11 is usually preferably 1000 nm or less, more preferably 50 nm or less, still more preferably 20 nm or less, from the viewpoint of sheet resistance, electromagnetic wave transmission, and productivity.
  • it is preferably 1 nm or more, and in order to ensure the discontinuous state, it is more preferably 3 nm or more. The above is more preferable.
  • the metallic luster layer 12 is formed on a substrate, contains a plurality of portions that are discontinuous with each other at least in part, and needs to contain aluminum or an aluminum alloy. When the metallic luster layer 12 is in a continuous state on the substrate, sufficient brilliance can be obtained, but the amount of radio wave transmission attenuation becomes very large, and therefore electromagnetic wave transmission cannot be ensured.
  • the details of the mechanism by which the metallic luster layer 12 becomes discontinuous on the substrate are not always clear, but it is presumed to be roughly as follows. That is, in the process of forming the thin film of the metallic luster layer 12, the ease of forming the discontinuous structure is related to the surface diffusion on the substrate to which the metallic luster layer 12 is applied, and the temperature of the substrate is high, so that the substrate has a high temperature. The smaller the wettability of the metallic luster layer and the lower the melting point of the material of the metallic luster layer, the easier it is to form a discontinuous structure.
  • the average particle size of the plurality of portions 12a means the average value of the equivalent circle diameters of the plurality of portions 12a.
  • the circle-equivalent diameter of the portion 12a is the diameter of a perfect circle corresponding to the area of the portion 12a.
  • the equivalent circle diameter of the portion 12a of the metallic luster layer 12 is not particularly limited, but is usually about 10 to 1000 nm.
  • the distance between the portions 12a is not particularly limited, but is usually about 10 to 1000 nm.
  • the brilliance can be further improved while maintaining high electromagnetic wave transmission.
  • the metallic luster layer 12 has a relatively low melting point as well as being able to exhibit sufficient brilliance and good transparency. This is because the metallic luster layer 12 is preferably formed by thin film growth using sputtering. For this reason, the metallic luster layer 12 is suitable for a metal having a melting point of about 1000 ° C. or lower, and needs to contain aluminum or an aluminum alloy. Further, in order to keep the transmission Y value of the electromagnetic wave transmitting metallic luster member 1 within the above range, it is preferable to reduce the film thickness of the metallic luster layer.
  • the metallic luster layer 12 is particularly preferably Al or an alloy thereof for reasons of brilliance, transparency, price and the like.
  • the aluminum content is preferably 50% by mass or more.
  • the thickness of the metallic luster layer 12 is preferably 3 nm or more, more preferably 5 nm or more, and further preferably 7 nm or more in order to suppress coloring and exhibit sufficient brilliance and good transparency. preferable. Further, from the viewpoint of facilitating the transmission Y value within a predetermined range, it is preferably 15 nm or less, more preferably 12 nm or less, and further preferably 10 nm or less. This thickness is also suitable for forming a uniform film with good productivity, and the appearance of the final product, such as a decorative member or a resin molded product, is also good.
  • the thickness of the metallic luster layer 12 can be measured by the method described in the column of Examples.
  • the sheet resistance of the metallic luster layer is preferably 100 ⁇ / ⁇ or more.
  • the electromagnetic wave transmission property is about 10 [ ⁇ dB] or less at a wavelength of 5 GHz. More preferably, it is 1000 ⁇ / ⁇ or more.
  • the sheet resistance of the electromagnetic wave transmitting metallic luster member is preferably 100 ⁇ / ⁇ or more. From the viewpoint of electromagnetic wave transmission, the sheet resistance is more preferably 200 ⁇ / ⁇ or more, further preferably 600 ⁇ / ⁇ or more, still more preferably 1000 ⁇ / ⁇ or more.
  • the value of this sheet resistance is greatly influenced not only by the material and thickness of the metallic luster layer but also by the material and thickness of the inorganic oxide-containing layer which is the base layer. Therefore, when the inorganic oxide-containing layer is provided, it is necessary to consider the relationship with the inorganic oxide-containing layer.
  • the electromagnetic wave-permeable metallic luster member of the present embodiment may be provided with other layers depending on the intended use, in addition to the above-mentioned metallic luster layer and inorganic oxide-containing layer, as long as the effects of the present invention are exhibited.
  • Other layers include an optical adjustment layer (color adjustment layer) such as a high-refractive-index material for adjusting the appearance such as color, and a protective layer (scratch resistance) for improving durability such as moisture resistance and scratch resistance.
  • a sex layer a resin layer such as an adhesive layer, and the like can be mentioned.
  • the electromagnetic wave-transmitting metallic luster member of the present embodiment may include a resin layer.
  • the resin layer may be provided on the surface of the metallic luster layer opposite to the surface of the metallic luster layer on the substrate side, or may be formed on the metallic luster layer.
  • the electromagnetic wave-transmitting metallic luster member of the present embodiment preferably has a resin layer on the surface of the metallic luster layer opposite to the surface on the substrate side, and the haze value of the resin layer is less than 20%.
  • the haze value of the resin layer is preferably less than 20%, more preferably 10% or less, still more preferably 5% or less, from the viewpoint of realizing an appearance having excellent transparency. Further, by adjusting the haze value of the resin layer, it is possible to control the L * value, the a * value, and the b * value of the obtained electromagnetic wave transmitting metallic luster member.
  • the haze value of the resin layer can be measured by a measuring device such as a haze meter HM-150N (manufactured by Murakami Color Science Laboratory Co., Ltd.), and can be measured by the method described in Examples.
  • the resin layer is an optical adjustment layer (color adjustment layer) such as a high-refractive-index material for adjusting the appearance such as color, and a protective layer (scratch resistance) for improving durability such as moisture resistance and scratch resistance.
  • Layer an easy-adhesion layer, an adhesive layer, the above-mentioned hard coat layer, an antireflection layer, a light extraction layer, an anti-glare layer and the like.
  • a plurality of resin layers can be provided.
  • FIG. 4 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member according to an embodiment of the present invention.
  • the electromagnetic wave-transmitting metallic luster member 1 includes a substrate 10, an inorganic oxide-containing layer 11, a metallic luster layer 12, and a pressure-sensitive adhesive layer 13a and a hard coat layer 13b as resin layers. May be good.
  • the electromagnetic wave-transmitting metallic luster member 1 of the present embodiment is provided with an inorganic oxide-containing layer 11, a metallic luster layer 12, and a pressure-sensitive adhesive layer 13a on a substrate 10 provided with a hard coat layer 13b.
  • the electromagnetic wave-transmitting metallic luster member 1 of the present embodiment may be attached to the adherend member via the pressure-sensitive adhesive layer 13a and used.
  • the adherent member can be decorated from the inside by attaching the electromagnetic wave-transmitting metallic luster member 1 to the transparent adherend member via the pressure-sensitive adhesive layer 13a.
  • the electromagnetic wave-transmitting metallic luster member 1 passes through the pressure-sensitive adhesive layer 13a with respect to the surface of the transparent adherend member on the side opposite to the visible side (hereinafter, also referred to as the outer side) (hereinafter, also referred to as the inner side).
  • the transparent adherend member for example, a member made of glass or plastic can be used, but the transparent member is not limited to this.
  • the pressure-sensitive adhesive layer is preferably a layer made of a transparent pressure-sensitive adhesive.
  • the electromagnetic wave-permeable metallic luster member of the present embodiment may be used by being attached to an adherend member via an adhesive layer.
  • the adherend can be decorated from the inside by attaching the substrate to the transparent adherend via the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited as long as it is a transparent pressure-sensitive adhesive.
  • either of the polyether adhesives can be used alone or in combination of two or more. From the viewpoint of transparency, processability, durability and the like, it is preferable to use an acrylic pressure-sensitive adhesive.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, but it should be 100 ⁇ m or less because thinning it contributes to thinning of the final product configuration and improves visible light transmission, film thickness accuracy, and flatness. It is more preferably 75 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the transmitted Y value of the entire pressure-sensitive adhesive layer is not particularly limited, but the value at an arbitrary visible light wavelength measured according to JIS K7361 is preferably 10% or more, more preferably 30% or more, and more preferably 50% or more. Is more preferable. The higher the permeation Y value of the pressure-sensitive adhesive layer, the more preferable.
  • the transparent adhesive constituting the adhesive layer may be colored.
  • the colored pressure-sensitive adhesive layer is visually recognized via the metallic luster layer having good transparency, so that the electromagnetic wave is transmitted.
  • the metallic luster member 1 can exhibit a colored metallic luster without changing the color tone of the pressure-sensitive adhesive layer.
  • the method of coloring the transparent adhesive is not particularly limited, but it can be colored by adding a small amount of a dye, for example.
  • a release liner may be provided on the pressure-sensitive adhesive layer in order to protect the pressure-sensitive adhesive layer until it is attached to the adherend member.
  • a method such as vacuum vapor deposition or sputtering can be used.
  • the inorganic oxide-containing layer 11 is formed on the substrate 10, the inorganic oxide-containing layer 11 is formed by vacuum deposition, sputtering, ion plating, or the like prior to the formation of the metallic luster layer 12.
  • sputtering is preferable because the thickness can be strictly controlled even in a large area.
  • the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is provided, it can be formed by applying a pressure-sensitive adhesive composition or the like to the surface on which the pressure-sensitive adhesive layer is provided.
  • the pressure-sensitive adhesive composition can be applied using a conventional coater, for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, or the like.
  • the drying temperature can be appropriately adopted, but is preferably 40 ° C. to 200 ° C., more preferably 50 ° C. to 180 ° C., and particularly preferably 70 ° C. to 120 ° C.
  • an appropriate time may be adopted as appropriate.
  • the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
  • the inorganic oxide-containing layer 11 When the inorganic oxide-containing layer 11 is provided between the substrate 10 and the metallic luster layer 12, the inorganic oxide-containing layer 11 and the metallic luster layer 12 are brought into direct contact with each other without interposing another layer. Is preferable.
  • the decorative member according to the present embodiment includes an adherend member and the above-mentioned electromagnetic wave-transmitting metallic luster member, and the electromagnetic wave-transmitting metallic luster member (electromagnetic wave-transmitting metallic luster member 1) is interposed via the pressure-sensitive adhesive layer. It is attached to the adherend member.
  • the decorative member according to the present embodiment includes an adherend member and the above-mentioned electromagnetic wave-permeable metallic luster member including a pressure-sensitive adhesive layer made of a transparent adhesive, and the electromagnetic wave-transmitting metallic luster member provides the pressure-sensitive adhesive layer. It is preferable that the material is attached to the adherend member via the material.
  • FIG. 3 shows a schematic cross-sectional view of the decorative member 2 according to the embodiment of the present invention.
  • the decorative member 2 according to the embodiment of the present invention is a schematic cross-sectional view of a state in which the electromagnetic wave transmitting metallic luster member 1 is attached to the adherend member 15.
  • the electromagnetic wave-transmitting metallic luster member 1 provided with the metallic luster layer 12, the inorganic oxide-containing layer 11, the substrate 10 (base film), and the pressure-sensitive adhesive layer 14 is the adherend member 15. It is affixed to.
  • the electromagnetic wave-transmitting metallic luster member 1 of the present embodiment is provided on the surface of the adherend member 15 because the electromagnetic wave-transmitting metallic luster member 1 has a metallic luster with suppressed coloring such as yellowish color and has excellent visibility. It is possible to obtain a decorative member 2 in which the adherend member 15 is decorated while making the best use of the design, color and texture as it is.
  • the electromagnetic wave transmitting metallic luster member 1 may be used by being attached to the inner surface of the transparent adherend member 15.
  • the transparent adherend member 15 for example, a member made of glass or plastic can be used, but the transparent adherend member 15 is not limited to this.
  • the method of attaching the electromagnetic wave-transmitting metallic luster member 1 to the adherend member 15 is not particularly limited, but it can be attached by, for example, vacuum forming.
  • Vacuum forming means that the electromagnetic wave-permeable metallic luster member 1 is stretched while being heated and softened, the space on the adherend side of the electromagnetic wave-transmitting metallic luster member 1 is depressurized, and the space on the opposite side is pressurized as necessary.
  • This is a method of pasting and laminating an electromagnetic wave-transmitting metallic luster member 1 while forming it along a three-dimensional three-dimensional shape of the surface of an adherend member.
  • the electromagnetic wave transmitting metallic luster member 1 the above description can be used as it is.
  • electromagnetic wave-permeable metallic luster members and decorative members Since the electromagnetic wave-transmitting metallic luster member and the metal thin film of the present embodiment have electromagnetic wave transmission properties, they are preferably used for devices, articles, and parts thereof that transmit and receive electromagnetic waves.
  • applications for household goods such as structural parts for vehicles, vehicle-mounted products, housings for electronic devices, housings for home appliances, structural parts, mechanical parts, various automobile parts, electronic device parts, furniture, kitchen supplies, etc. , Medical equipment, building material parts, other structural parts, exterior parts, etc.
  • ECU box electrical parts, engine peripheral parts, drive system / gear peripheral parts, intake / exhaust system parts, cooling system parts and the like.
  • home appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, TVs, watches, ventilation fans, projectors, speakers, personal computers, mobile phones , Smartphones, digital cameras, tablet PCs, portable music players, portable game machines, chargers, electronic information devices such as batteries, and the like.
  • An electromagnetic wave-transmitting metallic luster member was prepared and evaluated.
  • the details of the evaluation method are as follows. ⁇ Transparency characteristics>
  • the separator of the transparent adhesive CS9861UAS (manufactured by Nitto Denko Co., Ltd.) is peeled off and bonded to the water-rimmed glass S200200 (manufactured by Matsunami Glass Industry Co., Ltd.) with a hand roller, and then the other separator is peeled off to generate electromagnetic waves.
  • a transmittance measurement sample was obtained by laminating with a hand roller so that the transparent adhesive was bonded to the surface of the transparent metal gloss member on the metal gloss layer side.
  • the transmittance measurement sample was measured with an integrating sphere spectroscopic transmittance measuring device DOT-3C (manufactured by Murakami Color Technology Laboratory Co., Ltd.) using a standard light source D65 for visible light with a wavelength in the range of 380 nm to 700 nm.
  • the transmittance was measured by incident on the surface of the member on the substrate side, and the transmittance characteristics (transmission Y value, a * value and b * value) were obtained.
  • the obtained Y values, a * values and b * values are shown in Table 1.
  • the separator of the transparent adhesive CS9861UAS (manufactured by Nitto Denko Co., Ltd.) is peeled off and bonded to the water-rimmed glass S200200 (manufactured by Matsunami Glass Industry Co., Ltd.) with a hand roller, and then the other separator is peeled off to generate electromagnetic waves.
  • a transparent adhesive is attached to the surface of the transmissive metallic luster member on the side of the metallic luster layer with a hand roller so that the transparent adhesive is attached.
  • 21 Vinyl tape black (manufactured by Nitto Denko KK) was attached with a hand roller to obtain a reflectance measurement sample.
  • Reflectance measurement is performed by using a spectrophotometer CM-2600d (manufactured by Konica Minolta Co., Ltd.) to inject visible light in the wavelength range of 360 nm to 740 nm onto the glass side surface using a standard light source D65. This was performed to obtain reflection characteristics (reflection Y value, a * value and b * value). The obtained Y values, a * values and b * values are shown in Table 1.
  • the average value of the thickness of the portion 12a is the thickness of the metallic luster layer (Al film thickness (nm)). And said.
  • the thickness of each portion 12a was set to the thickness of the thickest part in the vertical direction from the substrate 10.
  • this average value is referred to as "maximum thickness" for convenience.
  • FIG. 6 shows an example of an electron micrograph (TEM image) of a cross section of an electromagnetic wave transmitting metallic luster member. In obtaining the maximum thickness, first, in the metallic luster layer appearing on the surface of the electromagnetic wave transmitting metallic luster member as shown in FIG.
  • a square region 3 having a side of 5 cm as shown in FIG. 5 is appropriately extracted.
  • a total of five points "a” to "e” obtained by dividing the center lines A and B of the vertical side and the horizontal side of the square region 3 into four equal parts were selected as measurement points.
  • a viewing angle region including approximately five portions 12a was extracted. Approximately 5 portions 12a at each of these 5 measurement points, that is, the individual thicknesses (nm) of 25 (5 ⁇ 5) portions 12a were obtained, and the average value thereof was set to “maximum”. "Thickness".
  • ⁇ Haze value> The haze value of the resin layer was measured using a haze meter (device name: HM-150N, manufactured by Murakami Color Science Laboratory Co., Ltd.) by the method specified by JIS7136.
  • the separator of the transparent adhesive CS9861UAS manufactured by Nitto Denko Co., Ltd. was peeled off from the water-rimmed glass S200200 (manufactured by Matsunami Glass Industry Co., Ltd.) and bonded with a hand roller, and then the other separator was peeled off, but the haze. When the value was measured, it was 1.0% or less.
  • a UV curable resin layer (hard coat layer) having a thickness of 2 ⁇ m is formed on a PET film 50-U483 (thickness 50 ⁇ m) manufactured by Toray Industries, Inc., and the haze value of the PET film with a UV curable resin layer is 2% or less. Film was used.
  • an ITO target is attached to a DC magnetron sputtering device, and by sputtering while introducing Ar gas and O 2 gas, an ITO layer having a thickness of 5 nm is placed on the ultraviolet curable resin layer along the surface of the base film. Formed directly to.
  • the temperature of the base film when forming the ITO layer was set to 50 ° C.
  • An aluminum (Al) target is attached to a DC magnetron sputtering apparatus, and an Al layer (metallic luster layer) having a thickness of 9 nm is formed on the ITO layer by sputtering while introducing Ar gas, and the laminate of Example 1 is formed. I got 1.
  • the obtained Al layer was a discontinuous layer.
  • the temperature of the base film when forming the Al layer was set to 50 ° C.
  • Example 1 an electromagnetic wave-transmitting metallic luster member of Example 1, which is a laminate of a base film, an ultraviolet curable resin layer, an indium oxide-containing layer, and a metallic luster layer, was obtained.
  • the transmission characteristics of the obtained electromagnetic wave-transmitting metallic luster member were measured by the above method and are shown in Table 1.
  • the adherend member As the adherend member, a glass having a thickness of 0.7 mm having a design on the surface was used.
  • the electromagnetic wave-permeable metallic luster member obtained above is attached to the adherend member using the adhesive CS9861UAS (manufactured by Nitto Denko KK), and adhered to the surface of the electromagnetic wave-transmitting metallic luster member on the base film side.
  • a decorative member was obtained in which the member was bonded to the member via an adhesive.
  • Example 2 to 3 The film thickness of the Al layer in Example 1 was changed to obtain an electromagnetic wave-transmitting metallic luster member and a decorative member exhibiting transmission characteristics and reflection characteristics as shown in Table 1.
  • a film obtained by forming an ultraviolet curable resin layer (hard coat layer) having a thickness of 2 ⁇ m on a PET film 50-U483 (thickness 50 ⁇ m) manufactured by Toray Industries, Inc. was used.
  • An In layer was formed on the ultraviolet curable resin layer of the base film at room temperature (25 ° C.) using a resistance heating type high vacuum vapor deposition apparatus.
  • the obtained In layer was discontinuous. Electromagnetic wave-transmitting metallic luster members and decorative members exhibiting transmission characteristics and reflection characteristics as shown in Table 1 were obtained in the same manner as in Example 1 except that the amount of In deposited was changed.
  • a film obtained by forming an ultraviolet curable resin layer (hard coat layer) having a thickness of 2 ⁇ m on a PET film 50-U483 (thickness 50 ⁇ m) manufactured by Toray Industries, Inc. was used.
  • a Sn layer was formed on the ultraviolet curable resin layer of the base film by using a resistance heating type high vacuum vapor deposition apparatus. The obtained Sn layer was discontinuous.
  • Electromagnetic wave-transmitting metallic luster members and decorative members exhibiting transmission characteristics and reflection characteristics as shown in Table 1 were obtained in the same manner as in Example 1 except that the amount of Sn deposited was changed.
  • FIG. 7 shows the relationship between the a * value and the b * value of the transmitted light of the electromagnetic wave transmitting metallic luster member of the example and the comparative example.
  • the relationship between the transmission Y value and the a * value is shown in FIG. 8, and the relationship between the transmission Y value and the b * value is shown in FIG.
  • FIG. 10 shows the relationship between the a * value and the b * value of the reflected light of the electromagnetic wave transmitting metallic luster member of the example and the comparative example.
  • the relationship between the reflected Y value and the a * value is shown in FIG. 11, and the relationship between the reflected Y value and the b * value is shown in FIG.
  • the electromagnetic wave transmitting metallic luster members of Examples 1 to 3 use aluminum as the metallic luster layer, have a reflected Y value of 10 to 25%, and have a transmitted Y value of 30 to 65%. Therefore, it has excellent electromagnetic wave transmission and has a metallic luster with suppressed coloring. Further, since the electromagnetic wave-transmitting metallic luster members of Examples 1 to 3 have excellent transparency, a decorative member whose surface shape of the adherend member can be visually recognized was obtained. Comparative Examples 1 to 4 in which indium was used for the metallic luster layer and Comparative Examples 5 to 7 in which tin was used for the metallic luster layer had a reflection a * value, a reflection b * value, a transmission a * value, and a transmission b * value. The value was far from 0 as compared with the examples, indicating that the degree of coloring was high.
  • the electromagnetic wave-permeable metallic luster member according to the present invention can be used for devices and articles that transmit and receive electromagnetic waves, and parts thereof.
  • applications for household goods such as structural parts for vehicles, vehicle-mounted products, housings for electronic devices, housings for home appliances, structural parts, mechanical parts, various automobile parts, electronic device parts, furniture, kitchen supplies, etc. It can also be used for various applications that require both design and electromagnetic wave transmission, such as medical equipment, building material parts, other structural parts and exterior parts.
  • Electromagnetic wave transmissive metallic luster member 2 Decorative member 10
  • Base material 11
  • Inorganic oxide-containing layer 12
  • Hard coat layer 15

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un élément de transmission d'ondes électromagnétiques ayant un éclat métallique, comprenant un substrat et une couche d'éclat métallique qui est formée sur le substrat, la couche d'éclat métallique comprenant une pluralité de sections qui ne sont pas continues les unes avec les autres dans au moins une partie, la couche d'éclat métallique comprend de l'aluminium ou un alliage d'aluminium, et la valeur Y de réflexion est de 10 à 25 % et la valeur Y de transmission est de 30 à 65 % selon un procédé SCI dans le système de couleur CIE-XYZ.
PCT/JP2021/024389 2020-06-30 2021-06-28 Élément de transmission d'ondes électromagnétiques à éclat métallique, et élément décoratif WO2022004670A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009166384A (ja) * 2008-01-17 2009-07-30 Toppan Printing Co Ltd 無線機器用化粧板
JP2011163903A (ja) * 2010-02-09 2011-08-25 Kanto Kasei Kogyo Kk 電磁波透過用金属被膜、電磁波透過用金属被膜の形成方法及び車載用レーダー装置
JP2018154878A (ja) * 2017-03-17 2018-10-04 株式会社Ｊｃｕ 電磁波透過用金属被膜、電磁波透過用金属被膜の形成方法及び車載用レーダー装置
JP2019123224A (ja) * 2018-01-12 2019-07-25 日東電工株式会社 電磁波透過性ハーフミラー調フィルム

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009166384A (ja) * 2008-01-17 2009-07-30 Toppan Printing Co Ltd 無線機器用化粧板
JP2011163903A (ja) * 2010-02-09 2011-08-25 Kanto Kasei Kogyo Kk 電磁波透過用金属被膜、電磁波透過用金属被膜の形成方法及び車載用レーダー装置
JP2018154878A (ja) * 2017-03-17 2018-10-04 株式会社Ｊｃｕ 電磁波透過用金属被膜、電磁波透過用金属被膜の形成方法及び車載用レーダー装置
JP2019123224A (ja) * 2018-01-12 2019-07-25 日東電工株式会社 電磁波透過性ハーフミラー調フィルム

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