WO2022004670A1 - Electromagnetic wave-transmissive member with metallic luster, and decorative member - Google Patents

Electromagnetic wave-transmissive member with metallic luster, and decorative member 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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French (fr)
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/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered 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
    • B32B15/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/02Physical, chemical or physicochemical properties
    • B32B7/023Optical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/02Physical, chemical or physicochemical properties
    • B32B7/025Electric or magnetic properties
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic 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

Abstract

The present invention relates to an electromagnetic wave-transmissive member with a metallic luster, comprising a substrate and a metallic luster layer that is formed on the substrate, wherein the metallic luster layer includes a plurality of sections that are not continuous with one another in at least one portion, the metallic luster layer includes aluminum or an aluminum alloy, and the reflection Y value is 10-25% and the transmission Y value is 30-65% according to an SCI method in the CIE-XYZ color system.

Description

電磁波透過性金属光沢部材、及び加飾部材Electromagnetic wave transmissive metallic luster member and decorative member
 本発明は、電磁波透過性金属光沢部材、及び加飾部材に関する。 The present invention relates to an electromagnetic wave transmitting metallic luster member and a decorative member.
 従来、電磁波透過性及び金属光沢を有する部材が、その金属光沢に由来する外観の高級感と、電磁波透過性とを兼ね備えることから、電磁波を送受信する装置に好適に用いられている。
 金属光沢調の部材に金属を使用した場合には、電磁波の送受信が実質的に不可能、或いは、妨害されてしまう。したがって、電磁波の送受信を妨げることなく、意匠性を損なわせないために、金属光沢と電磁波透過性の双方を兼ね備えた電磁波透過性金属光沢部材が必要とされている。
Conventionally, 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.
When 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.
 このような電磁波透過性金属光沢部材は、電磁波を送受信する装置として、通信を必要とする様々な機器、例えば、スマートキーを設けた自動車のドアハンドル、車載通信機器、携帯電話、パソコン等の電子機器等への応用が期待されている。更に、近年では、IoT技術の発達に伴い、従来は通信等行われることがなかった、冷蔵庫等の家電製品、生活機器等、幅広い分野での応用も期待されている。 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.
 電磁波透過性金属光沢部材に関して、特許文献1には、クロム(Cr)又はインジウム(In)より成る金属被膜を含む樹脂製品が開示されている。この樹脂製品は、樹脂基材と、当該樹脂基材の上に成膜された無機化合物を含む無機質下地膜と、当該無機質下地膜の上に物理蒸着法により成膜された光輝性及び不連続構造のクロム(Cr)又はインジウム(In)よりなる金属皮膜を含む。無機質下地膜として、特許文献1では、(a)金属化合物の薄膜、例えば、酸化チタン(TiO、TiO、Ti等)等のチタン化合物;酸化ケイ素(SiO、SiO等)、窒化ケイ素(Si等)等のケイ素化合物;酸化アルミニウム(Al)等のアルミニウム化合物;酸化鉄(Fe)等の鉄化合物;酸化セレン(CeO)等のセレン化合物;酸化ジルコン(ZrO)等のジルコン化合物;硫化亜鉛(ZnS)等の亜鉛化合物等、(b)無機塗料の塗膜、例えば、シリコン、アモルファスTiO等(その他、上記例示の金属化合物)を主成分とする無機塗料による塗膜が使用されている。 Regarding the electromagnetic wave transmitting metallic luster member, 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. 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. 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.
日本国特開2007-144988号公報Japanese Patent Application Laid-Open No. 2007-144988
 従来技術における金属光沢部材は、一般的には平滑面に金属光沢層を形成したものである。また、従来の金属光沢部材は、意匠性の観点から、光沢度の高い金属光沢を有するものが検討されている。
 また、金属光沢部材の意匠に対するニーズは多様化しており、金属光沢部材を被着部材に貼付し加飾部材とした際に、被着部材の表面形状や色を金属光沢部材を介して視認し得る、透明性を備えた金属光沢部材も望まれている。
 しかしながら、電磁波透過性金属光沢部材の透明性を高めると、透過光が黄色がかる等、着色された金属光沢部材となる場合があり、被着部材の色味を損なうという課題が新たに生じた。
 本願発明は、上記に鑑みてなされたものであり、電磁波透過性を有し、着色を抑えた金属光沢と透明性とを兼ね備えた電磁波透過性金属光沢部材、及び加飾部材を提供することを目的とする。
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.
However, if the transparency of the electromagnetically transmissive metallic luster member is increased, the transmitted light may become yellowish or the like, and the metallic luster member may be colored, which newly raises a problem of impairing the color of the adherend member.
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.
 本発明者等は、上記課題を解決するために鋭意検討を重ねた結果、通常は不連続構造になり難いアルミニウム又はアルミニウム合金を含有する金属光沢層を不連続構造とし、かつ反射特性と透過特性を特定の範囲内とすることにより、優れた電磁波透過性を有し、着色を抑えた金属光沢と透明性を兼ね備えた電磁波透過性金属光沢部材が得られることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have made a metallic glossy layer containing aluminum or an aluminum alloy, which normally does not easily have a discontinuous structure, into a discontinuous structure, and have reflection characteristics and transmission characteristics. To complete the present invention, it has been found that an electromagnetic wave-transmitting metal gloss member having excellent electromagnetic wave transmission property and having both metallic gloss and transparency with suppressed coloring can be obtained by setting the temperature within a specific range. I arrived.
 すなわち、本発明は以下のとおりである。
〔1〕
 基体と、前記基体上に形成された金属光沢層とを備え、
 前記金属光沢層は、少なくとも一部において互いに不連続の状態にある複数の部分を含み、
 前記金属光沢層はアルミニウム又はアルミニウム合金を含有し、
 CIE-XYZ表色系のSCI方式の反射Y値が10~25%であり、かつ透過Y値が30~65%である、電磁波透過性金属光沢部材。
〔2〕
 前記基体と前記金属光沢層との間に無機酸化物含有層をさらに備える、〔1〕に記載の電磁波透過性金属光沢部材。
〔3〕
 前記無機酸化物含有層が酸化インジウム含有層である、〔2〕に記載の電磁波透過性金属光沢部材。
〔4〕
 前記酸化インジウム含有層は、酸化インジウム(In)、インジウム錫酸化物(ITO)、又はインジウム亜鉛酸化物(IZO)のいずれかを含む、〔3〕に記載の電磁波透過性金属光沢部材。
〔5〕
 前記無機酸化物含有層は連続状態で設けられている、〔2〕~〔4〕のいずれか1項に記載の電磁波透過性金属光沢部材。
〔6〕
 前記無機酸化物含有層の厚さは、1nm~1000nmである、〔2〕~〔5〕のいずれか1項に記載の電磁波透過性金属光沢部材。
〔7〕
 前記金属光沢層の基体側の面と反対側の面に樹脂層を備え、該樹脂層のヘイズ値が20%未満である、〔1〕~〔6〕のいずれか1項に記載の電磁波透過性金属光沢部材。
〔8〕
 前記金属光沢層の厚さは、3nm~10nmである、〔1〕~〔7〕のいずれか1項に記載の電磁波透過性金属光沢部材。
〔9〕
 シート抵抗が、100Ω/□以上である、〔1〕~〔8〕のいずれか1項に記載の電磁波透過性金属光沢部材。
〔10〕
 前記複数の部分は島状に形成されている、〔1〕~〔9〕のいずれか1項に記載の電磁波透過性金属光沢部材。
〔11〕
 前記基体は、基材フィルム、樹脂成型物基材、ガラス基材、又は金属光沢を付与すべき物品のいずれかである、〔1〕~〔10〕のいずれか1項に記載の電磁波透過性金属光沢部材。
〔12〕
 透明粘着剤からなる粘着剤層をさらに備える、〔1〕~〔11〕のいずれか1項に記載の電磁波透過性金属光沢部材。
〔13〕
 被着部材と、〔12〕に記載の電磁波透過性金属光沢部材とを備え、前記電磁波透過性金属光沢部材が前記粘着剤層を介して前記被着部材に貼付されている、加飾部材。
That is, the present invention is as follows.
[1]
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%.
[2]
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.
[3]
The electromagnetic wave-permeable metallic luster member according to [2], wherein the inorganic oxide-containing layer is an indium oxide-containing layer.
[4]
The electromagnetic wave transmissive metal gloss member according to [3], wherein the indium oxide-containing layer contains any one of indium oxide (In 2 O 3 ), indium tin oxide (ITO), and indium zinc oxide (IZO). ..
[5]
The electromagnetic wave-transmitting metallic luster member according to any one of [2] to [4], wherein the inorganic oxide-containing layer is provided in a continuous state.
[6]
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.
[7]
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.
[9]
The electromagnetic wave transmissive metallic luster member according to any one of [1] to [8], wherein the sheet resistance is 100 Ω / □ or more.
[10]
The electromagnetic wave-transmitting metallic luster member according to any one of [1] to [9], wherein the plurality of portions are formed in an island shape.
[11]
The electromagnetic wave transmittance according to any one of [1] to [10], wherein the substrate 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.
[12]
The electromagnetic wave-transmitting metallic luster member according to any one of [1] to [11], further comprising a pressure-sensitive adhesive layer made of a transparent pressure-sensitive adhesive.
[13]
A decorative member comprising an adherend member and the electromagnetic wave-permeable metallic luster member according to [12], wherein the electromagnetic wave-permeable metallic luster member is attached to the adherend member via the pressure-sensitive adhesive layer.
 本発明によれば、優れた電磁波透過性を有し、着色を抑えた金属光沢と透明性とを兼ね備えた電磁波透過性金属光沢部材、及び加飾部材を提供することができる。 According to the present invention, it is possible to provide 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.
図1は、本発明の一実施形態による電磁波透過性金属光沢部材の概略断面図である。FIG. 1 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member according to an embodiment of the present invention. 図2は、本発明の一実施形態に係る電磁波透過性金属光沢部材の表面の電子顕微鏡写真(SEM画像)を示す図である。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. 図3は、本発明の一実施形態による加飾部材の概略断面図である。FIG. 3 is a schematic cross-sectional view of a decorative member according to an embodiment of the present invention. 図4は、本発明の一実施形態による電磁波透過性金属光沢部材の概略断面図である。FIG. 4 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member according to an embodiment of the present invention. 図5は、本発明の一実施形態に係る電磁波透過性金属光沢部材の金属光沢層の厚さの測定方法を説明するための図である。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. 図6は、本発明の一実施形態に係る電磁波透過性金属光沢部材の断面の電子顕微鏡写真(TEM画像)を示す図である。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. 図7は、実施例及び比較例の電磁波透過性金属光沢部材の透過光のa値とb値との関係を示す図である。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. 図8は、実施例及び比較例の電磁波透過性金属光沢部材の透過光の透過Y値とa値との関係を示す図である。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. 図9は、実施例及び比較例の電磁波透過性金属光沢部材の透過光の透過Y値とb値との関係を示す図である。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. 図10は、実施例及び比較例の電磁波透過性金属光沢部材の反射光のa値とb値との関係を示す図である。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. 図11は、実施例及び比較例の電磁波透過性金属光沢部材の反射光の反射Y値とa値との関係を示す図である。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. 図12は、実施例及び比較例の電磁波透過性金属光沢部材の反射光の反射Y値とb値との関係を示す図である。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.
 以下、添付図面を参照しつつ、本発明の好適な実施形態について説明する。以下においては、説明の便宜のために本発明の好適な実施形態のみを示すが、勿論、これによって本発明を限定しようとするものではない。 Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. In the following, for convenience of explanation, only preferred embodiments of the present invention are shown, but of course, this is not intended to limit the present invention.
<1.基本構成>
 本発明の実施形態にかかる電磁波透過性金属光沢部材は、基体と、前記基体上に形成された金属光沢層とを備え、
 前記金属光沢層は、少なくとも一部において互いに不連続の状態にある複数の部分を含み、
 前記金属光沢層はアルミニウム又はアルミニウム合金を含有し、
 CIE-XYZ表色系のSCI方式の反射Y値が10~25%であり、かつ透過Y値が30~65%である。
<1. Basic configuration>
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%.
 図1に、本発明の一実施形態による電磁波透過性金属光沢部材1の概略断面図を示す。また、図2に、本発明の一実施形態による電磁波透過性金属光沢部材1の表面の電子顕微鏡写真(SEM画像)の一例を示す。 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. Further, 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.
 図1に示すように、電磁波透過性金属光沢部材1は、基体10と、基体10の上に形成された、金属光沢層12とを含む。電磁波透過性金属光沢部材1は、基体10と金属光沢層12との間に無機酸化物含有層をさらに備えていてもよく、無機酸化物含有層11は酸化インジウム含有層であってもよい。金属光沢層12は酸化インジウム含有層の上に形成されることが好ましい。 As shown in FIG. 1, 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.
 無機酸化物含有層11は、基体10の面に設けられている。無機酸化物含有層11は、基体10の面に直接設けられていてもよいし、基体10の面に設けた保護層等を介して間接的に設けられてもよい。無機酸化物含有層11は、基体10の面に連続状態で、言い換えれば、隙間なく、設けるのが好ましい。連続状態で設けることにより、無機酸化物含有層11、ひいては、電磁波透過性金属光沢部材1の平滑性や耐食性を向上させることができ、また、無機酸化物含有層11を面内にばらつきなく成膜することも容易となる。 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. By providing the inorganic oxide-containing layer 11 in a continuous state, 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.
 金属光沢層12は無機酸化物含有層11に積層される。金属光沢層12は複数の部分12aを含む。無機酸化物含有層11に積層されることにより、これらの部分12aは、少なくとも一部において互いに不連続の状態、言い換えれば、少なくとも一部において隙間12bによって隔てられる。隙間12bによって隔てられるため、これらの部分12aのシート抵抗は大きくなり、電波との相互作用が低下するため、電波を透過させることができる。これらの各部分12aは金属を蒸着、スパッタ等することによって形成されたスパッタ粒子の集合体である。スパッタ粒子が基体10等の基体上で薄膜を形成する際には、基体上での粒子の表面拡散性が薄膜の形状に影響を及ぼす。 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.
 なお、本明細書でいう「不連続の状態」とは、隙間12bによって互いに隔てられており、この結果、互いに電気的に絶縁されている状態を意味する。電気的に絶縁されることにより、シート抵抗が大きくなり、所望とする電磁波透過性が得られることになる。不連続の形態は、特に限定されるものではなく、例えば、島状、クラック等が含まれる。 Note that the "discontinuous state" as used herein 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.
 ここで「島状」とは、図2の電磁波透過性金属光沢部材の金属光沢層の表面の電子顕微鏡写真(SEM画像)に示されているように、スパッタ粒子の集合体である粒子同士が各々独立しており、それらの粒子が、互いに僅かに離間し又は一部接触した状態で敷き詰められてなる構造を意味する。 Here, 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. Each is independent and means a structure in which the particles are spread so as to be slightly separated from each other or partially in contact with each other.
 また、クラック構造とは、金属薄膜がクラックにより分断された構造である。
 クラック構造の金属光沢層12は、例えば基体上に形成した無機酸化物含有層上に、金属薄膜層を設け、屈曲延伸して金属薄膜層にクラックを生じさせることにより形成することができる。この際、無機酸化物含有層と金属薄膜層の間に伸縮性に乏しい、即ち延伸によりクラックを生成しやすい素材からなる脆性層を設けることにより、容易にクラック構造の金属光沢層12を形成することができる。
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. At this time, 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.
 上述のとおり金属光沢層12が不連続となる態様は特に限定されないが、生産性の観点からは「島状」とすることが好ましい。 As described above, 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".
 本発明の実施形態にかかる電磁波透過性金属光沢部材は、CIE-XYZ表色系のSCI方式の反射Y値が10~25%であり、かつ透過Y値が30~65%である。 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.
 本発明の実施形態にかかる電磁波透過性金属光沢部材1の反射Y値は、分光測色計を用いて、透過Y値は、積分球式分光透過率測定器を用いて、JIS Z 8722に準じて測定できる。具体的には、実施例の欄に記載の方法で測定できる。
 電磁波透過性金属光沢部材における反射Y値及び透過Y値を特定の範囲とすることにより、優れた電磁波透過性を有し、着色を抑えた金属光沢が得られ、かつ、良好な透明性が得られることを見出した。これにより、電磁波透過性金属光沢部材を被着部材に貼付して加飾部材とした際に、電磁波透過性金属光沢部材を介しても被着部材の表面形状や色を損なうことなく視認し得る。
 電磁波透過性金属光沢部材1の反射Y値及び透過Y値は、金属層の膜厚により調整できる。
The reflected Y value of the electromagnetic wave transmissive metal gloss member 1 according to the embodiment of the present invention 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. As a result, when the electromagnetic wave-permeable metallic luster member is attached to the adherend member to form a decorative member, 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.
 反射Y値(視感反射率)は、光を電磁波透過性金属光沢部材における金属光沢層側の面(金属光沢層の基体を有する側とは反対側の面)に入射して測定した、測定波長の範囲の視感度および光源の光強度で荷重した平均反射率である。
 反射Y値は、着色を抑えた金属光沢を示す外観を得る観点から10%以上であることが好ましい。また、透過によるデザインの視認性の観点から25%以下であることが好ましい。
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.
 本実施形態に係る電磁波透過性金属光沢部材1は、被着部材側における反射光のCIE-L表色系において、
 a値及びb値はいずれも0に近いことが好ましい。
The electromagnetic wave transmissive metallic luster member 1 according to the present embodiment 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.
 CIE-L表色系は、CIE(国際照明委員会)が1976年に推奨した表色系で、Lは明度を表し、0から100までで数値が大きいほど明るくなる。色度はa、bで表わし、aは色調の赤から緑の度合いを示す指数であり、aの値がプラス方向に大きいと赤色の色調になる。さらに、bは色調の黄から青の度合いを示す指数であり、bの値がプラス方向に大きいと黄色の色調になる。a、bともに0の場合には無彩色となる。 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. Further, 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. When both a * and b * are 0, the color is achromatic.
 また、透過Y値(視感透過率)は、光を電磁波透過性金属光沢部材における基体側の面(基体の金属光沢層を有する側とは反対側の面)に入射して測定した、測定波長の範囲の視感度および光源の光強度で荷重した平均透過率である。
 透過Y値は、透過によるデザインの視認性の観点から30%以上であることが好ましい。また、金属光沢外観の観点から65%以下であることが好ましい。
 本発明の実施形態にかかる電磁波透過性金属光沢部材における透過特性(透過Y値、a値及びb値)は、電磁波透過性金属光沢部材を水縁磨ガラスS200200(松浪硝子工業(株)製)に、透明粘着剤CS9861UAS(日東電工(株)製)で貼り合せて得た透過率測定サンプルを測定することにより得た値である。
Further, 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.). It is a value obtained by measuring a transmittance measurement sample obtained by laminating the transparent pressure-sensitive adhesive CS9861UAS (manufactured by Nitto Denko Co., Ltd.) on (manufactured by Nitto Denko Co., Ltd.).
 本実施形態に係る電磁波透過性金属光沢部材1は、被着部材側における透過光のCIE-L表色系において、a値及びb値はいずれも0に近いことが好ましい。 In the electromagnetic wave transmissive metallic luster member 1 according to the present embodiment, 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.
 また、電磁波透過性金属光沢部材1の電磁波透過性は、シート抵抗と相関を有する。
 電磁波透過性金属光沢部材のシート抵抗は、100Ω/□以上であるのが好ましい。この場合、電磁波透過性は、5GHzの波長において、10[-dB]程度以下となる。
 シート抵抗は、電磁波透過性の観点から、200Ω/□以上であるのがより好ましく、600Ω/□以上であることが更に好ましく、より更に好ましくは、1000Ω/□以上である。
 マイクロ波帯域(5GHz)における電波透過減衰量は、10[-dB]未満であることが好ましく、5[-dB]未満であることがより好ましく、2[-dB]未満であることが更に好ましい。マイクロ波帯域(5GHz)における電波透過減衰量が10[-dB]以上であると、90%以上の電波が遮断されるという問題がある。
Further, 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 Ω / □ or more. In this case, the electromagnetic wave transmission property is about 10 [−dB] or less at a wavelength of 5 GHz.
From the viewpoint of electromagnetic wave transmission, the sheet resistance is more preferably 200 Ω / □ or more, further preferably 600 Ω / □ or more, still more preferably 1000 Ω / □ 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]. .. When 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.
 電磁波透過性金属光沢部材1の電波透過減衰量及びシート抵抗は、無機酸化物含有層11や金属光沢層12の材質や厚さ等により影響を受ける。 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.
<2.基体>
 本実施形態にかかる電磁波透過性金属光沢部材において、基体10としては、電磁波透過性の観点から、樹脂、ガラス、セラミックス等が挙げられる。
 基体10は、基材フィルム、樹脂成型物基材、ガラス基材、又は金属光沢を付与すべき物品のいずれかであってもよい。
 より具体的には、基材フィルムとしては、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリブチレンテレフタレート、ポリアミド、ポリ塩化ビニル、ポリカーボネート(PC)、シクロオレフィンポリマー(COP)、ポリスチレン、ポリプロピレン(PP)、ポリエチレン、ポリシクロオレフィン、ポリウレタン、アクリル(PMMA)、ABSなどの単独重合体や共重合体からなる透明フィルムを用いることができる。
<2. Hypokeimenon>
In the electromagnetic wave-transmitting metallic luster member according to the present embodiment, 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.
More specifically, examples of the base film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, polycarbonate (PC), cycloolefin polymer (COP), and polystyrene. , Polypropylene (PP), polyethylene, polycycloolefin, polyurethane, acrylic (PMMA), ABS and other homopolymers and copolymers can be used.
 これらの部材によれば、光輝性や電磁波透過性に影響を与えることもない。但し、無機酸化物含有層11や金属光沢層12を後に形成する観点から、蒸着やスパッタ等の高温に耐え得るものであることが好ましく、従って、上記材料の中でも、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、アクリル、ポリカーボネート、シクロオレフィンポリマー、ABS、ポリプロピレン、ポリウレタンが好ましい。なかでも、耐熱性とコストとのバランスがよいことからポリエチレンテレフタレートやシクロオレフィンポリマー、ポリカーボネート、アクリルが好ましい。 According to these members, it does not affect the brilliance or electromagnetic wave transmission. However, from the viewpoint of later forming the inorganic oxide-containing layer 11 and the metallic glossy layer 12, it is preferable that 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.
 基材フィルムは、単層フィルムでもよいし積層フィルムでもよい。加工のし易さ等から、厚さは、例えば、6μm~250μm程度が好ましい。無機酸化物含有層11や金属光沢層12との付着力を強くするために、プラズマ処理や易接着処理などが施されてもよい。
 基体10が基材フィルムの場合、金属光沢層12は基材フィルム上の少なくとも一部に設ければよく、基材フィルムの片面のみに設けてもよく、両面に設けてもよい。
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 μm to 250 μm. 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.
When the substrate 10 is a base film, 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.
 基材フィルムは、必要に応じて平滑性、或いは防眩性ハードコート層が形成されていてもよい。ハードコート層が設けられることにより、金属薄膜の耐擦傷性を向上させる事ができる。平滑性ハードコート層が設けられることにより、金属光沢感が増し、逆に防眩性ハードコート層によりギラツキを防止する事が出来る。ハードコート層は、硬化性樹脂を含有する溶液を塗布する事により形成できる。 The base film may be formed with a smooth or antiglare hard coat layer, if necessary. By providing the hard coat layer, the scratch resistance of the metal thin film can be improved. 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.
 硬化性樹脂としては、熱硬化型樹脂、紫外線硬化型樹脂、電子線硬化型樹脂等が挙げられる。硬化性樹脂の種類としてはポリエステル系、アクリル系、ウレタン系、アクリルウレタン系、アミド系、シリコーン系、シリケート系、エポキシ系、メラミン系、オキセタン系、アクリルウレタン系等の各種の樹脂が挙げられる。これら硬化性樹脂は、一種または二種以上を、適宜に選択して使用できる。これらの中でも、硬度が高く、紫外線硬化が可能で生産性に優れることから、アクリル系樹脂、アクリルウレタン系樹脂、およびエポキシ系樹脂が好ましい。 Examples of the curable resin include thermosetting resins, ultraviolet curable resins, and electron beam curable resins. Examples of the curable resin 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. As these curable resins, one kind or two or more kinds can be appropriately selected and used. Among these, 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.
 ここで、基材フィルムは、その表面上に金属光沢層12を形成することができる対象(基体10)の一例にすぎない点に注意すべきである。基体10には、上記のとおり基材フィルムの他、樹脂成型物基材、ガラス基材、金属光沢を付与すべき物品それ自体も含まれる。樹脂成型物基材、及び金属光沢を付与すべき物品としては、例えば、車両用構造部品、車両搭載用品、電子機器の筐体、家電機器の筐体、構造用部品、機械部品、種々の自動車用部品、電子機器用部品、家具、台所用品等の家財向け用途、医療機器、建築資材の部品、その他の構造用部品や外装用部品等が挙げられる。 It should be noted here that the base film is only an example of an object (base 10) on which the metallic luster layer 12 can be formed. As described above, 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. Examples of 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.
 金属光沢層12は、これら全ての基体上に形成することができ、基体の表面の一部に形成してもよく、基体の表面の全てに形成してもよい。この場合、金属光沢層12を付与すべき基体10は、上記の基材フィルムと同様の材質、条件を満たしていることが好ましい。 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. In this case, 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.
<3.無機酸化物含有層>
 また、一実施形態に係る電磁波透過性金属光沢部材1は、図1に示されるように、基体10と金属光沢層12の間に、無機酸化物含有層11をさらに備えてもよい。無機酸化物含有層11は、基体10の面に直接設けられていてもよいし、基体10の面に設けられた保護膜等を介して間接的に設けられてもよい。無機酸化物含有層11は、金属光沢を付与すべき基体10の面に連続状態で、言い換えれば、隙間なく、設けられるのが好ましい。連続状態で設けられることにより、無機酸化物含有層11、ひいては、金属光沢層12や電磁波透過性金属光沢部材1の平滑性や耐食性を向上させることができ、また、無機酸化物含有層11を面内ばらつきなく成膜することも容易となる。
<3. Inorganic oxide-containing layer>
Further, as shown in FIG. 1, the electromagnetic wave-transmitting metallic luster member 1 according to the embodiment 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. By being provided in a continuous state, 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.
 このように、基体10と金属光沢層12の間に、無機酸化物含有層11をさらに備えること、すなわち、基体10の上に無機酸化物含有層11を形成し、その上に金属光沢層12を形成することによれば、金属光沢層12を不連続の状態で形成しやすくなるため好ましい。そのメカニズムの詳細は必ずしも明らかではないが、金属の蒸着やスパッタによるスパッタ粒子が基体上で薄膜を形成する際には、基体上での粒子の表面拡散性が薄膜の形状に影響を及ぼし、基体の温度が高く、基体に対する金属光沢層の濡れ性が小さく、金属光沢層の材料の融点が低い方が不連続構造を形成しやすいと考えられる。そして、基体上に無機酸化物含有層を設けることにより、その表面上の金属粒子の表面拡散性が促進されて、金属光沢層を不連続の状態で成長させやすくなると考えられる。 As described above, 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. 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. It is considered that the higher the temperature, the smaller the wettability of the metallic gloss layer to the substrate, and the lower the melting point of the material of the metallic gloss layer, the easier it is to form a discontinuous structure. It is considered that the provision of the inorganic oxide-containing layer on the substrate promotes the surface diffusivity of the metal particles on the surface thereof and facilitates the growth of the metallic luster layer in a discontinuous state.
 無機酸化物含有層11としては、酸化インジウム含有層であることが好ましい。
 酸化インジウム含有層として、酸化インジウム(In)そのものを使用することもできるし、例えば、インジウム錫酸化物(ITO)や、インジウム亜鉛酸化物(IZO)のような金属含有物を使用することもできる。酸化インジウム含有層は、酸化インジウム(In)、インジウム錫酸化物(ITO)、又はインジウム亜鉛酸化物(IZO)のいずれかを含むことが好ましい。但し、第二の金属を含有したITOやIZOの方が、スパッタリング工程での放電安定性が高い点で、より好ましい。これらの無機酸化物含有層11を用いることにより、基体の面に沿って連続状態の膜を形成することもでき、また、この場合には、無機酸化物含有層の上に積層される金属光沢層を、例えば、島状の不連続構造としやすくなるため、好ましい。更に、後述するように、この場合には、金属光沢層に、クロム(Cr)又はインジウム(In)だけでなく、通常は不連続構造になり難く、本用途には適用が難しかった、アルミニウム又はアルミニウム合金を含めやすくなる。
The inorganic oxide-containing layer 11 is preferably an indium oxide-containing layer.
As the 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). However, ITO and IZO containing a second metal are more preferable because they have high discharge stability in the sputtering process. By using these inorganic oxide-containing layers 11, 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.
 ITOに含まれる酸化錫(SnО)の質量比率である含有率(含有率=(SnO/(In+SnO))×100)は特に限定されるものではないが、例えば、2.5質量%~30質量%、より好ましくは、3質量%~10質量%である。また、IZOに含まれる酸化亜鉛(ZnO)の質量比率である含有率(含有率=(ZnO/(In+ZnO))×100)は、例えば、2質量%~20質量%である。
 無機酸化物含有層11の厚さは、シート抵抗や電磁波透過性、生産性の観点から、通常1000nm以下が好ましく、50nm以下がより好ましく、20nm以下が更に好ましい。一方、積層される金属光沢層12を不連続状態としやすくするためには、1nm以上であることが好ましく、確実に不連続状態にしやすくするためには、3nm以上であることがより好ましく、5nm以上であることが更に好ましい。
The content rate (content rate = (SnO 2 / (In 2 O 3 + SnO 2 )) × 100) which is the mass ratio of tin oxide (SnО 2 ) contained in ITO is not particularly limited, but is not particularly limited, for example, 2 It is 5.5% by mass to 30% by mass, more preferably 3% by mass to 10% by mass. Further, the content rate (content rate = (ZnO / (In 2 O 3 + ZnO)) × 100), which is the mass ratio of zinc oxide (ZnO) contained in IZO, is, for example, 2% by mass to 20% by mass.
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. On the other hand, in order to facilitate the discontinuous state of the laminated metallic luster layer 12, 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.
<4.金属光沢層>
 金属光沢層12は基体上に形成され、少なくとも一部において互いに不連続の状態にある複数の部分を含み、アルミニウム又はアルミニウム合金を含有する必要がある。
 金属光沢層12が基体上で連続状態である場合、十分な光輝性は得られるものの、電波透過減衰量が非常に大きくなり、従って、電磁波透過性を確保することはできない。
<4. Metallic luster layer>
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.
 金属光沢層12が基体上で不連続状態となるメカニズムの詳細は必ずしも明らかではないが、おおよそ、次のようなものであると推測される。即ち、金属光沢層12の薄膜形成プロセスにおいて、不連続構造の形成しやすさは、金属光沢層12が付与される基体上での表面拡散と関連性があり、基体の温度が高く、基体に対する金属光沢層の濡れ性が小さく、金属光沢層の材料の融点が低い方が不連続構造を形成しやすい、というものである。 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.
 ここで、複数の部分12aの平均粒径とは、複数の部分12aの円相当径の平均値を意味する。部分12aの円相当径とは、部分12aの面積に相当する真円の直径のことである。
 金属光沢層12の部分12aの円相当径は特に限定されないが、通常10~1000nm程度である。また、各部分12a同士の距離は特に限定されないが、通常は10~1000nm程度である。
Here, 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.
 金属光沢層が含む互いに不連続の状態にある複数の部分12aの平均粒径を上記の範囲とすることにより、高い電磁波透過性を維持したまま、光輝性がより向上できる。 By setting the average particle size of the plurality of portions 12a included in the metallic luster layer in a discontinuous state within the above range, the brilliance can be further improved while maintaining high electromagnetic wave transmission.
 金属光沢層12は、十分な光輝性及び良好な透明性を発揮し得ることは勿論、融点が比較的低いものであることが好ましい。金属光沢層12は、スパッタリングを用いた薄膜成長によって形成するのが好ましいためである。
 このような理由から、金属光沢層12としては、融点が約1000℃以下の金属が適しており、アルミニウム又はアルミニウム合金を含有する必要がある。
 また、電磁波透過性金属光沢部材1の透過Y値を上記の範囲にするためには金属光沢層の膜厚を薄くすることが好ましい。しかし、従来の技術では、インジウムや錫等の金属を用いて透過Y値を特定の範囲とした金属光沢層を形成すると、黄色味の強い金属光沢層が得られ、意匠性を損なう。しかしながら、本発明者らは、金属光沢層の形成にアルミニウム又はアルミニウム合金を用いると、透過Y値を特定の範囲とした電磁波透過性金属光沢部材であっても着色を抑えた金属光沢を得られることを見出した。
 金属光沢層12としては、特に、光輝性や透明性、価格等の理由からAl及びそれらの合金であることが好ましい。また、アルミニウム合金を用いる場合には、アルミニウム含有量を50質量%以上とすることが好ましい。
It is preferable that 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. However, in the conventional technique, when a metallic luster layer having a transmission Y value in a specific range is formed by using a metal such as indium or tin, a metallic luster layer having a strong yellowish color is obtained, which impairs the design. However, when aluminum or an aluminum alloy is used to form the metallic luster layer, the present inventors can obtain a metallic luster with suppressed coloring even in an electromagnetically transmissive metallic luster member having a transmission Y value in a specific range. I found that.
The metallic luster layer 12 is particularly preferably Al or an alloy thereof for reasons of brilliance, transparency, price and the like. When an aluminum alloy is used, the aluminum content is preferably 50% by mass or more.
 金属光沢層12の厚さは、着色を抑え十分な光輝性及び良好な透明性を発揮するには3nm以上であることが好ましく、5nm以上であることがより好ましく、7nm以上であることがさらに好ましい。また、透過Y値を所定の範囲としやすくする観点から15nm以下であることが好ましく、12nm以下であることがより好ましく、10nm以下であることがさらに好ましい。
 この厚さは、均一な膜を生産性良く形成するのにも適しており、また、最終製品である加飾部材や樹脂成形品の見栄えも良い。なお、金属光沢層12の厚さは実施例の欄に記載の方法で測定できる。
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.
 金属光沢層のシート抵抗は、100Ω/□以上であるのが好ましい。この場合、電磁波透過性は、5GHzの波長において、10[-dB]程度以下となる。更に好ましくは、1000Ω/□以上である。 The sheet resistance of the metallic luster layer is preferably 100Ω / □ or more. In this case, the electromagnetic wave transmission property is about 10 [−dB] or less at a wavelength of 5 GHz. More preferably, it is 1000 Ω / □ or more.
 無機酸化物含有層を更に設ける場合、電磁波透過性金属光沢部材のシート抵抗も、100Ω/□以上であるのが好ましい。
 シート抵抗は、電磁波透過性の観点から、200Ω/□以上であるのがより好ましく、600Ω/□以上であることが更に好ましく、より更に好ましくは、1000Ω/□以上である。このシート抵抗の値は、金属光沢層の材質や厚さは勿論のこと、下地層である無機酸化物含有層の材質や厚さからも大きな影響を受ける。よって、無機酸化物含有層を設ける場合は、無機酸化物含有層との関係も考慮したうえで設定する必要がある。
When the inorganic oxide-containing layer is further provided, the sheet resistance of the electromagnetic wave transmitting metallic luster member is preferably 100 Ω / □ or more.
From the viewpoint of electromagnetic wave transmission, the sheet resistance is more preferably 200 Ω / □ or more, further preferably 600 Ω / □ or more, still more preferably 1000 Ω / □ 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.
 本実施形態の電磁波透過性金属光沢部材には、本発明の効果を奏する限りにおいて上述の金属光沢層、無機酸化物含有層の他に、用途に応じてその他の層を設けてもよい。その他の層としては色味等の外観を調整するための高屈折材料等の光学調整層(色味調整層)、耐湿性や耐擦傷性等の耐久性を向上させるための保護層(耐擦傷性層)、粘着剤層等の樹脂層等が挙げられる。 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.
<5.樹脂層>
 本実施形態の電磁波透過性金属光沢部材は、樹脂層を備えていてもよい。樹脂層は、金属光沢層の基体側の面と反対側の面に備えていてもよく金属光沢層上に形成してもよい。
<5. Resin layer>
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.
 本実施形態の電磁波透過性金属光沢部材は、金属光沢層の基体側の面と反対側の面に樹脂層を備え、該樹脂層のヘイズ値が20%未満であることが好ましい。
 樹脂層のヘイズ値は、透明性に優れた外観を実現する観点から20%未満が好ましく、10%以下がより好ましく、5%以下が更に好ましい。また、樹脂層のヘイズ値を調整することで、得られる電磁波透過性金属光沢部材のL値、及びa値、及びb値の制御が可能である。
 樹脂層のヘイズ値は、ヘイズメーターHM-150N((株)村上色彩科学研究所製)等の測定機器により測定することができ、実施例に記載の方法により測定することができる。
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.
 樹脂層は、色味等の外観を調整するための高屈折材料等の光学調整層(色味調整層)、耐湿性や耐擦傷性等の耐久性を向上させるための保護層(耐擦傷性層)、易接着層、粘着剤層、上述したハードコート層、反射防止層、光取出し層、アンチグレア層等であってもよい。
 樹脂層は複数設けることができる。
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.
 図4は、本発明の一実施形態による電磁波透過性金属光沢部材の概略断面図である。電磁波透過性金属光沢部材1は、図4に示すとおり、基体10と、無機酸化物含有層11と、金属光沢層12と、樹脂層として粘着剤層13a及びハードコート層13bとを備えていてもよい。本実施形態の電磁波透過性金属光沢部材1は、ハードコート層13bを備えた基体10上に、無機酸化物含有層11と、金属光沢層12と、粘着剤層13aとが設けられている。 FIG. 4 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member according to an embodiment of the present invention. As shown in FIG. 4, 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.
 本実施形態の電磁波透過性金属光沢部材1は、粘着剤層13aを介して被着部材に貼付されて用いられてもよい。例えば、電磁波透過性金属光沢部材1を、粘着剤層13aを介して透明な被着部材に貼付することで被着部材を内側から装飾することができる。
 電磁波透過性金属光沢部材1が透明な被着部材の視認される側(以下、外側ともいう)の面とは反対側(以下、内側ともいう)の面に対して粘着剤層13aを介して貼付された場合、被着部材を通して粘着剤層13aと、金属光沢層12が視認される。透明な被着部材としては、例えば、ガラスやプラスチックからなる部材を使用することができるが、これに限定されるものではない。
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. For example, 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). When attached, the pressure-sensitive adhesive layer 13a and the metallic luster layer 12 are visually recognized through the adherend member. As 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.
 粘着剤層は、透明粘着剤からなる層であることが好ましい。本実施形態の電磁波透過性金属光沢部材は、粘着剤層を介して被着部材に貼付されて用いられてもよい。例えば、基体が基材フィルムやガラス基材の場合、粘着剤層を介して透明な被着部材に貼付することで被着部材を内側から装飾することができる。 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. For example, when the substrate is a substrate film or a glass substrate, the adherend can be decorated from the inside by attaching the substrate to the transparent adherend via the pressure-sensitive adhesive layer.
 粘着剤層を形成する粘着剤は透明粘着剤であれば特に限定されず、例えばアクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ウレタン系粘着剤、エポキシ系粘着剤、及びポリエーテル系粘着剤のいずれかを単独で、或いは、2種類以上を組み合わせて使用することができる。透明性、加工性及び耐久性などの観点から、アクリル系粘着剤を用いることが好ましい。 The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited as long as it is a transparent pressure-sensitive adhesive. , And 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.
 粘着剤層の厚みは特に限定されないが、薄くすることで最終製品構成の薄型化への寄与や可視光透過性や膜厚精度、平坦性を向上させることができるため、100μm以下であることが好ましく、75μm以下であることがより好ましく、50μm以下であることがさらに好ましい。 The thickness of the pressure-sensitive adhesive layer is not particularly limited, but it should be 100 μm 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 μm or less, and even more preferably 50 μm or less.
 粘着剤層全体の透過Y値は特に限定はされないが、JIS K7361に従って測定した任意の可視光波長における値で10%以上であることが好ましく、30%以上であることがより好ましく、50%以上であることがさらに好ましい。粘着剤層の透過Y値は、高いほど好ましい。 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.
 また、粘着剤層を構成する透明粘着剤は着色されていてもよい。
 この場合、例えば、図3中に示す電磁波透過性金属光沢部材の構成においては、良好な透明性を有する金属光沢層を介して着色された粘着剤層が視認されることとなるので、電磁波透過性金属光沢部材1は粘着剤層の色調を変えることなく着色された金属光沢を発現することができる。
Further, the transparent adhesive constituting the adhesive layer may be colored.
In this case, for example, in the configuration of the electromagnetically transmissive metallic luster member shown in FIG. 3, 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.
 透明粘着剤を着色する方法は特に限定されないが、例えば色素を微量添加することにより着色することができる。 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.
 粘着剤層の上には、被着部材に貼付する際まで粘着剤層を保護するために、剥離ライナーを設けてもよい。 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.
<6.電磁波透過性金属光沢部材の製造>
 電磁波透過性金属光沢部材の製造方法の一例について、説明する。特に説明しないが、基材フィルム以外の基体を用いた場合についても同様の方法で製造することができる。
<6. Manufacture of electromagnetic wave-permeable metallic luster members>
An example of a method for manufacturing an electromagnetic wave-transmitting metallic luster member will be described. Although not particularly described, it can be produced by the same method when a substrate other than the substrate film is used.
 基体10上に金属光沢層12を形成するにあたっては、例えば、真空蒸着、スパッタリング等の方法を用いることができる。 In forming the metallic luster layer 12 on the substrate 10, for example, a method such as vacuum vapor deposition or sputtering can be used.
 また、基体10上に無機酸化物含有層11を形成する場合には、金属光沢層12の形成に先立ち、無機酸化物含有層11を、真空蒸着、スパッタリング、イオンプレーティング等によって形成する。但し、大面積でも厚さを厳密に制御できる点から、スパッタリングが好ましい。 When 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. However, sputtering is preferable because the thickness can be strictly controlled even in a large area.
 粘着剤層を設ける場合には、粘着剤層を設ける面に粘着剤組成物を塗布等することにより形成できる。
 粘着剤組成物の塗布は、慣用のコーター、例えば、グラビヤロールコーター、リバースロールコーター、キスロールコーター、ディップロールコーター、バーコーター、ナイフコーター、スプレーコーターなどを用いて行うことができる。乾燥温度は、適宜採用可能であるが、好ましくは40℃~200℃であり、さらに好ましくは、50℃~180℃であり、特に好ましくは70℃~120℃である。乾燥時間は、適宜、適切な時間が採用され得る。上記乾燥時間は、好ましくは5秒~20分、さらに好ましくは5秒~10分、特に好ましくは、10秒~5分である。
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. As the drying time, 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.
 尚、基体10と金属光沢層12の間に無機酸化物含有層11を設ける場合、無機酸化物含有層11と金属光沢層12の間には、他の層を介在させずに直接接触させるのが好ましい。 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.
<7.加飾部材>
 本実施形態に係る加飾部材は、被着部材と、上述の電磁波透過性金属光沢部材とを備え、前記電磁波透過性金属光沢部材(電磁波透過性金属光沢部材1)が前記粘着剤層を介して前記被着部材に貼付されている。
 本実施形態に係る加飾部材は、被着部材と、透明粘着剤からなる粘着剤層を備える上述の電磁波透過性金属光沢部材とを備え、前記電磁波透過性金属光沢部材が前記粘着剤層を介して前記被着部材に貼付されていることが好ましい。
<7. Decorative material >
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.
 図3に、本発明の一実施形態による加飾部材2の概略断面図を示す。本発明の一実施形態による加飾部材2は、電磁波透過性金属光沢部材1が被着部材15に貼付された状態の概略断面図である。本実施形態の加飾部材2は、金属光沢層12、無機酸化物含有層11、基体10(基材フィルム)、及び粘着剤層14を備えた電磁波透過性金属光沢部材1が被着部材15に貼付されている。
 本実施形態の電磁波透過性金属光沢部材1は、電磁波透過性金属光沢部材1が黄色味等の着色を抑えた金属光沢を有し、視認性に優れるため、被着部材15の表面に設けた意匠、色及び質感をそのまま活かしつつ被着部材15を装飾した加飾部材2を得ることができる。
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. In the decorative member 2 of the present embodiment, 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.
 電磁波透過性金属光沢部材1は、透明な被着部材15の内側の面に貼付して用いてもよい。透明な被着部材15としては、例えば、ガラスやプラスチックからなる部材を使用することもできるが、これに限定されるものではない。 The electromagnetic wave transmitting metallic luster member 1 may be used by being attached to the inner surface of the transparent adherend member 15. As 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.
 電磁波透過性金属光沢部材1を被着部材15に貼付する方法は特に限定されないが、例えば真空成形により貼付することができる。真空成形とは、電磁波透過性金属光沢部材1を加熱軟化しつつ展張し、電磁波透過性金属光沢部材1の被着部材側の空間を減圧し、必要に応じ反対側の空間を加圧することにより、電磁波透過性金属光沢部材1を被着部材の表面の三次元立体形状に沿って成形しつつ貼付積層する方法である。
 電磁波透過性金属光沢部材1としては、上述の説明をそのまま援用し得る。
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.
As the electromagnetic wave transmitting metallic luster member 1, the above description can be used as it is.
<8.電磁波透過性金属光沢部材及び加飾部材の用途>
 本実施形態の電磁波透過性金属光沢部材及び金属薄膜は、電磁波透過性を有することから電磁波を送受信する装置や物品及びその部品等に使用することが好ましい。例えば、車両用構造部品、車両搭載用品、電子機器の筐体、家電機器の筐体、構造用部品、機械部品、種々の自動車用部品、電子機器用部品、家具、台所用品等の家財向け用途、医療機器、建築資材の部品、その他の構造用部品や外装用部品等が挙げられる。
 より具体的には、車両関係では、インスツルメントパネル、コンソールボックス、ドアノブ、ドアトリム、シフトレバー、ペダル類、グローブボックス、バンパー、ボンネット、フェンダー、トランク、ドア、ルーフ、ピラー、座席シート、ステアリングホイール、ECUボックス、電装部品、エンジン周辺部品、駆動系・ギア周辺部品、吸気・排気系部品、冷却系部品等が挙げられる。
 電子機器および家電機器としてより具体的には、冷蔵庫、洗濯機、掃除機、電子レンジ、エアコン、照明機器、電気湯沸かし器、テレビ、時計、換気扇、プロジェクター、スピーカー等の家電製品類、パソコン、携帯電話、スマートフォン、デジタルカメラ、タブレット型PC、携帯音楽プレーヤー、携帯ゲーム機、充電器、電池等電子情報機器等が挙げられる。
<8. Applications of 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. For example, 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.
More specifically, in the vehicle field, instrument panels, console boxes, door knobs, door trims, shift levers, pedals, glove boxes, bumpers, bonnets, fenders, trunks, doors, roofs, pillars, seats, steering wheels. , ECU box, electrical parts, engine peripheral parts, drive system / gear peripheral parts, intake / exhaust system parts, cooling system parts and the like.
More specifically as electronic devices and home appliances, 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.
 以下、実施例及び比較例を挙げて、本発明をより具体的に説明する。電磁波透過性金属光沢部材を作製し評価を行った。なお、基体10としては、基材フィルムを用いた。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. An electromagnetic wave-transmitting metallic luster member was prepared and evaluated. As the substrate 10, a substrate film was used.
 評価方法の詳細は以下のとおりである。
<透過特性>
 水縁磨ガラスS200200(松浪硝子工業(株)製)に、透明粘着剤CS9861UAS(日東電工(株)製)のセパレーターを剥離しハンドローラーで貼り合せた後、もう一方のセパレーターを剥離し、電磁波透過性金属光沢部材の金属光沢層側の面に透明粘着剤が貼り合されるようにハンドローラーで貼り合せて透過率測定サンプルを得た。
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.
 透過率測定サンプルを、積分球式分光透過率測定器 DOT-3C((株)村上色彩技術研究所製)で波長380nm~700nmの範囲の可視光線を標準光源D65を用いて電磁波透過性金属光沢部材の基体側の面に入射して透過率測定を行い、透過特性(透過Y値、a値及びb値)を得た。得られたY値、a値及びb値を表1に記載した。 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.
<反射特性>
 水縁磨ガラスS200200(松浪硝子工業(株)製)に、透明粘着剤CS9861UAS(日東電工(株)製)のセパレーターを剥離しハンドローラーで貼り合せた後、もう一方のセパレーターを剥離し、電磁波透過性金属光沢部材の金属光沢層側の面に透明粘着剤が貼り合されるようにハンドローラーで貼り合せ、さらにその反対面に遮光のためNo.21ビニールテープ黒(日東電工(株)製)をハンドローラーで貼り合せて反射率測定サンプルを得た。
<Reflection 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 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.
 反射率測定サンプルを、分光測色計CM-2600d(コニカミノルタ(株)製)で波長360nm~740nmの範囲の可視光線を標準光源D65を用いてガラス側の面に入射して反射率測定を行い、反射特性(反射Y値、a値及びb値)を得た。得られたY値、a値及びb値を表1に記載した。 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.
<シート抵抗>
 ナプソン社製非接触式抵抗測定装置NC-80MAPを用い、JIS-Z2316に準拠し、渦電流測定法により電磁波透過性金属光沢部材のシート抵抗を測定した。
<Sheet resistance>
Using a non-contact resistance measuring device NC-80MAP manufactured by Napson, the sheet resistance of the electromagnetic wave transmitting metallic luster member was measured by an eddy current measuring method in accordance with JIS-Z2316.
<膜厚>
 金属光沢層におけるバラツキ、更に詳細には、図2に示す部分12aの厚さにおけるバラツキを考慮して、部分12aの厚さの平均値を金属光沢層の厚さ(Al膜厚(nm))とした。なお、個々の部分12aの厚さは、基体10から垂直方向に最も厚いところの厚さとした。以下、この平均値を、便宜上、「最大の厚さ」と呼ぶ。図6に、電磁波透過性金属光沢部材の断面の電子顕微鏡写真(TEM画像)の例を示す。
 最大の厚さを求めるに際し、まず、図6に示すような電磁波透過性金属光沢部材の表面に現れた金属光沢層において、図5に示すような一辺5cmの正方形領域3を適当に抽出し、該正方形領域3の縦辺及び横辺それぞれの中心線A、Bをそれぞれ4等分することによって得られる計5箇所の点「a」~「e」を測定箇所として選択した。
 次いで、選択した測定箇所それぞれにおける、図6に示すような断面画像において、おおよそ5個の部分12aが含まれる視野角領域を抽出した。これら計5箇所の測定箇所それぞれにおける、おおよそ5個の部分12a、即ち、25個(5個×5箇所)の部分12aの個々の厚さ(nm)を求め、それらの平均値を「最大の厚さ」とした。
<Film thickness>
Considering the variation in the metallic luster layer, and more specifically, the variation in the thickness of the portion 12a shown in FIG. 2, 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. Hereinafter, 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. 6, 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.
Next, in the cross-sectional image as shown in FIG. 6 at each of the selected 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".
<ヘイズ値>
 樹脂層のヘイズ値について、JIS7136で定める方法により、ヘイズメーター(装置名:HM-150N、(株)村上色彩科学研究所製)を用いて測定した。
 水縁磨ガラスS200200(松浪硝子工業(株)製)に、透明粘着剤CS9861UAS(日東電工(株)製)のセパレーターを剥離しハンドローラーで貼り合せた後、もう一方のセパレーターを剥離したもののヘイズ値を測定したところ、1.0%以下であった。
<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.
[実施例1]
 基材フィルムとして、東レ株式会社製PETフィルム50-U483(厚さ50μm)に厚み2μmの紫外線硬化樹脂層(ハードコート層)を形成し、紫外線硬化樹脂層付きPETフィルムのヘイズ値が2%以下のフィルムを用いた。
 先ず、DCマグネトロンスパッタリング装置にITOターゲットを取り付け、ArガスとOガスを導入しながらスパッタリングをする事で基材フィルムの面に沿って、5nmの厚さのITO層を紫外線硬化樹脂層の上に直接形成した。ITO層を形成する際の基材フィルムの温度は、50℃に設定した。ITOに含まれる酸化錫(SnO)の含有率(含有率=(SnO/(In+SnO))×100)は10質量%である。
[Example 1]
As a base film, a UV curable resin layer (hard coat layer) having a thickness of 2 μm is formed on a PET film 50-U483 (thickness 50 μm) 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.
First, 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. The content of tin oxide (SnO 2 ) contained in ITO (content rate = (SnO 2 / (In 2 O 3 + SnO 2 )) × 100) is 10% by mass.
 DCマグネトロンスパッタリング装置にアルミニウム(Al)ターゲットを取り付け、Arガスを導入しながらスパッタリングする事でITO層の上に、9nmの厚さのAl層(金属光沢層)を形成し実施例1の積層体1を得た。得られたAl層は不連続層であった。Al層を形成する際の基材フィルムの温度は、50℃に設定した。 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.
 以上により基材フィルム、紫外線硬化樹脂層、酸化インジウム含有層、金属光沢層の積層体である実施例1の電磁波透過性金属光沢部材を得た。得られた電磁波透過性金属光沢部材の透過特性を上記の方法により測定し、表1に記載した。 From the above, 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.
 <加飾部材の製造>
 被着部材として、表面に意匠を施した厚み0.7mmのガラスを用いた。
 上記で得られた電磁波透過性金属光沢部材を、粘着剤CS9861UAS(日東電工(株)製)を用いて被着部材に貼付し、電磁波透過性金属光沢部材の基材フィルム側の面と被着部材とが粘着剤を介して貼り合わされた加飾部材を得た。
<Manufacturing of decorative materials>
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.
[実施例2~3]
 実施例1におけるAl層の膜厚を変更し、表1に記載のとおりの透過特性及び反射特性を示す電磁波透過性金属光沢部材及び加飾部材を得た。
[Examples 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.
[比較例1~4]
 基材フィルムとして、東レ株式会社製PETフィルム50-U483(厚さ50μm)に厚み2μmの紫外線硬化樹脂層(ハードコート層)を形成したフィルムを用いた。
 抵抗加熱式高真空蒸着装置を用いて、基材フィルムの紫外線硬化樹脂層の上に室温(25℃)でIn層を形成した。得られたIn層は不連続であった。Inの堆積量を変化させること以外は実施例1と同様にして表1に記載のとおりの透過特性及び反射特性を示す電磁波透過性金属光沢部材及び加飾部材を得た。
[Comparative Examples 1 to 4]
As the base film, a film obtained by forming an ultraviolet curable resin layer (hard coat layer) having a thickness of 2 μm on a PET film 50-U483 (thickness 50 μm) 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.
[比較例5~7]
 基材フィルムとして、東レ株式会社製PETフィルム50-U483(厚さ50μm)に厚み2μmの紫外線硬化樹脂層(ハードコート層)を形成したフィルムを用いた。
 抵抗加熱式高真空蒸着装置を用いて、基材フィルムの紫外線硬化樹脂層の上にSn層を形成した。得られたSn層は不連続であった。Snの堆積量を変化させること以外は実施例1と同様にして表1に記載のとおりの透過特性及び反射特性を示す電磁波透過性金属光沢部材及び加飾部材を得た。
[Comparative Examples 5 to 7]
As the base film, a film obtained by forming an ultraviolet curable resin layer (hard coat layer) having a thickness of 2 μm on a PET film 50-U483 (thickness 50 μm) 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.
 以下の表1に、評価結果を示す。また、実施例と比較例の電磁波透過性金属光沢部材の透過光のa値とb値との関係を図7に示す。透過Y値とa値との関係を図8に、また、透過Y値とb値との関係を図9に示す。更に、実施例と比較例の電磁波透過性金属光沢部材の反射光のa値とb値との関係を図10に示す。反射Y値とa値との関係を図11に、また、反射Y値とb値との関係を図12に示す。 The evaluation results are shown in Table 1 below. Further, 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. Further, 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 表1から明らかなように、実施例1~3の電磁波透過性金属光沢部材は、金属光沢層にアルミニウムを用い、反射Y値が10~25%であり、かつ透過Y値が30~65%であることから、優れた電磁波透過性を有し、着色を抑えた金属光沢を示した。また、実施例1~3の電磁波透過性金属光沢部材は透明性に優れるため、被着部材の表面形状が視認可能な加飾部材が得られた。
 インジウムを金属光沢層に用いた比較例1~4、及びスズを金属光沢層に用いた比較例5~7は、反射a値、反射b値、透過a値、透過b値の値が実施例に比べ0から離れ、着色の度合いが高いことを示した。
As is clear from Table 1, 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.
 本発明は前記実施例に限定されるものではなく、発明の趣旨から逸脱しない範囲で適宜変更して具体化することもできる。 The present invention is not limited to the above embodiment, and can be appropriately modified and embodied without departing from the spirit of the invention.
 本発明に係る電磁波透過性金属光沢部材は、電磁波を送受信する装置や物品及びその部品等に使用することができる。例えば、車両用構造部品、車両搭載用品、電子機器の筐体、家電機器の筐体、構造用部品、機械部品、種々の自動車用部品、電子機器用部品、家具、台所用品等の家財向け用途、医療機器、建築資材の部品、その他の構造用部品や外装用部品等、意匠性と電磁波透過性の双方が要求される様々な用途にも利用できる。 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. For example, 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.
 本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
 本出願は、2020年6月30日出願の日本特許出願(特願2020-112898)に基づくものであり、その内容はここに参照として取り込まれる。
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on June 30, 2020 (Japanese Patent Application No. 202-112898), the contents of which are incorporated herein by reference.
1 電磁波透過性金属光沢部材
2 加飾部材
10 基体
11 無機酸化物含有層
12 金属光沢層
12a 部分
12b 隙間
13a、14 粘着剤層
13b ハードコート層
15 被着部材
1 Electromagnetic wave transmissive metallic luster member 2 Decorative member 10 Base material 11 Inorganic oxide-containing layer 12 Metallic luster layer 12a Part 12b Gap 13a, 14 Adhesive layer 13b Hard coat layer 15 Adhesive member

Claims (13)

  1.  基体と、前記基体上に形成された金属光沢層とを備え、
     前記金属光沢層は、少なくとも一部において互いに不連続の状態にある複数の部分を含み、
     前記金属光沢層はアルミニウム又はアルミニウム合金を含有し、
     CIE-XYZ表色系のSCI方式の反射Y値が10~25%であり、かつ透過Y値が30~65%である、電磁波透過性金属光沢部材。
    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%.
  2.  前記基体と前記金属光沢層との間に無機酸化物含有層をさらに備える、請求項1に記載の電磁波透過性金属光沢部材。 The electromagnetic wave-transmitting metallic luster member according to claim 1, further comprising an inorganic oxide-containing layer between the substrate and the metallic luster layer.
  3.  前記無機酸化物含有層が酸化インジウム含有層である、請求項2に記載の電磁波透過性金属光沢部材。 The electromagnetic wave-permeable metallic luster member according to claim 2, wherein the inorganic oxide-containing layer is an indium oxide-containing layer.
  4.  前記酸化インジウム含有層は、酸化インジウム(In)、インジウム錫酸化物(ITO)、又はインジウム亜鉛酸化物(IZO)のいずれかを含む、請求項3に記載の電磁波透過性金属光沢部材。 The electromagnetic wave transmissive metal gloss member according to claim 3, wherein the indium oxide-containing layer contains any one of indium oxide (In 2 O 3 ), indium tin oxide (ITO), and indium zinc oxide (IZO). ..
  5.  前記無機酸化物含有層は連続状態で設けられている、請求項2~4のいずれか1項に記載の電磁波透過性金属光沢部材。 The electromagnetic wave-transmitting metallic luster member according to any one of claims 2 to 4, wherein the inorganic oxide-containing layer is provided in a continuous state.
  6.  前記無機酸化物含有層の厚さは、1nm~1000nmである、請求項2~5のいずれか1項に記載の電磁波透過性金属光沢部材。 The electromagnetic wave-transmitting metallic luster member according to any one of claims 2 to 5, wherein the thickness of the inorganic oxide-containing layer is 1 nm to 1000 nm.
  7.  前記金属光沢層の基体側の面と反対側の面に樹脂層を備え、該樹脂層のヘイズ値が20%未満である、請求項1~6のいずれか1項に記載の電磁波透過性金属光沢部材。 The electromagnetic wave transmitting metal according to any one of claims 1 to 6, wherein the metallic luster layer is provided with a resin layer on the surface opposite to the surface on the substrate side, and the haze value of the resin layer is less than 20%. Glossy member.
  8.  前記金属光沢層の厚さは、3nm~10nmである、請求項1~7のいずれか1項に記載の電磁波透過性金属光沢部材。 The electromagnetic wave-transmitting metallic luster member according to any one of claims 1 to 7, wherein the metallic luster layer has a thickness of 3 nm to 10 nm.
  9.  シート抵抗が、100Ω/□以上である、請求項1~8のいずれか1項に記載の電磁波透過性金属光沢部材。 The electromagnetic wave transmissive metallic luster member according to any one of claims 1 to 8, wherein the sheet resistance is 100 Ω / □ or more.
  10.  前記複数の部分は島状に形成されている、請求項1~9のいずれか1項に記載の電磁波透過性金属光沢部材。 The electromagnetic wave-transmitting metallic luster member according to any one of claims 1 to 9, wherein the plurality of portions are formed in an island shape.
  11.  前記基体は、基材フィルム、樹脂成型物基材、ガラス基材、又は金属光沢を付与すべき物品のいずれかである、請求項1~10のいずれか1項に記載の電磁波透過性金属光沢部材。 The electromagnetic wave transmissive metallic luster according to any one of claims 1 to 10, wherein the substrate is any of a substrate film, a resin molded substrate, a glass substrate, or an article to which metallic luster should be imparted. Element.
  12.  透明粘着剤からなる粘着剤層をさらに備える、請求項1~11のいずれか1項に記載の電磁波透過性金属光沢部材。 The electromagnetic wave-transmitting metallic luster member according to any one of claims 1 to 11, further comprising a pressure-sensitive adhesive layer made of a transparent pressure-sensitive adhesive.
  13.  被着部材と、請求項12に記載の電磁波透過性金属光沢部材とを備え、前記電磁波透過性金属光沢部材が前記粘着剤層を介して前記被着部材に貼付されている、加飾部材。
     
    A decorative member comprising the adherend member and the electromagnetic wave-permeable metallic luster member according to claim 12, wherein the electromagnetic wave-permeable metallic luster member is attached to the adherend member via the pressure-sensitive adhesive layer.
PCT/JP2021/024389 2020-06-30 2021-06-28 Electromagnetic wave-transmissive member with metallic luster, and decorative member WO2022004670A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009166384A (en) * 2008-01-17 2009-07-30 Toppan Printing Co Ltd Decorative plate for wireless apparatus
JP2011163903A (en) * 2010-02-09 2011-08-25 Kanto Kasei Kogyo Kk Electromagnetic-wave transmitting metal coating, method for forming metal coating for electromagnetic-wave transmission, and in-vehicle radar apparatus
JP2018154878A (en) * 2017-03-17 2018-10-04 株式会社Jcu Metal film for electromagnetic wave transmission, formation method of metal film for electromagnetic wave transmission, and on-vehicle radar device
JP2019123224A (en) * 2018-01-12 2019-07-25 日東電工株式会社 Electromagnetic wave transmissible half mirror-tone film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009166384A (en) * 2008-01-17 2009-07-30 Toppan Printing Co Ltd Decorative plate for wireless apparatus
JP2011163903A (en) * 2010-02-09 2011-08-25 Kanto Kasei Kogyo Kk Electromagnetic-wave transmitting metal coating, method for forming metal coating for electromagnetic-wave transmission, and in-vehicle radar apparatus
JP2018154878A (en) * 2017-03-17 2018-10-04 株式会社Jcu Metal film for electromagnetic wave transmission, formation method of metal film for electromagnetic wave transmission, and on-vehicle radar device
JP2019123224A (en) * 2018-01-12 2019-07-25 日東電工株式会社 Electromagnetic wave transmissible half mirror-tone film

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