CN112004663B - Electromagnetic wave-transparent metallic glossy article and metallic film - Google Patents
Electromagnetic wave-transparent metallic glossy article and metallic film Download PDFInfo
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- CN112004663B CN112004663B CN201980027636.6A CN201980027636A CN112004663B CN 112004663 B CN112004663 B CN 112004663B CN 201980027636 A CN201980027636 A CN 201980027636A CN 112004663 B CN112004663 B CN 112004663B
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 137
- 239000002184 metal Substances 0.000 claims abstract description 137
- 239000000758 substrate Substances 0.000 claims abstract description 49
- 239000002932 luster Substances 0.000 claims abstract description 32
- 238000001228 spectrum Methods 0.000 claims abstract description 12
- 229910003437 indium oxide Inorganic materials 0.000 claims description 42
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 3
- 238000002310 reflectometry Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 144
- 239000010408 film Substances 0.000 description 48
- 239000010409 thin film Substances 0.000 description 24
- -1 zinc sulfide (ZnS) Chemical class 0.000 description 15
- 230000035699 permeability Effects 0.000 description 14
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- 238000000034 method Methods 0.000 description 12
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- 239000011651 chromium Substances 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
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- 238000000635 electron micrograph Methods 0.000 description 2
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- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/14—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
Landscapes
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The present invention relates to an electromagnetic wave-transparent metallic luster article (1), which comprises: a substrate (10) and a metal layer (12) formed on the substrate (10), wherein the maximum value of the reflectance in the total reflection spectrum of the metal layer (12) is in the range of 380nm to 780 nm.
Description
Technical Field
The present invention relates to an electromagnetic wave-transparent metallic glossy article and a metallic film.
Background
Conventionally, a member having electromagnetic wave permeability and metallic luster has both an excellent appearance derived from metallic luster and electromagnetic wave permeability, and is therefore suitable for use in a device for transmitting/receiving electromagnetic waves.
For example, there is a demand for a metallic luster article having both brightness and electromagnetic wave permeability, which is decorated on a cover member of a millimeter wave radar mounted on a front part of an automobile, such as a front grille or a emblem.
Millimeter wave radar can measure the distance to a target object, the direction of the target object, and the size by transmitting electromagnetic waves in the millimeter wave band (frequency of about 77GHz, wavelength of about 4 mm) to the front of an automobile, receiving reflected waves from the target object, and measuring and analyzing the reflected waves.
The measurement results can be used for inter-vehicle distance measurement, automatic speed adjustment, automatic braking adjustment and the like.
The front part of an automobile equipped with such millimeter wave radar can be said to be the face of the automobile, and is a part that has a great influence on the user, and therefore, it is preferable to exhibit a sense of high quality by metallic luster-like front decoration. However, in the case where a metal is used for the front part of the automobile, transmission/reception of electromagnetic waves based on millimeter wave radar is virtually impossible or may be hindered. Therefore, in order not to interfere with the function of the millimeter wave radar and not to impair the external appearance of the automobile, a metallic glossy article having both of the brightness and the electromagnetic wave permeability is required.
Such a metallic luster article can be expected to be applied not only to millimeter wave radars but also to various devices requiring communication, for example, door handles of automobiles provided with smart keys, in-vehicle communication devices, electronic devices such as mobile phones and personal computers, and the like. Further, in recent years, with the development of IoT technology, applications in a wide range of fields such as home appliances such as refrigerators and living facilities, in which communication has not been performed conventionally, have been expected.
Regarding the metallic luster member, japanese patent application laid-open No. 2007-144988 (patent document 1) discloses a resin product including a metal coating film formed of chromium (Cr) or indium (In). The resin article comprises: a resin substrate, an inorganic base film comprising an inorganic compound formed on the resin substrate, and a metal coating film comprising chromium (Cr) or indium (In) having a brightness and a discontinuous structure formed on the inorganic base film by a physical vapor deposition method. As the inorganic base film, patent document 1 uses (a) a thin film of a metal compound, for example, titanium oxide (TiO ) 2 、Ti 3 O 5 Etc.) and the like; silicon oxide (SiO ) 2 Etc.), silicon nitride (Si 3 N 4 Etc.) and the like; aluminum oxide (Al) 2 O 3 ) An isopoly compound; iron oxide (Fe) 2 O 3 ) An isoiron compound; selenium compounds such as selenium oxide (CeO); zirconium compounds such as zirconium oxide (ZrO); zinc compounds such as zinc sulfide (ZnS), and the like, (b) coating films of inorganic paints, for example, silica and amorphous TiO z And the like (and the above-exemplified metal compounds) as a main component.
On the other hand, japanese patent application laid-open No. 2009-298006 (patent document 2) discloses an electromagnetic wave transparent bright resin product In which not only chromium (Cr) or indium (In) but also aluminum (Al), silver (Ag), and nickel (Ni) can be formed into metal films.
Japanese patent application laid-open No. 2010-5999 (patent document 3) describes the following method: a method for manufacturing a metallic film decorative sheet having slit electromagnetic wave permeability by forming a metallic film layer on a base sheet, applying tension to the base sheet, and performing heat treatment.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2007-144988
Patent document 2: japanese patent laid-open No. 2009-298006
Patent document 3: japanese patent application laid-open No. 2010-5999
Disclosure of Invention
Problems to be solved by the invention
However, the inventors of the present invention have found that it is difficult to obtain a good metallic appearance in the conventional metallic glossy article because the reflection spectrum of the metal layer has a frequency characteristic, that is, the reflectance differs at each wavelength of light.
The present invention has been made in view of the above, and an object thereof is to provide an electromagnetic wave-transparent metallic glossy article having a good metallic appearance.
Solution for solving the problem
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by controlling the wavelength at which the maximum value of reflectance is displayed in the total reflection spectrum of a metal layer to an appropriate range for an electromagnetic wave-transparent metallic glossy article having the metal layer.
An electromagnetic wave-transparent metallic luster article according to the present invention comprises: the metal layer has a maximum reflectance in a total reflection spectrum in a range of 380nm to 780 nm.
In one aspect of the electromagnetic wave-transparent metallic lustrous article according to the present invention, the metallic layer preferably includes a plurality of portions, at least a part of the plurality of portions being discontinuous with each other, and an average particle diameter of the plurality of portions is 100 to 500nm.
In one embodiment of the electromagnetic wave-transparent metallic glossy article according to the present invention, it is preferable that a layer containing indium oxide is further provided between the base and the metal layer.
In one embodiment of the electromagnetic wave-transparent metallic glossy article according to the present invention, the indium oxide-containing layer is preferably provided in a continuous state.
In one embodiment of the electromagnetic wave-transparent metallic glossy article according to the present invention, the indium oxide-containing layer preferably contains indium oxide (In 2 O 3 ) Any of Indium Tin Oxide (ITO), or Indium Zinc Oxide (IZO).
In one embodiment of the electromagnetic wave-transparent metallic glossy article according to the present invention, the indium oxide-containing layer preferably has a thickness of 1nm to 1000nm.
In one embodiment of the electromagnetic wave-transparent metallic glossy article according to the present invention, the thickness of the metal layer is preferably 20nm to 100nm.
In one embodiment of the electromagnetic wave-transparent metallic lustrous article according to the present invention, the ratio of the thickness of the metal layer to the thickness of the indium oxide-containing layer (the thickness of the metal layer/the thickness of the indium oxide-containing layer) may be 0.02 to 100.
In one embodiment of the electromagnetic wave-transparent metallic lustrous article of the present invention, the sheet resistance may be 100 Ω/≡or more.
In one embodiment of the electromagnetic wave-transparent metallic lustrous article according to the present invention, the plurality of portions may be formed in an island shape.
In one embodiment of the electromagnetic wave-transparent metallic glossy article according to the present invention, the metal layer is preferably any one of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag), or an alloy thereof.
In one embodiment of the electromagnetic wave-transparent metallic lustrous article according to the present invention, the base is preferably any one of a base film, a resin molded base, a glass base, and an article to which metallic lustrous is to be imparted.
The metal film of the present invention is a metal film formed on a substrate,
the metal thin film has a thickness of 20nm to 100nm, and a maximum value of reflectance in a total reflection spectrum is in a range of 380nm to 780 nm.
In one embodiment of the metal thin film of the present invention, it is preferable that the metal thin film includes a plurality of island-like portions, at least a part of the island-like portions are in a discontinuous state, and an average particle diameter of the island-like portions is 100 to 500nm.
In one embodiment of the metal thin film of the present invention, the metal thin film is preferably any one of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag), or an alloy thereof.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, an electromagnetic wave-transparent metallic glossy article having a good metallic appearance can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view of an electromagnetic wave-transparent metallic glossy article according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of an electromagnetic wave-transparent metallic glossy article according to an embodiment of the present invention.
Fig. 3 is an electron micrograph of the surface of an electromagnetic wave-transparent metallic glossy article according to an embodiment of the present invention.
Fig. 4 is a diagram for explaining a method of measuring the film thickness of the metal layer of the electromagnetic wave-transparent metal luster article according to an embodiment of the present invention.
Fig. 5 is a view showing a transmission electron micrograph (TEM image) of a cross section of a metal layer in an embodiment of the present invention.
Detailed Description
Hereinafter, a preferred embodiment of the present invention will be described with reference to the accompanying drawings. Hereinafter, for convenience of explanation, only suitable embodiments of the present invention are shown, but it is needless to say that the present invention is not limited thereto.
<1. Basic constitution >
Fig. 1 shows a schematic cross-sectional view of an electromagnetic wave-transparent metal luster article (hereinafter referred to as "metal luster article") 1 according to an embodiment of the present invention, and fig. 3 shows an electron micrograph (SEM image) of the surface of the metal luster article 1 according to an embodiment of the present invention. Fig. 5 shows a transmission electron micrograph (TEM image) of a cross section of the island-structured metal layer 12 according to an embodiment of the present invention.
The metallic luster article 1 comprises: a substrate 10, and a metal layer 12 formed on the substrate 10.
A metal layer 12 is formed on the substrate 10. The metal layer 12 preferably includes a plurality of portions 12a, at least a portion of the plurality of portions 12a being in a discontinuous state with respect to each other. At least a part of these portions 12a in the metal layer 12 are in a state of being discontinuous with each other, in other words, at least a part is separated by a gap 12 b. When the gap 12b is used, the sheet resistance of the metallic lustrous article increases and interaction with the radio wave decreases, so that the radio wave is easily transmitted, which is preferable. Each of these portions 12a may be an aggregate of sputtered particles formed by vapor deposition, sputtering, or the like of metal.
The structure of the metal layer 12 is not limited to the structure including a plurality of portions 12a at least a part of which is in a discontinuous state, and may be a continuous structure as long as electromagnetic wave permeability can be ensured.
The term "discontinuous state" as used herein refers to a state in which the two are separated by the gap 12b, and as a result, the two are electrically insulated from each other. By electrically insulating, the sheet resistance of the metallic luster article increases, and the desired electromagnetic wave permeability is easily obtained. That is, by using the metal layer 12 formed in a discontinuous state, sufficient brightness is easily obtained, and electromagnetic wave permeability is easily ensured. The discontinuous form is not particularly limited, and includes, for example, an island structure, a crack structure, and the like. The "island structure" here means, as shown in fig. 3, a structure in which metal particles are independent of each other and the particles are spread apart from each other slightly or in a state where a part of the particles are in contact with each other.
The slit structure refers to a structure in which a metal thin film is ruptured by a slit.
The metal layer 12 having a slit structure can be formed by, for example, providing a metal thin film layer on a base film, and bending and stretching the metal thin film layer to cause a slit. In this case, by providing a brittle layer formed of a material that lacks stretchability, that is, is susceptible to the formation of cracks by stretching, between the base film and the metal film layer, the metal layer 12 having a crack structure can be easily formed.
As described above, the discontinuous form of the metal layer 12 is not particularly limited, and an island structure is preferably used from the viewpoint of productivity.
The electromagnetic wave permeability of the metallic lustrous article 1 can be evaluated by, for example, the amount of attenuation of radio wave transmission. In the metallic lustrous article 1, the attenuation of radio wave transmission in the microwave band (5 GHz) measured by the method described in the column of the examples is preferably 10 < -dB > or less, more preferably 5 < -dB > or less, and still more preferably 2 < -dB > or less. If the ratio is more than 10 < -dB >, more than 90% of the radio waves are blocked. Since the radio wave transmission attenuation amount in the microwave band (1 GHz) and the radio wave transmission attenuation amount in the frequency band (76 to 80 GHz) of the millimeter wave radar have a correlation and show relatively close values, the metallic luster article excellent in the electromagnetic wave transmission in the microwave band is also excellent in the electromagnetic wave transmission in the frequency band of the millimeter wave radar.
The sheet resistance of the metallic lustrous article 1 also has a correlation with the electromagnetic wave permeability. Sheet resistance of metallic luster article 1Preferably 100 Ω/≡or more, in this case, the radio wave transmission attenuation in the microwave band (5 GHz) is 10 to 0.01 < -dB >]Left and right. The sheet resistance of the metallic lustrous article is more preferably 200Ω/≡or more, and still more preferably 600Ω/≡or more. In addition, it is particularly preferably 1000Ω/≡or more. The upper limit of the sheet resistance is not particularly limited, but is preferably 10 15 Ω/≡or less.
The sheet resistance of the metallic lustrous article 1 may be as defined in JIS-Z2316-1:2014 is determined by eddy current measurement.
The radio wave transmission attenuation amount and sheet resistance of the metallic luster article 1 are affected by the material, thickness, and the like of the metal layer 12. In addition, in the case where the metallic luster article 1 includes the layer 11 containing indium oxide, the metallic luster article is also affected by the material, thickness, and the like of the layer 11 containing indium oxide.
<2 > matrix >
The substrate 10 may be a resin, glass, ceramic, or the like from the viewpoint of electromagnetic wave permeability.
The substrate 10 may be any of a substrate film, a resin molded substrate, a glass substrate, or an article to which metallic luster should be imparted.
More specifically, as the base film, for example, a transparent film formed of a homopolymer or copolymer such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, polycarbonate (PC), cyclic Olefin Polymer (COP), polystyrene, polypropylene (PP), polyethylene, polycycloolefin, polyurethane, acryl (PMMA), ABS, or the like can be used.
When these members are used, the brightness and electromagnetic wave permeability are not affected. However, from the viewpoint of forming the indium oxide-containing layer 11 and the metal layer 12 later, a material that can withstand high temperatures such as vapor deposition and sputtering is preferable, and among these materials, for example, polyethylene terephthalate, polyethylene naphthalate, acryl, polycarbonate, cycloolefin polymer, ABS, polypropylene, and polyurethane are preferable. Among them, polyethylene terephthalate, cycloolefin polymer, polycarbonate and acryl are preferable in terms of good balance between heat resistance and cost.
The base film may be a single-layer film or a laminated film. The thickness is preferably about 6 μm to 250 μm, for example, from the viewpoint of ease of processing. In order to enhance the adhesion to the indium oxide-containing layer 11 and the metal layer 12, plasma treatment, adhesion-facilitating treatment, or the like may be performed.
In the case where the base 10 is a base film, the metal layer 12 may be provided on at least a part of the base film, and may be provided on only one side or both sides of the base film.
Here, it should be noted that the base material film is merely an example of an object (base body 10) on which the metal layer 12 can be formed on the surface thereof. The base 10 includes, in addition to the base film, a resin molded base material, a glass base material, and an article itself to which metallic luster should be imparted. Examples of the resin molded article base material and the article to be provided with metallic luster include structural parts for vehicles, vehicle-mounted articles, housings for electronic devices, housings for home appliances, structural parts, mechanical parts, various automobile parts, parts for electronic devices, household uses such as furniture and kitchen articles, parts for medical devices, building materials, other structural parts, and exterior parts.
The metal layer 12 may be formed on the entire substrate, or may be formed on a part of the surface of the substrate, or may be formed on the entire surface of the substrate. In this case, the substrate 10 to be provided with the metal layer 12 preferably satisfies the same materials and conditions as those of the above-described base film.
<3 > indium oxide-containing layer >
As shown in fig. 2, the electromagnetic wave-transparent metallic lustrous article 1 according to the embodiment may further include a layer 11 containing indium oxide between the base 10 and the metal layer 12. The layer 11 containing indium oxide may be directly provided 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 indium oxide-containing layer 11 is preferably provided in a continuous state, in other words, without gaps, on the surface of the substrate 10 to which metallic luster should be imparted. By providing the indium oxide-containing layer 11 in a continuous state, the smoothness and corrosion resistance of the metal layer 12 and the electromagnetic wave-transparent metallic lustrous article 1 can be improved, and the indium oxide-containing layer 11 can be easily formed without in-plane deviation.
In this way, if the indium oxide-containing layer 11 is further provided between the substrate 10 and the metal layer 12, that is, if the indium oxide-containing layer 11 is formed on the substrate 10 and the metal layer 12 is formed thereon, it becomes easy to form the metal layer 12 in a discontinuous state, which is preferable. The details of the mechanism are not clear, and it is considered that when a thin film is formed on a substrate by sputtering particles obtained by vapor deposition or sputtering of a metal, the surface diffusivity of the particles on the substrate affects the shape of the thin film, and when the temperature of the substrate is high, the wettability of the metal layer to the substrate is small, and the melting point of the material of the metal layer is low, a discontinuous structure is easily formed. Further, by providing the indium oxide-containing layer on the substrate, the surface diffusivity of the metal particles on the surface thereof can be promoted, and it becomes easy to grow the metal layer in a discontinuous state.
As the layer 11 containing indium oxide, indium oxide (In 2 O 3 ) In itself, a metal-containing substance such as Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO) may be used. Among them, ITO and IZO containing the second metal are more preferable in view of high discharge stability in the sputtering process. By using these indium oxide-containing layers 11, a film in a continuous state can be formed along the surface of the substrate, and in this case, for example, a discontinuous structure in an island shape is easily formed in the metal layer laminated on the indium oxide-containing layer, which is preferable. Further, as will be described later, in this case, the metal layer contains not only chromium (Cr) or indium (In), but also various metals such as aluminum, which are generally difficult to form a discontinuous structure and are difficult to apply In the present application.
Tin oxide (Sn) contained in ITO 2 ) The mass ratio of the components (content= (SnO) 2 /(In 2 O 3 +SnO 2 ) X 100), for example, is 2.5 to 30wt%, more preferably 3 to 10wt%. In addition, IZOThe mass ratio of zinc oxide (ZnO) contained, that is, the content ratio (content ratio= (ZnO/(In) 2 O 3 +ZnO). Times.100) is, for example, 2 to 20wt%. The thickness of the indium oxide-containing layer 11 is usually 1000nm or less, more preferably 50nm or less, and still more preferably 20nm or less, from the viewpoints of sheet resistance, attenuation of radio wave transmission, and productivity. On the other hand, the metal layer 12 to be stacked is preferably 1nm or more for easy formation of a discontinuous state, more preferably 2nm or more, and still more preferably 5nm or more for easy and reliable formation of a discontinuous state.
<4. Metal layer >
The metal layer 12 is formed on the substrate 10, and the maximum value of the reflectance in the total reflection spectrum is in the range of 380nm to 780 nm. The metal layer 12 includes a plurality of portions 12a at least a part of which is discontinuous with each other, and the average particle diameter of the plurality of portions 12a is preferably 100 to 500nm.
Here, the average particle diameter of the plurality of portions 12a refers to an average of the equivalent circle diameters of the plurality of portions 12 a. The circle equivalent diameter of the plurality of portions 12a means a diameter of a perfect circle corresponding to the area of the plurality of portions 12 a. The average particle diameter of the plurality of portions 12a can be measured by the method described in the column of examples.
For the metal layer 12, in order to exhibit a good metal-like appearance, it is preferable that the maximum value of reflectance in the total reflection spectrum of the metal layer 12 is around the visible light region. Hereinafter, a wavelength having a reflectance extremely large in the total reflection spectrum is also referred to as a "reflection peak wavelength". If the reflection peak wavelength of the metal layer 12 is too short, the metallic lustrous article 1 appears blue, whereas if the reflection peak wavelength is too long, the metallic lustrous article 1 appears red, and in either case, the glossiness is lowered, and a good metallic appearance is not obtained. In the present invention, the reflection peak wavelength of the metal layer 12 is set to a range of 380nm to 780nm, whereby a good metal-like appearance is obtained. The reflection peak wavelength of the metal layer 12 is more preferably 400nm to 700nm.
The reflection peak wavelength of the metal layer 12 varies depending on the material and structure of the metal layer. When the metal layer 12 includes a plurality of portions 12a at least a part of which is in a discontinuous state, the reflection peak wavelength of the metal layer 12 tends to be different depending on the average particle diameter of the plurality of portions 12a, as follows: the reflection peak wavelength becomes shorter when the average particle diameter of the plurality of portions 12a becomes smaller, and the reflection peak wavelength becomes longer when the average particle diameter of the plurality of portions becomes larger. When the metal layer 12 includes a plurality of portions 12a at least a part of which is discontinuous with each other, the average particle diameter of the plurality of portions 12a is preferably 100 to 500nm, more preferably 150 to 450nm, in order to achieve the above-described appropriate reflection peak wavelength.
The distance between the portions 12a is not particularly limited, and is usually about 10 to 1000nm.
It is not to mention that the metal layer 12 is expected to exhibit sufficient brightness, but it is also expected to have a low melting point. This is because the metal layer 12 is preferably formed by film growth using sputtering. For this reason, a metal having a melting point of about 1000 ℃ or lower is preferable as the metal layer 12, and for example, it is preferable to include at least one metal selected from aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), and silver (Ag), and an alloy containing the metal as a main component. In particular, al and an alloy thereof are preferable for the reasons of brightness, stability, price, and the like of the substance. In the case of using an aluminum alloy, the aluminum content is preferably 50 mass% or more.
The thickness of the metal layer 12 is usually preferably 20nm or more for exhibiting sufficient brightness, and is usually preferably 100nm or less from the viewpoints of sheet resistance and attenuation of radio wave transmission. For example, it is preferably 20nm to 100nm, more preferably 30nm to 70nm. The thickness is also suitable for forming a uniform film with good productivity, and the appearance of a resin molded product as a final product is also good. The thickness of the metal layer 12 can be measured, for example, as follows.
(method for measuring thickness of Metal layer)
First, as shown in fig. 4, a square region 3 having a side length of 5cm is appropriately extracted from a metallic lustrous article, and points "a" to "e" of a total of 5 points obtained by dividing the center lines A, B of the longitudinal and lateral sides of the square region 3 by 4 are selected as measurement points.
Next, sectional images (transmission electron microscope photographs (TEM images)) as shown in fig. 5 at the selected measurement sites are measured, and a view angle region including 5 or more metal portions 12a is extracted from the obtained TEM images.
The thickness of the metal layer in each viewing angle region was obtained by dividing the total cross-sectional area of the metal layer in the viewing angle region extracted from each of the 5 measurement sites by the lateral width of the viewing angle region, and the average value of the thicknesses of the metal layer in each viewing angle region at each of the 5 measurement sites was obtained as the thickness of the metal layer.
For the same reason, the ratio of the thickness of the metal layer 12 to the thickness of the indium oxide-containing layer 11 (the thickness of the metal layer 12/the thickness of the indium oxide-containing layer 11) is preferably in the range of 0.1 to 100, more preferably in the range of 0.3 to 35.
The metallic lustrous article of the present embodiment may further include other layers in addition to the above-described metal layer and the indium oxide-containing layer according to the application.
Examples of the other layer include an optical adjustment layer (color tone adjustment layer) such as a high refractive material for adjusting the appearance of color tone or the like, a protective layer (scratch resistance layer) for improving durability such as moisture resistance and scratch resistance, a barrier layer (anticorrosive layer), an easy-to-adhere layer, a hard coat layer, an antireflection layer, a light extraction layer, an antiglare layer, and the like.
<5 > production of metallic glossy article >
An example of a method for producing the metallic lustrous article 1 will be described. Although not particularly described, the substrate other than the base film 10 may be produced by the same method.
When the metal layer 12 is formed on the substrate 10, for example, vacuum deposition, sputtering, or the like can be used.
In the case of forming the layer 11 containing indium oxide on the substrate 10, the layer 11 containing indium oxide is formed by vacuum evaporation, sputtering, ion plating, or the like before the formation of the metal layer 12. Among them, sputtering is preferable in that the thickness can be strictly controlled even in a large area.
In the case where the layer 11 containing indium oxide is provided between the substrate 10 and the metal layer 12, it is preferable that the layer 11 containing indium oxide is in direct contact with the metal layer 12 without interposing another layer.
<6. Metal film >
The metal thin film according to the present embodiment is a metal thin film formed on a substrate, the metal thin film having a thickness of 20nm to 100nm, and a maximum value of reflectance in a total reflection spectrum being in a range of 380nm to 780 nm. The metal thin film according to the present embodiment includes a plurality of island-shaped portions, at least a part of which are discontinuous with each other, and the average particle diameter of the island-shaped portions is preferably 100 to 500nm.
The metal layer 12 may be formed to have a thickness of 20nm to 100nm, and may be used only as a metal thin film. For example, the metal layer 12 is formed by sputtering on the indium oxide-containing layer 11 laminated on a substrate such as a base film, to obtain a film with a metal film. Separately from this, an adhesive is applied to a substrate to prepare a substrate with an adhesive layer. The metal layer (metal thin film) 12 present on the outermost surface of the metal thin film is transferred to the outermost surface of the adhesive layer-carrying substrate by bonding the metal thin film to the adhesive layer-carrying substrate so that the metal layer 12 contacts the adhesive layer and then sufficiently adheres to the adhesive layer-carrying substrate, and then peeling off the metal thin film from the substrate.
The above description may be directly incorporated as the average particle diameter of the substrate, the metal thin film, and the plurality of portions.
<7. Use of metallic glossy article and metallic film >
The metallic lustrous article 1 and the metallic thin film according to the present embodiment have electromagnetic wave permeability, and are therefore preferably used for an apparatus for transmitting/receiving electromagnetic waves, an article, a component thereof, and the like. For example, structural parts for vehicles, vehicle mounted articles, housings for electronic devices, housings for home appliances, structural parts, mechanical parts, various automobile parts, parts for electronic devices, furniture applications such as kitchen articles, parts for medical devices, building materials, other structural parts, exterior parts, and the like can be cited.
More specifically, examples of the vehicle include dashboards, center console boxes, door handles, door trim (door trim), shift levers, pedals, glove boxes, bumpers, hoods, fenders, trunk boxes (trunk), doors, roof caps, pillars (pilar), seats, steering wheels, ECU boxes, electric components, engine peripheral components, drive system/gear peripheral components, intake/exhaust system components, and cooling system components.
More specifically, examples of the electronic device and the home electric device include home electric products such as a refrigerator, a washing machine, a vacuum cleaner, a microwave oven, an air conditioner, a lighting device, an electric water heater, a television, a clock, a ventilator, a projector, and a speaker, and electronic information devices such as a personal computer, a mobile phone, a smart phone, a digital camera, a tablet PC, a portable music player, a portable game machine, a charger, and a battery.
Examples
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The metallic luster articles of examples 1 to 7 and comparative examples 1 to 3 were prepared, and the average particle diameter, reflection peak wavelength, glossiness, thickness (film thickness) of the metal layer, and sheet resistance of the portions constituting the metal layer were measured. As the base 10, a base film was used.
The 20 ° gloss is an evaluation on the gloss, and is preferably larger.
The details of the evaluation method are as follows.
(1) Average particle diameter
Using a Scanning Electron Microscope (SEM), 5-ten thousand-fold SEM images of a region of 1.92 μm×2.56 μm of the metal layer of the metal gloss article were obtained. The area V of each portion was obtained from the SEM image obtained, and r=2× (V/pi) 0.5 The particle diameter R of each fraction was obtained and the average value thereof was used as the average particle diameter of the plurality of fractions. When the average value is obtained, R is not more than 0.05 μm and is ignored as noise.
Fig. 3 shows an example of the obtained SEM image. Fig. 3 is an SEM image of the metal layer of the metal luster article of example 3.
(2) Reflection peak wavelength
The black tape was attached to the substrate side of the metal-glossy article, and the surface on the metal layer side was irradiated with light, and the spectrum of total reflection light was obtained using a spectrophotometer U4100 (manufactured by Hitachi High-Technologies Corporation). Then, in the obtained spectrum, a wavelength having a reflectance extremely large in a wavelength range of 200nm to 2000nm is detected as a reflection peak wavelength.
(3) 20 degree gloss
A black tape was attached to the substrate side of a metallic glossy article, and the 20℃gloss was measured in accordance with JIS Z8741 (1997 edition). Specifically, the measurement was performed using PG-IIM (manufactured by Nippon Denshoku Kogyo Co., ltd.). The 20 ° gloss was measured on the surface of the metal layer side. The brightness of the metallic lustrous article was judged based on the obtained value of the glossiness according to the following criteria.
(evaluation criterion of Brightness)
Exceeding 1000: o (good)
500-1000: delta (slightly bad)
Less than 500: x (bad)
(4) Thickness of metal layer (film thickness)
The thickness (film thickness) of the metal layer was measured by the method described above using a Transmission Electron Microscope (TEM).
(5) Sheet resistance
The sheet resistance of the laminate of the metal layer and the indium oxide-containing layer was measured by an eddy current measurement method according to JIS-Z2316 using a non-contact resistance measuring device NC-80MAP (upper limit of measurement: 3000. OMEGA/. Times.in accordance with NAPSON CORPORATION).
The evaluation results are shown in table 1 below.
TABLE 1
Example 1
As the base film, a PET film (thickness: 38 μm) manufactured by Mitsubishi resin Co., ltd was used.
First, an ITO layer of 5nm thickness was formed directly on the substrate film along the surface thereof using DC magnetron sputtering. The temperature of the substrate film at the time of forming the ITO layer was set to 130 ℃. Tin oxide (Sn) contained in ITO 2 ) The content of (content= (SnO) 2 /(In 2 O 3 +SnO 2 ) 100) is 10wt%.
Then, an aluminum (Al) layer was formed on the ITO layer by alternating current sputtering (AC: 40 kHz) to obtain a metallic glossy article (metallic thin film). The temperature of the base film at the time of forming the Al layer was set to 130 ℃.
Examples 2 to 7 and comparative examples 1 to 3
The same procedure as in example 1 was repeated except that the sputtering time for forming an aluminum (Al) layer on the ITO layer was changed, to obtain metallic glossy articles (metallic thin films) of examples 2 to 7 and comparative examples 1 to 3.
The metallic lustrous articles of examples 1 to 7 all had good brightness and exhibited excellent metallic appearance.
On the other hand, with respect to the metallic lustrous articles of comparative examples 1 and 2, the average particle diameter of the portions of the metallic layer was small, the reflection peak wavelength was short, the appearance of bluish color was exhibited, the glossiness was small, and the brightness was poor.
In addition, the metallic luster article of comparative example 3 had a large average particle diameter, a long reflection peak wavelength, a reddish appearance, a small luster, and poor brightness in the multiple portions of the metallic layer.
It is considered that metals other than aluminum (Al) particularly used in the above examples may have a discontinuous structure with respect to metals having relatively low melting points such as zinc (Zn), lead (Pb), copper (Cu), and silver (Ag) by the same method.
The present invention is not limited to the foregoing embodiments, and may be modified and embodied as appropriate within a scope not departing from the gist of the invention.
While the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments, and various modifications and substitutions may be made to the above embodiments without departing from the scope of the present invention.
The present application is based on japanese patent application No. 2018, 4-month 23 (japanese patent application No. 2018-082657), and japanese patent application No. 2019, 4-month 22 (japanese patent application No. 2019-080636), the contents of which are incorporated herein by reference.
Industrial applicability
The metallic luster article of the present invention can be used for a device for transmitting/receiving electromagnetic waves, an article, a component thereof, and the like. For example, the present invention can be used for various applications requiring both of appearance and electromagnetic wave permeability, such as structural members for vehicles, vehicle-mounted articles, housings for electronic devices, housings for home appliances, structural members, mechanical members, various automobile members, electronic device members, household applications such as furniture and kitchen articles, members for medical devices and building materials, other structural members, and exterior members.
Description of the reference numerals
1. Metallic luster article
10. Matrix body
11. Indium oxide containing layer
12. Metal layer
Part 12a
12b gap
Claims (8)
1. An electromagnetic wave-transparent metallic luster article comprising: a substrate, and a metal layer formed on the substrate,
the metal layer includes a plurality of portions, at least a portion of which is in a discontinuous state with each other, the plurality of portions being formed in an island shape and having an average particle diameter of 100 to 500nm,
a layer containing indium oxide is further provided between the substrate and the metal layer,
the indium oxide-containing layer is provided in a continuous state,
the thickness of the matrix is 6-250 μm and not 125 μm,
the maximum value of the reflectivity in the total reflection spectrum of the metal layer is in the range of 380nm to 780 nm.
2. The electromagnetic wave-transparent metallic lustrous article according to claim 1, wherein the indium oxide-containing layer comprises indium oxide (In 2 O 3 ) Any of Indium Tin Oxide (ITO), or Indium Zinc Oxide (IZO).
3. The electromagnetic wave-transparent metallic glossy article according to claim 1 or 2, wherein the thickness of the indium oxide-containing layer is 1nm to 1000nm.
4. The electromagnetic wave-transparent metallic glossy article according to claim 1 or 2, wherein the thickness of the metal layer is 20nm to 100nm.
5. The electromagnetic wave-transparent metallic glossy article according to claim 1 or 2, wherein a ratio of a thickness of the metal layer to a thickness of the indium oxide-containing layer, i.e., a thickness of the metal layer/a thickness of the indium oxide-containing layer is 0.02 to 100.
6. The electromagnetic wave-transparent metallic lustrous article as described in claim 1 or 2, having a sheet resistance of 100 Ω/≡s or more.
7. The electromagnetic wave-transparent metallic luster article according to claim 1 or 2, wherein the metal layer is any one of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag), or an alloy thereof.
8. The electromagnetic wave-transparent metallic luster article according to claim 1 or 2, wherein the base is any one of a base film, a resin molded base, a glass base, and an article to which metallic luster should be imparted.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2018-082657 | 2018-04-23 | ||
| JP2018082657 | 2018-04-23 | ||
| PCT/JP2019/017017 WO2019208494A1 (en) | 2018-04-23 | 2019-04-22 | Electromagnetic wave transmissive metallic luster product and metal thin film |
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| CN102282288A (en) * | 2009-01-20 | 2011-12-14 | 信越聚合物株式会社 | Radio wave-transmitting decorative member and method for producing same |
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| JP4863906B2 (en) * | 2007-03-12 | 2012-01-25 | 株式会社アルバック | Glittering film and method for producing the glittering film |
| JP2009298006A (en) | 2008-06-12 | 2009-12-24 | Toyoda Gosei Co Ltd | Electromagnetic wave permeable glittering resin product and manufacturing method |
| JP2010005999A (en) | 2008-06-30 | 2010-01-14 | Nissha Printing Co Ltd | Method of manufacturing metal film decorative sheet which has crack |
| US20150293025A1 (en) * | 2012-12-18 | 2015-10-15 | Toray Industries Inc. | Metal dot substrate and method of manufacturing metal dot substrate |
| JP6400062B2 (en) * | 2016-10-24 | 2018-10-03 | 日東電工株式会社 | Electromagnetic wave transmitting metallic luster member, article using the same, and metallic thin film |
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