CN112004663A - Electromagnetic wave-permeable metallic luster article and metallic thin film - Google Patents
Electromagnetic wave-permeable metallic luster article and metallic thin film Download PDFInfo
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- CN112004663A CN112004663A CN201980027636.6A CN201980027636A CN112004663A CN 112004663 A CN112004663 A CN 112004663A CN 201980027636 A CN201980027636 A CN 201980027636A CN 112004663 A CN112004663 A CN 112004663A
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- 239000010409 thin film Substances 0.000 title claims description 34
- 239000002932 luster Substances 0.000 title claims description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 135
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- 239000000758 substrate Substances 0.000 claims abstract description 54
- 238000001228 spectrum Methods 0.000 claims abstract description 13
- 239000010408 film Substances 0.000 claims description 47
- 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 44
- 229910003437 indium oxide Inorganic materials 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 23
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
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- 239000004332 silver Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
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- 238000002310 reflectometry Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 144
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- 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
- 229910052804 chromium Inorganic materials 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
- 150000007529 inorganic bases Chemical class 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910020923 Sn-O Inorganic materials 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
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- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
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- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910009815 Ti3O5 Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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- 229920002647 polyamide Polymers 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000009423 ventilation 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
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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 transmissive metallic lustrous article (1) comprising: 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 transmissive metallic glossy article and a metallic thin film.
Background
Conventionally, a member having electromagnetic wave permeability and metallic luster has both a high-grade feeling derived from the appearance of the metallic luster and electromagnetic wave permeability, and therefore is suitably used for an apparatus for transmitting/receiving electromagnetic waves.
For example, there is a demand for a metallic glossy article having both of a glittering property and an electromagnetic wave transmitting property, which is decorated with a cover member of a millimeter wave radar mounted on a front body portion of an automobile such as a front grille and a emblem.
The 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 (about 77GHz, about 4mm in wavelength) to the front of the automobile, receiving reflected waves from the target object, and measuring and analyzing the reflected waves.
The measurement results may be used for inter-vehicle distance measurement, automatic speed adjustment, automatic brake adjustment, etc.
The front body of the automobile equipped with such a millimeter wave radar is a face of the automobile, and is a part that greatly affects the user, and therefore it is preferable to exhibit a high-grade feeling by a metallic luster-like front body decoration. However, in the case where metal is used for the front part of the automobile, transmission/reception of electromagnetic waves by the millimeter wave radar is substantially impossible or is hindered. Therefore, in order not to impair the function of the millimeter wave radar and not to impair the appearance of the automobile, there is a need for a metallic glossy article having both of the glittering property and the electromagnetic wave permeability.
Such a metallic luster article is expected to be applied not only to millimeter-wave radars but also to various devices requiring communication, for example, door handles of automobiles equipped with smart keys, in-vehicle communication devices, electronic devices such as mobile phones and personal computers. Further, in recent years, with the development of the IoT technology, it is expected to be applied to a wide range of fields such as household electric appliances such as refrigerators and living equipment, which have not been subjected to communication or the like.
As for 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 product comprises: the inorganic base film is characterized by comprising a resin base material, an inorganic base film containing an inorganic compound and formed on the resin base material, and a metal coating film which is formed on the inorganic base film by a physical vapor deposition method and is formed by chromium (Cr) or indium (In) and has a bright and discontinuous structure. As the inorganic base film, a film using (a) a metal compound, for example, titanium oxide (TiO ) in patent document 12、Ti3O5Etc.) titanium compounds; silicon oxide (SiO )2Etc.), silicon nitride (Si)3N4Etc.) silicon compounds; aluminum oxide (Al)2O3) And the like aluminum compounds; iron oxide (Fe)2O3) An isoiron compound; selenium compounds such as selenium oxide (CeO); zirconium compounds such as zirconium oxide (ZrO); zinc compounds such as zinc sulfide (ZnS), etc., (b) coating films of inorganic paints made of, for example, silicon or amorphous TiOzAnd the like (and the metal compounds exemplified above) as the main component.
On the other hand, japanese patent laid-open No. 2009-298006 (patent document 2) discloses an electromagnetic wave transmissive 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 a metal film.
Japanese patent application laid-open No. 2010-5999 (patent document 3) describes the following method: a method for producing a metallic film decorative sheet having electromagnetic wave permeability and cracks by forming a metallic film layer on a base material sheet, applying tension to the base material sheet, and heating the base material sheet.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2007-144988
Patent document 2: japanese laid-open patent publication No. 2009-298006
Patent document 3: japanese patent laid-open publication No. 2010-5999
Disclosure of Invention
Problems to be solved by the invention
However, the present inventors have found that in the metallic lustrous article of the related art, since the reflection spectrum of the metal layer has frequency characteristics, that is, the reflectance is different at each wavelength of light, it is difficult to obtain a good metallic appearance.
The present invention has been made in view of the above, and an object thereof is to provide an electromagnetic wave transmissive metallic lustrous article having a good metallic appearance.
Means for solving the problems
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 a wavelength that exhibits a maximum value of reflectance in a total reflection spectrum of a metal layer to an appropriate range in an electromagnetic wave-transmissive metallic glossy article having the metal layer.
The electromagnetic wave transmissive metallic luster article of the invention comprises: and a metal layer formed on the substrate, wherein a maximum value of reflectance in a total reflection spectrum of the metal layer is in a range of 380nm to 780 nm.
In one embodiment of the electromagnetic wave transmissive metallic luster article according to the invention, the metal layer preferably includes a plurality of portions, at least one of the plurality of portions being discontinuous with respect to each other, and the plurality of portions having an average particle diameter of 100 to 500 nm.
In one embodiment of the electromagnetic wave transmissive metallic lustrous article of the present invention, a layer containing indium oxide is preferably further provided between the substrate and the metal layer.
In one embodiment of the electromagnetic wave transmissive metallic luster article of the invention, the layer containing indium oxide is preferably provided in a continuous state.
In one embodiment of the electromagnetic wave transmissive metallic luster article of the invention, the layer containing indium oxide preferably contains indium oxide (In)2O3) Indium Tin Oxide (ITO), or Indium Zinc Oxide (IZO).
In one embodiment of the electromagnetic wave transmissive metallic lustrous article of the present invention, the layer containing indium oxide preferably has a thickness of 1nm to 1000 nm.
In one embodiment of the electromagnetic wave transmissive metallic lustrous article of the present invention, the thickness of the metal layer is preferably 20nm to 100 nm.
In one embodiment of the electromagnetic wave transmissive metallic luster article of the invention, a ratio of the thickness of the metal layer to the thickness of the indium oxide-containing layer (thickness of the metal layer/thickness of the indium oxide-containing layer) may be 0.02 to 100.
In one embodiment of the electromagnetic wave transmissive metallic lustrous article of the present invention, the sheet resistance may be 100 Ω/□ or more.
In one embodiment of the electromagnetic wave transmissive metallic lustrous article of the present invention, the plurality of portions may be formed in an island shape.
In one embodiment of the electromagnetic wave transmissive metallic lustrous article of 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 transmissive metallic lustrous article of the present invention, the substrate is preferably any one of a substrate film, a resin molded product substrate, a glass substrate, and an article to be provided with metallic lustrous.
The metal thin film of the present invention is a metal thin film formed on a substrate,
the metal thin film has a thickness of 20nm to 100nm, and the maximum value of the reflectance in the total reflection spectrum is in the range of 380nm to 780 nm.
In one embodiment of the metal thin film of the present invention, the metal thin film preferably includes a plurality of island-like portions, at least a part of the plurality of island-like portions being discontinuous with each other, and the plurality of island-like portions preferably have an average particle diameter of 100 to 500 nm.
In one embodiment of the metal thin film of the present invention, the metal thin film is preferably any 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-transmissive metallic lustrous article having a good metallic appearance can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view of an electromagnetic wave transmissive metallic lustrous article according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of an electromagnetic wave transmissive metallic lustrous article according to an embodiment of the present invention.
Fig. 3 is an electron micrograph of the surface of an electromagnetic wave transmissive metallic lustrous 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 transmissive metallic lustrous article according to the embodiment of the present invention.
Fig. 5 is a transmission electron micrograph (TEM image) showing a cross section of the metal layer in the embodiment of the present invention.
Detailed Description
Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. Hereinafter, for convenience of explanation, only preferred embodiments of the present invention will be described, but the present invention is not limited thereto.
<1. basic constitution >
Fig. 1 shows a schematic cross-sectional view of an electromagnetic wave transmissive metallic lustrous article (hereinafter, referred to as "metallic lustrous article") 1 according to an embodiment of the present invention, and fig. 3 shows an electron micrograph (SEM image) of the surface of the metallic lustrous 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-shaped metal layer 12 according to the embodiment of the present invention.
The metallic lustrous article 1 includes: a substrate 10, and a metal layer 12 formed on the substrate 10.
The metal layer 12 is formed on the substrate 10. The metal layer 12 preferably includes a plurality of portions 12a, at least a part of the plurality of portions 12a being in a discontinuous state with each other. At least a part of these portions 12a in the metal layer 12 is in a state of being discontinuous from each other, in other words, at least a part is separated by a gap 12 b. When the metallic luster article is separated by the gap 12b, the sheet resistance of the metallic luster article increases, and the interaction with the radio wave decreases, so that the radio wave is easily transmitted, which is preferable. These portions 12a may be an aggregate of sputtering particles formed by evaporating or sputtering a metal.
The structure of the metal layer 12 is not limited to a structure including a plurality of portions 12a at least a portion of which is discontinuous from each other, and may be a continuous structure as long as electromagnetic wave permeability can be secured.
The "discontinuous state" referred to in the present specification means a state in which they are separated from each other by the gap 12b and are electrically insulated from each other as a result. By performing electrical insulation, the sheet resistance of the metallic lustrous article becomes large, and desired electromagnetic wave permeability becomes easily obtained. That is, sufficient brightness is easily obtained by the metal layer 12 formed in a discontinuous state, 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. Here, the "island-like structure" refers to a structure in which the metal particles are independent of each other and the particles are spread out in a state of being slightly separated from each other or partially contacting each other, as shown in fig. 3.
The crack structure refers to a structure in which the metal film is cracked by the crack.
The metal layer 12 having a crack structure can be formed, for example, by providing a metal thin film layer on a base film and bending and stretching the base film to crack the metal thin film layer. In this case, the metal layer 12 having a crack structure can be easily formed by providing a brittle layer made of a material which is poor in stretchability, i.e., is likely to crack by stretching, between the base film and the metal thin film layer.
As described above, the discontinuous form of the metal layer 12 is not particularly limited, and an island-like structure is preferably employed from the viewpoint of productivity.
The electromagnetic wave permeability of the metallic lustrous article 1 can be evaluated by, for example, the radio wave transmission attenuation. In the metallic lustrous article 1, the radio wave transmission attenuation in the microwave band (5GHz) measured by the method described in the section of the examples is preferably 10 < -dB or less, more preferably 5 < -dB or less, and still more preferably 2 < -dB or less. If it exceeds 10 < -dB >, there is a problem that 90% or more of the radio wave is blocked. Since the radio wave transmission attenuation in the microwave band (1GHz) and the radio wave transmission attenuation in the frequency band (76 to 80GHz) of the millimeter wave radar have a correlation and show relatively close values, the metallic lustrous article having excellent electromagnetic wave transmission in the microwave band is also excellent in 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. The sheet resistance of the metallic luster article 1 is preferably 100 Ω/□ or more, and the attenuation of the transmission of radio waves in the microwave band (5GHz) is 10 to 0.01 < -dB]Left and right. The sheet resistance of the metallic lustrous article is more preferably 200 Ω/□ or more, and still more preferably 600 Ω/□ or more. In addition, 1000 Ω/□ or more is particularly preferable. The upper limit of the sheet resistance is not particularly limited, but is preferably 1015Omega/□ or less.
The sheet resistance of the metallic lustrous article 1 may be measured in accordance with JIS-Z2316-1: 2014 is determined by eddy current measurements.
The radio wave transmission attenuation and the sheet resistance of the metallic lustrous article 1 are affected by the material, thickness, etc. of the metal layer 12. In addition, when the metallic lustrous article 1 includes the layer 11 containing indium oxide, the material, thickness, and the like of the layer 11 containing indium oxide also affect it.
<2. base >
Examples of the substrate 10 include resin, glass, and ceramics from the viewpoint of electromagnetic wave permeability.
The substrate 10 may be any of a substrate film, a resin molded product substrate, a glass substrate, or an article to which a metallic luster should be imparted.
More specifically, as the substrate film, for example, a transparent film formed of homopolymers or copolymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, Polycarbonate (PC), cycloolefin polymer (COP), polystyrene, polypropylene (PP), polyethylene, polycycloolefin, polyurethane, acryl (PMMA), ABS, and the like can be used.
When these members are used, the brightness and the electromagnetic wave permeability are not affected. However, from the viewpoint of forming the layer 11 containing indium oxide and the metal layer 12 later, materials that can withstand high temperatures such as vapor deposition and sputtering are preferable, and among the above 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 a 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 from the viewpoint of ease of processing. In order to enhance adhesion to the indium oxide-containing layer 11 and the metal layer 12, plasma treatment, easy adhesion treatment, or the like may be performed.
When 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 only on one surface or both surfaces of the base film.
Here, it should be noted that the base film is merely an example of an object (base 10) on which the metal layer 12 can be formed on the surface. The base 10 includes, as described above, a resin molded product substrate, a glass substrate, and an article itself to be provided with a metallic luster, in addition to the substrate film. Examples of the resin molded product substrate and the article to be provided with a metallic luster include a vehicle structural member, a vehicle-mounted article, a housing of an electronic device, a housing of a household electrical appliance, a structural member, a mechanical member, various automobile members, a member for an electronic device, furniture, a household use such as a kitchen appliance, a medical device, a member for a building material, another structural member, and an exterior member.
The metal layer 12 may be formed on all of the substrate, 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 base 10 to be provided with the metal layer 12 preferably satisfies the same material and conditions as those of the base film.
<3 > layer containing indium oxide >
As shown in fig. 2, the electromagnetic wave transmissive metallic lustrous article 1 according to the embodiment may further include a layer 11 containing indium oxide between the substrate 10 and the metal layer 12. The layer 11 containing indium oxide may be provided directly on the surface of the substrate 10, or may be provided indirectly via a protective film or the like provided on the surface of the substrate 10. The layer 11 containing indium oxide is preferably provided in a continuous state, in other words, without a gap, on the surface of the substrate 10 to be provided with metallic luster. By providing the layer 11 containing indium oxide, the smoothness and corrosion resistance of the metal layer 12 and the electromagnetic wave transmissive metallic lustrous article 1 can be improved, and the layer 11 containing indium oxide can be easily formed without in-plane variation.
In this way, if the layer 11 containing indium oxide is further provided between the substrate 10 and the metal layer 12, that is, the layer 11 containing indium oxide is formed on the substrate 10 and the metal layer 12 is formed thereon, the metal layer 12 is easily formed 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 diffusion property 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 with respect to the substrate is low, and the melting point of the material of the metal layer is low, a discontinuous structure is easily formed. Further, by providing a layer containing indium oxide on the substrate, the surface diffusion of the metal particles on the surface thereof can be promoted, and the metal layer can be easily grown in a discontinuous state.
As the layer 11 containing indium oxide, indium oxide (In) can be used2O3) As such, 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 terms of high discharge stability in the sputtering step. By using the layer 11 containing indium oxide, a film in a continuous state can be formed along the surface of the base, and in this case, the metal layer stacked on the layer containing indium oxide is preferable because, for example, an island-shaped discontinuous structure is easily formed. Further, as described later, In this case, the metal layer easily contains various metals such as aluminum, which is generally difficult to form a discontinuous structure and is difficult to apply to the present application, In addition to chromium (Cr) and indium (In).
Tin oxide (Sn-O) contained in ITO2) The content ratio (SnO) is a mass ratio of (b) to (c)2/(In2O3+SnO2) X 100) is not particularly limited, and is, for example, 2.5 to 30% by weight, more preferably 3 to 10% by weight. The content ratio (content ratio) that is the mass ratio of zinc oxide (ZnO) contained In IZO is (ZnO/(In)/2O3+ ZnO)). times.100) is, for example, from 2 to 20% by weight. The thickness of the layer 11 containing indium oxide is usually preferably 1000nm or less, more preferably 50nm or less, and still more preferably 20nm or less, from the viewpoint of sheet resistance, radio wave transmission attenuation, and productivity. On the other hand, the thickness of the metal layer 12 is preferably 1nm or more for facilitating the formation of a discontinuous state, and more preferably 2nm or more, and still more preferably 5nm or more for facilitating the reliable formation of a discontinuous state.
<4. Metal layer >
The metal layer 12 is formed on the base 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 500 nm.
Here, the average particle diameter of the plurality of portions 12a refers to an average value of circle-equivalent diameters of the plurality of portions 12 a. The circle-equivalent diameter of the plurality of portions 12a means the 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.
In order for the metal layer 12 to have a good metallic appearance, the maximum value of the reflectance in the total reflection spectrum of the metal layer 12 is preferably around the visible light region. Hereinafter, the wavelength at which the reflectance is extremely high in the total reflection spectrum is also referred to as "reflection peak wavelength". If the reflection peak wavelength of the metal layer 12 is too short, the metallic lustrous article 1 looks bluish, whereas if the reflection peak wavelength is too long, the metallic lustrous article 1 looks reddish, 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 be in the range of 380nm to 780nm, thereby obtaining a good metallic appearance. The reflection peak wavelength of the metal layer 12 is more preferably 400nm to 700 nm.
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 discontinuous from each other, the reflection peak wavelength of the metal layer 12 varies depending on the average particle diameter of the plurality of portions 12a, and has a following orientation: 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 parts 12a is not particularly limited, but is usually about 10 to 1000 nm.
The metal layer 12 is required to have a low melting point, not only to exhibit sufficient brightness. This is because the metal layer 12 is preferably formed by thin film growth using sputtering. For this reason, as the metal layer 12, a metal having a melting point of about 1000 ℃ or lower is preferable, 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 alloys thereof are preferable for reasons such as the brightness, stability and price of the material. When an aluminum alloy is used, the aluminum content is preferably 50 mass% or more.
The thickness of the metal layer 12 is preferably 20nm or more in order to exhibit sufficient brightness, and is preferably 100nm or less in view of sheet resistance and radio wave transmission attenuation. For example, it is preferably 20nm to 100nm, more preferably 30nm to 70 nm. This 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 of 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 the metallic lustrous article, and points "a" to "e" of 5 sites in total obtained by dividing the center line A, B of each of the vertical and horizontal sides of the square region 3 by 4 equally are selected as measurement sites.
Next, a cross-sectional image (transmission electron micrograph (TEM image)) as shown in fig. 5 at each selected measurement site is measured, and a viewing angle region including 5 or more metal portions 12a is extracted from the obtained TEM image.
The thickness of the metal layer in each viewing angle region was determined as a value obtained by dividing the total cross-sectional area of the metal layer in the viewing angle region extracted at each of the 5 measurement portions by the lateral width of the viewing angle region, and the average value of the thicknesses of the metal layers in each viewing angle region at each of the 5 measurement portions was determined 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 layer 11 containing indium oxide (thickness of the metal layer 12/thickness of the layer 11 containing indium oxide) is preferably in the range of 0.1 to 100, and more preferably in the range of 0.3 to 35.
The metallic lustrous article of the present embodiment may include other layers depending on the application, in addition to the above-described metal layer and the layer containing indium oxide.
Examples of the other layers include an optical adjustment layer (color adjustment layer) such as a high refractive material for adjusting the appearance such as color tone, a protective layer (scratch resistant layer) for improving the durability such as moisture resistance and scratch resistance, a barrier layer (anti-corrosion layer), an easy-adhesion layer, a hard coat layer, an antireflection layer, a light extraction layer, and an antiglare layer.
<5. production of metallic luster article >
An example of the method for producing the metallic lustrous article 1 will be described. Although not particularly described, the substrate other than the base material film 10 can be manufactured by the same method.
For forming the metal layer 12 on the substrate 10, for example, a method such as vacuum deposition or sputtering may be used.
In the case where the layer 11 containing indium oxide is formed on the substrate 10, the layer 11 containing indium oxide is formed by vacuum evaporation, sputtering, ion plating, or the like before the metal layer 12 is formed. Among them, sputtering is preferable because the thickness can be strictly controlled even in a large area.
When the layer 11 containing indium oxide is provided between the substrate 10 and the metal layer 12, the layer 11 containing indium oxide and the metal layer 12 are preferably in direct contact with each other without interposing another layer therebetween.
<6. Metal thin film >
The metal thin film of the present embodiment is a metal thin film formed on a substrate, the metal thin film has a thickness of 20nm to 100nm, and the maximum value of the reflectance in the total reflection spectrum is in the range of 380nm to 780 nm. The metal thin film of the present embodiment includes a plurality of island-like portions, at least a part of the plurality of island-like portions being discontinuous with each other, and the average particle diameter of the plurality of island-like portions is preferably 100 to 500 nm.
The metal layer 12 may be formed to a thickness of 20nm to 100nm and used only as a metal thin film. For example, a metal layer 12 is formed by sputtering on an indium oxide-containing layer 11 laminated on a base such as a base thin film, thereby obtaining a thin film with a metal thin film. Separately from this, an adhesive is applied to the base material to produce a base material with an adhesive layer. The metal layer (metal film) 12 present on the outermost surface of the metal film-attached film can be transferred to the outermost surface of the adhesive layer-attached substrate by adhering the metal film-attached film to the adhesive layer-attached substrate so that the metal layer 12 is in contact with the adhesive layer and sufficiently adheres to the substrate, and then peeling the film from the substrate.
The average particle diameter of the substrate, the metal thin film, and the plurality of portions may be referred to as it is.
<7 > use of metallic luster article and metallic film
The metallic lustrous article 1 and the metallic thin film of the present embodiment have electromagnetic wave permeability, and therefore are preferably used for devices, articles, and parts thereof, etc. that transmit/receive electromagnetic waves. Examples thereof include structural members for vehicles, vehicle-mounted appliances, housings for electronic devices, housings for household electrical appliances, structural members, mechanical members, various automotive members, electronic device members, furniture applications such as furniture and kitchen supplies, medical devices, members for building materials, other structural members, and exterior members.
More specifically, examples of the vehicle include an instrument panel, a console box, a door handle, a door trim (door trim), a shift lever, pedals, a glove box, a bumper, an engine hood, a fender (fender), a trunk (trunk), a door, a roof, a pillar (pillar), a seat, a steering wheel, an ECU box, electric components, engine peripheral components, a drive system/gear peripheral components, intake/exhaust system components, and cooling system components.
More specifically, the electronic devices and home electric appliances include home electric appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting devices, electric water heaters, televisions, clocks, ventilation fans, projectors, speakers, and electronic information devices such as personal computers, mobile phones, smart phones, digital cameras, tablet PCs, portable music players, portable game machines, chargers, and batteries.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples. The metallic glossy 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) and sheet resistance of a plurality of portions constituting the metal layer were measured. A base film is used as the base 10.
The 20 ° gloss is evaluated for the shine, and is preferably larger.
Details of the evaluation method are as follows.
(1) Average particle diameter
Using a Scanning Electron Microscope (SEM), an SEM image of 5 ten thousand times the area of 1.92 μm × 2.56 μm of the metal layer of the metallic lustrous article was obtained. The area V of each portion was determined from the SEM image obtained, and R2 × (V/π)0.5The particle diameter R of each fraction was determined and the average value thereof was defined as the average particle diameter of a plurality of fractions. When the average value is obtained, the noise having an R of 0.05 μm or less is ignored.
Fig. 3 shows an example of the obtained SEM image. Fig. 3 is an SEM image of the metal layer of the metallic lustrous article of example 3.
(2) Reflection peak wavelength
A black tape was attached to the base side of the metallic luster article, and the surface on the metallic layer side was irradiated with light, and a spectrum of total reflection light was obtained using a spectrophotometer U4100 (manufactured by Hitachi High-Technologies Corporation). Then, in the obtained spectrum, a wavelength at which the reflectance is maximum 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 base side of the metallic luster article, and the 20 ° glossiness was measured according to JIS Z8741 (1997 edition). Specifically, PG-IIM (manufactured by Nippon Denshoku industries Co., Ltd.) was used for the measurement. The 20 ° gloss was measured on the surface on the metal layer side. The glossiness of the metallic lustrous article was judged based on the obtained glossiness values according to the following criteria.
(evaluation criteria for Brightness)
Over 1000: good (good)
500-1000: delta (slightly poor)
Less than 500: x (bad)
(4) Thickness of the Metal layer (film thickness)
The thickness (film thickness) of the metal layer was measured by the above-described method using a Transmission Electron Microscope (TEM).
(5) Sheet resistance
The sheet resistance of a laminate of a metal layer and an indium oxide-containing layer was measured by an eddy current measurement method in accordance with JIS-Z2316 using a non-contact resistance measuring device NC-80MAP (upper limit of measurement: 3000. omega./□) manufactured by 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 corporation was used.
First, an ITO layer having a thickness of 5nm was directly formed thereon along the face of the substrate film using DC magnetron sputtering. The temperature of the substrate film in forming the ITO layer was set to 130 ℃. Tin oxide (Sn-O) contained in ITO2) Content ratio (SnO ═ content ratio)2/(In2O3+SnO2) 100) is 10 wt.%.
Next, an aluminum (Al) layer was formed on the ITO layer by alternating current sputtering (AC: 40kHz) to obtain a metallic glossy article (metal thin film). The temperature of the base material film in forming the Al layer was set to 130 ℃.
Examples 2 to 7 and comparative examples 1 to 3
Metallic glossy articles (metal thin films) of examples 2 to 7 and comparative examples 1 to 3 were obtained in the same manner as in example 1, except that the sputtering time for forming the aluminum (Al) layer on the ITO layer was changed.
The metallic lustrous articles of examples 1 to 7 all had good glitter and exhibited excellent metallic appearance.
On the other hand, in the metallic lustrous articles of comparative examples 1 and 2, the metallic layer had a small average particle diameter at a plurality of portions, a short reflection peak wavelength, a bluish appearance, a low glossiness, and a poor glitter.
In the metallic lustrous article of comparative example 3, the metallic layer had a large average particle diameter at a plurality of portions, a long reflection peak wavelength, a reddish appearance, a low glossiness, and a poor glitter.
It is considered that, as for metals other than aluminum (Al) particularly used in the above examples, metals having a low melting point, such as zinc (Zn), lead (Pb), copper (Cu), and silver (Ag), can be formed into a discontinuous structure by the same method.
The present invention is not limited to the above-described embodiments, and can be appropriately modified and embodied 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.
It should be noted that the present application is based on japanese patent application published on 23/4/2018 (japanese patent application 2018-.
Industrial applicability
The metallic lustrous article of the present invention can be used for devices for transmitting/receiving electromagnetic waves, articles and parts thereof, and the like. For example, the present invention can be used in various applications requiring both of appearance and electromagnetic wave permeability, such as structural members for vehicles, housings for vehicle-mounted articles, housings for electronic devices, housings for household electrical appliances, structural members, mechanical members, various automotive members, members for electronic devices, home use such as furniture and kitchen supplies, medical devices, members for building materials, other structural members, and exterior members.
Description of the reference numerals
1 metallic lustrous article
10 base body
11 layer containing indium oxide
12 metal layer
12b gap
Claims (15)
1. An electromagnetic wave transmissive metallic lustrous article, comprising: a base, and a metal layer formed on the base,
the maximum value of the reflectivity in the total reflection spectrum of the metal layer is in the range of 380 nm-780 nm.
2. The electromagnetic wave transmissive metallic lustrous article of claim 1, wherein the metallic layer includes a plurality of portions, at least a part of which are in a state of discontinuity with each other,
the average particle diameter of the plurality of portions is 100 to 500 nm.
3. The electromagnetic wave transmissive metallic lustrous article according to claim 2, wherein the plurality of portions are formed in an island shape.
4. The electromagnetic wave transmissive metallic luster article according to any one of claims 1 to 3, further comprising a layer containing indium oxide between the substrate and the metal layer.
5. The electromagnetic wave transmissive metallic lustrous article according to claim 4, wherein the indium oxide-containing layer is provided in a continuous state.
6. The electromagnetic wave transmissive metallic lustrous article according to claim 4 or 5, wherein the layer containing indium oxide contains indium oxide (In)2O3) Indium Tin Oxide (ITO), or Indium Zinc Oxide (IZO).
7. The electromagnetic wave transmissive metallic luster article according to any one of claims 4 to 6, wherein the layer containing indium oxide has a thickness of 1nm to 1000 nm.
8. The electromagnetic wave transmissive metallic lustrous article as claimed in any one of claims 1 to 7, wherein the thickness of the metallic layer is 20nm to 100 nm.
9. The electromagnetic wave transmissive metallic luster article according to any one of claims 4 to 7, wherein the ratio of the thickness of the metal layer to the thickness of the indium oxide-containing layer, i.e., the thickness of the metal layer/the thickness of the indium oxide-containing layer, is 0.02 to 100.
10. The electromagnetic wave transmissive metallic lustrous article as claimed in any one of claims 1 to 9, having a sheet resistance of 100 Ω/□ or more.
11. The electromagnetic wave transmissive metallic luster article according to any one of claims 1 to 10, wherein the metal layer is any one of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag), or an alloy thereof.
12. The electromagnetic wave transmissive metallic lustrous article as claimed in any one of claims 1 to 11, wherein the substrate is any one of a substrate film, a resin molded product substrate, a glass substrate, or an article to which metallic lustrous is to be imparted.
13. A metal thin film formed on a substrate,
the metal thin film has a thickness of 20nm to 100nm, and the maximum value of the reflectance in the total reflection spectrum is in the range of 380nm to 780 nm.
14. The metal thin film according to claim 13, comprising a plurality of island-like portions, at least a part of the plurality of island-like portions being in a state of discontinuity with each other, the plurality of island-like portions having an average particle diameter of 100 to 500 nm.
15. The metal thin film according to claim 13 or 14, wherein the metal thin film is any of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag), or an alloy thereof.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2018082657 | 2018-04-23 | ||
| JP2018-082657 | 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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| JP (1) | JP7319080B2 (en) |
| KR (1) | KR102680362B1 (en) |
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| CN114635113A (en) * | 2022-03-09 | 2022-06-17 | 北京科技大学 | Preparation method of high-brightness silvery white electromagnetic wave transmission composite film |
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- 2019-04-22 JP JP2019080636A patent/JP7319080B2/en active Active
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| CN114635113B (en) * | 2022-03-09 | 2023-04-07 | 北京科技大学 | Preparation method of high-brightness silvery white electromagnetic wave transmission composite film |
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| TW202003233A (en) | 2020-01-16 |
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| JP2019188807A (en) | 2019-10-31 |
| KR102680362B1 (en) | 2024-07-01 |
| JP7319080B2 (en) | 2023-08-01 |
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