WO2022209779A1 - Organe métallique brillant émettant les ondes électromagnétiques et son procédé de production - Google Patents

Organe métallique brillant émettant les ondes électromagnétiques et son procédé de production Download PDF

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Publication number
WO2022209779A1
WO2022209779A1 PCT/JP2022/011028 JP2022011028W WO2022209779A1 WO 2022209779 A1 WO2022209779 A1 WO 2022209779A1 JP 2022011028 W JP2022011028 W JP 2022011028W WO 2022209779 A1 WO2022209779 A1 WO 2022209779A1
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metal layer
electromagnetic wave
metallic luster
substrate
layer
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PCT/JP2022/011028
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English (en)
Japanese (ja)
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秀幸 北井
一斗 山形
基希 拝師
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日東電工株式会社
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Priority to JP2023510847A priority Critical patent/JPWO2022209779A1/ja
Publication of WO2022209779A1 publication Critical patent/WO2022209779A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B3/26—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 particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—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 particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon

Definitions

  • the present invention relates to an electromagnetic wave transmitting metallic luster member and a manufacturing method thereof.
  • members having electromagnetic wave permeability and metallic luster have been suitably used for devices that transmit and receive electromagnetic waves because they have both a luxurious appearance derived from the metallic luster and electromagnetic wave permeability.
  • Such an electromagnetic wave permeable metallic luster member can be used as a device for transmitting and receiving electromagnetic waves in various devices that require communication, such as door handles of automobiles equipped with smart keys, in-vehicle communication devices, mobile phones, electronic devices such as personal computers. It is expected to be applied to equipment and the like. Furthermore, in recent years, with the development of IoT technology, it is expected to be applied in a wide range of fields, such as household appliances such as refrigerators and household appliances, where communication has not been performed in the past.
  • Patent Document 1 discloses an indium oxide-containing layer provided on a surface of a substrate, and a metal layer laminated on the indium oxide-containing layer, wherein the metal layer is at least partially describes an electromagnetic wave transmitting metallic luster member characterized by comprising a plurality of portions that are discontinuous with each other.
  • the present invention was made to solve the above problems, and has excellent electromagnetic wave permeability and brightness, suppresses white turbidity and discoloration caused by stretching, and has excellent durability against humidification and heating.
  • An object of the present invention is to provide a durable metallic luster member.
  • the present inventors have found that by discontinuously providing a metal layer containing an aluminum element and an indium element and containing a specific amount of indium element on a substrate, , found that the above problems can be solved, and completed the present invention.
  • the present invention is as follows. [1] comprising a substrate and a metal layer formed on the substrate; The metal layer includes a plurality of portions that are discontinuous at least in part, The metal layer contains an aluminum element and an indium element, The content of the indium element in the metal layer is more than 90% by mass and 98% by mass or less, Electromagnetic wave permeable metal luster member. [2] The electromagnetic wave transmitting metallic luster member according to [1], wherein the aluminum element is unevenly distributed in the metal layer. [3] The electromagnetic wave transmitting metallic glossy member according to [1] or [2], wherein the metal layer contains at least one element selected from Sn, Si, Ga, Ge, and Pb.
  • an electromagnetic wave-transmitting metallic luster member that has excellent electromagnetic wave transmittance and luster, suppresses cloudiness and discoloration caused by stretching, and has excellent durability against humidification and heating.
  • FIG. 1 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member 1 according to one embodiment of the present invention.
  • FIG. 2 is an electron micrograph (SEM image) drawing of the surface of the electromagnetic wave transmitting metallic luster member 1 according to Example 2.
  • FIG. 3 is a diagram for explaining a method for measuring the thickness of the metal layer of the electromagnetic wave transmitting metallic luster member according to one embodiment of the present invention.
  • FIG. 4 is a photographic drawing showing the distribution of Al element and In element when elemental analysis was performed on the electromagnetic wave transmitting metallic luster member of Example 2.
  • FIG. 1 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member 1 according to one embodiment of the present invention.
  • FIG. 2 is an electron micrograph (SEM image) drawing of the surface of the electromagnetic wave transmitting metallic luster member 1 according to Example 2.
  • FIG. 3 is a diagram for explaining a method for measuring the thickness of the metal layer of the electromagnetic wave transmitting metallic luster member according to one embodiment of the present invention.
  • FIG. 4 is a photographic diagram in which a TEM image showing the distribution of Al elements in a metal layer and a TEM image showing the distribution of In elements are superimposed.
  • An electromagnetic wave transmitting metallic luster member comprises a base and a metal layer formed on the base,
  • the metal layer includes a plurality of portions that are discontinuous at least in part,
  • the metal layer contains an aluminum element and an indium element,
  • the content of the indium element in the metal layer is more than 90% by mass and 98% by mass or less.
  • An electromagnetic wave transmitting metallic luster member comprises a base and a metal layer formed on the base, wherein the metal layer has a plurality of portions that are discontinuous at least in part. including.
  • FIG. 1 shows a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster member 1 according to one embodiment of the present invention
  • FIG. 2 shows the surface of the electromagnetic wave transmitting metallic luster member 1 according to one embodiment of the present invention.
  • An example (Example 2) of an electron micrograph (SEM image) is shown. The image size in the electron micrograph is 6 ⁇ m ⁇ 5 ⁇ m.
  • the electromagnetic wave transmitting metallic luster member 1 includes a substrate 10 and a metal layer 12 formed on the substrate 10. As shown in FIG. In the electromagnetic wave transmitting metallic luster member 1, it is preferable that a discontinuous metal layer 12 is formed on a substrate 10 without forming an underlying layer between the substrate 10 and the metal layer 12. FIG. Since no underlayer is formed between the substrate 10 and the metal layer 12, cloudiness and discoloration due to stretching can be suppressed. It should be noted that any layer (protective layer or the like) that is less likely to cause cloudiness or discoloration due to stretching may be provided between the substrate 10 and the metal layer 12 . See ⁇ 4. other layers>.
  • the metal layer 12 includes a plurality of portions 12a. These portions 12a are at least partially discontinuous from each other, in other words, at least partially separated by gaps 12b. Since these portions 12a are separated by the gap 12b, the sheet resistance of these portions 12a is increased and the interaction with radio waves is reduced, so that the radio waves can be transmitted.
  • Each of these portions 12a is an aggregate of sputtered particles formed by vapor-depositing metal. When sputtered particles form a thin film on a substrate such as substrate 10, the surface diffusivity of the particles on the substrate affects the shape of the thin film.
  • discontinuous state means a state in which they are separated from each other by the gap 12b and, as a result, are electrically insulated from each other. By being electrically insulated, the sheet resistance is increased and the desired electromagnetic wave permeability can be obtained.
  • the form of discontinuity is not particularly limited, and includes, for example, an island shape, a crack structure, and the like.
  • FIG. 2 is an example of an electron micrograph (SEM image) of the surface of the metal layer of the electromagnetic wave permeable metallic luster member 1 .
  • the “island shape” means that the particles, which are aggregates of sputtered particles, are independent of each other, and the particles are slightly separated from each other or partially in contact with each other. It means a structure that is spread all over.
  • a crack structure is a structure in which a metal thin film is divided by cracks. It should be noted that such a crack structure is distinguished from the aforementioned cracks that occur during stretching.
  • the metal layer 12 having a crack structure can be formed, for example, by providing a metal thin film layer on a substrate and bending and stretching the metal thin film layer to cause cracks in the metal thin film layer. At this time, the metal layer 12 having a crack structure can be easily formed by providing a brittle layer made of a material having poor stretchability, that is, being easily cracked by stretching, between the substrate and the metal thin film layer.
  • the mode in which the metal layer 12 becomes discontinuous is not particularly limited, but from the viewpoint of productivity, it is preferably "island-shaped".
  • the electromagnetic wave permeability of the electromagnetic wave transparent metallic luster member 1 can be evaluated, for example, by the amount of radio wave transmission attenuation.
  • the radio wave transmission attenuation can be measured, for example, by the method described later in Examples.
  • the radio wave transmission attenuation at 28 GHz can be evaluated using a KEC method measurement evaluation jig and Agilent's spectrum analyzer CXA Signal Analyzer NA9000A.
  • a KEC method measurement evaluation jig and Agilent's spectrum analyzer CXA Signal Analyzer NA9000A There is a correlation between the electromagnetic wave permeability in the millimeter wave radar frequency band (76 to 80 GHz) and the electromagnetic wave permeability in the microwave band (28 GHz).
  • the electromagnetic wave permeability that is, the microwave electric field transmission attenuation amount is used as an index.
  • the radio wave transmission attenuation in the microwave band (28 GHz) is preferably 1 [-dB] or less, more preferably 0.3 [-dB] or less, and 0.1 [-dB] or less. is more preferred.
  • the radio wave transmission attenuation in the microwave band (28 GHz) is preferably 1 [-dB] or less, more preferably 0.3 [-dB] or less, and 0.1 [-dB] or less. is more preferred.
  • the brilliance (appearance) of the electromagnetic wave transmitting metallic luster member 1 can be evaluated by measuring, for example, the Y value (SCI, SCE) and ⁇ E value.
  • the Y value (SCI, SCE) and ⁇ E value can be measured using a spectrophotometer according to geometric condition c of JIS Z 8722.
  • the durability of the electromagnetic wave transparent metallic luster member 1 to humidified heating can be evaluated by each index of the above-mentioned luster (appearance) before and after the humidified heating test at 65°C and 90% RH.
  • the Y value (SCI) after the humidified heating test is preferably 40% or higher, more preferably 50% or higher, and even more preferably 60% or higher. When the Y value (SCI) is 40% or more, the gloss is good and the appearance is excellent. Also, the upper limit of the Y value (SCI) after the humidification heating test is not particularly limited, but is, for example, 70% or less.
  • the ⁇ E value is an index that indicates a change in color tone, and is the L * value, a * value, and b * value (L 1 * , a 1 * , b 1 * ) before the humidification heat test, and the L value after the humidification heat test.
  • a smaller ⁇ E value indicates that the change in color tone due to humidification and heating can be suppressed.
  • the ⁇ E value is preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less.
  • the stretching resistance of the electromagnetic wave transmitting metallic luster member 1 is evaluated using a tensile tester under the conditions of 150° C., 5 mm/min stretching speed, and 20% elongation rate before and after the above-mentioned brilliance (appearance). can be evaluated by each index.
  • the Y value (SCI) after the tensile test is preferably 40% or more, more preferably 50% or more, even more preferably 55% or more. When the Y value (SCI) is 40% or more, the gloss is good and the appearance is excellent.
  • the Y value (SCE) after the tensile test is preferably 1 or less, more preferably 0.3 or less, and even more preferably 0.1 or less. If the Y value (SCE) is more than 1, there is a problem that the appearance becomes cloudy and the appearance is not excellent.
  • the stretchability of the electromagnetic wave transmitting metallic luster member 1 can also be evaluated by measuring the crack width of the metal layer after the tensile test.
  • the tensile test is performed, for example, by the same method as for the luster (appearance). It can be said that the smaller the crack width of the metal layer after the tensile test is, the more the crack generation due to stretching can be suppressed, and the better the stretching resistance is.
  • the crack width of the metal layer after the tensile test is preferably 170 nm or less, more preferably 160 nm or less, even more preferably 150 nm or less.
  • the substrate 10 includes, for example, a substrate film, a resin molding substrate, or an article to which metallic luster is to be imparted.
  • the base film includes, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, polycarbonate (PC), cycloolefin polymer (COP), polystyrene , polypropylene (PP), polyethylene, polycycloolefin, polyurethane, acrylic (PMMA), ABS, and other homopolymers or copolymers.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • COP cycloolefin polymer
  • PP polystyrene
  • polypropylene PP
  • polyethylene polycycloolefin
  • polyurethane acrylic
  • ABS and other homopolymers or copolymers.
  • polyethylene terephthalate, polyethylene naphthalate, acrylic, polycarbonate, cycloolefin polymer, ABS, polypropylene, and polyurethane are preferable.
  • polyethylene terephthalate, cycloolefin polymer, polycarbonate, and acrylic are preferable because they have a good balance between heat resistance and cost.
  • the base film may be a single layer film or a laminated film.
  • the thickness is preferably, for example, about 6 ⁇ m to 250 ⁇ m from the viewpoint of ease of processing.
  • a plasma treatment, an easy-adhesion treatment, or the like may be applied.
  • the base film is only an example of the object (substrate 10) on which the metal layer 12 can be formed.
  • the substrate 10 includes the base film as described above, as well as a resin molding base and the article itself to which metallic luster is to be imparted.
  • Resin molded substrates and articles to be imparted with metallic luster include, for example, vehicle structural parts, vehicle-mounted goods, housings for electronic equipment, housings for home appliances, structural parts, mechanical parts, and various automobiles. parts for electronic equipment, household goods such as furniture and kitchen utensils, medical equipment, parts for building materials, other structural parts and exterior parts.
  • a metal layer 12 is formed over the substrate 10 .
  • the metal layer 12 may be provided directly on the surface of the substrate 10, or may be provided indirectly via a layer such as a protective layer provided on the surface of the substrate 10, which is unlikely to cause cracks due to stretching. may be
  • the metal layer 12 is a layer having a metallic appearance, and is preferably a layer having metallic luster.
  • the metal layer 12 contains aluminum element and indium element. Among them, it is preferable that the aluminum element is unevenly distributed in the metal layer 12 . That is, as shown in FIG. 4, it is preferable that the aluminum element is unevenly distributed in one region of the metal layer 12 instead of being uniformly dispersed in the metal layer 12. . As long as the aluminum element is unevenly distributed in the metal layer 12, there is no limitation on the aspect thereof, but as shown in FIG. preferable. In other words, it is preferable that the aluminum element is unevenly distributed in the metal layer 12 so as to surround the indium element. Moreover, it is preferable that the aluminum element and the indium element in the metal layer 12 are not substantially compatible with each other.
  • the aluminum element and the indium element are not compatible with each other (not alloyed) in a range deeper than 14 nm from the surface of the metal layer 12.
  • the reason why the aluminum element and the indium element are substantially incompatible with each other and exist in the metal layer is that the sputtering temperature is low.
  • the content of the indium element in the metal layer 12 is more than 90% by mass and 98% by mass or less.
  • the content of the indium element is more than 90% by mass, the shape of the island becomes disc-shaped, and thus the durability against humidification and heating is excellent.
  • the content of the indium element is 98% by mass or less, aluminum is present in the surroundings, so that the durability is excellent.
  • the content of the indium element in the metal layer 12 is preferably 92% by mass or more.
  • the content of the indium element in the metal layer 12 is preferably 96% by mass or less.
  • the above indium element is not particularly limited and may be contained as an indium alloy as well as indium alone. Examples include In--Sn, In--Cr, and In--Zn. However, as described above, alloys of indium and aluminum are not included.
  • the content of the aluminum element in the metal layer 12 is preferably 2% by mass or more, more preferably 4% by mass or more.
  • An aluminum oxide film is formed around the indium by being 2% by mass or more.
  • the content of the aluminum element in the metal layer 12 is preferably 10% by mass or less, more preferably 8% by mass or less.
  • the above aluminum element is not particularly limited and may be contained as an aluminum alloy in addition to aluminum alone. Examples include Cu, Mn, Si, Mg, Zn and Ni. However, as described above, alloys of indium and aluminum are not included.
  • the metal layer 12 may contain other metal elements. Preferably, it contains at least one element of Sn, Si, Ga, Ge, and Pb. These may exist singly in the metal layer, or may be contained in the form of an alloy. For example, Sn may be included in the metal layer in the form of ITM (indium-tin-metal alloy), which is an alloy with the element indium. By including the other metal elements, the metal layer 12 is more excellent in durability against humidification and heating.
  • ITM indium-tin-metal alloy
  • the thickness of the metal layer 12 is preferably 10 nm or more, more preferably 40 nm or more, even more preferably 60 nm or more, and particularly preferably 80 nm or more.
  • the thickness is preferably 100 nm or less, more preferably 80 nm or less, and even more preferably 60 nm or less. This thickness is also suitable for forming a uniform film with good productivity, and the appearance of the resin molded product, which is the final product, is also good.
  • the thickness of the metal layer 12 can be measured, for example, by the method described later in Examples.
  • the metal layer 12 is formed on the substrate 10 and includes a plurality of portions that are discontinuous at least in part. If the metal layer 12 is in a continuous state on the substrate 10, sufficient metallic luster can be obtained, but the amount of radio wave transmission attenuation becomes very large, and therefore the electromagnetic wave permeability cannot be ensured.
  • the oxygen concentration in the metal layer 12 In order to discontinuously form the metal layer 12 on the substrate 10, it is preferable to lower the oxygen concentration in the metal layer 12.
  • the surface diffusibility of the particles on the substrate affects the shape of the thin film. It is considered that a discontinuous structure is likely to be formed when it is small and the melting point of the material of the metal layer is low.
  • the surface diffusibility of the metal particles on the substrate surface is promoted to form a metal layer. can be formed in a discontinuous state.
  • the equivalent circle diameter of the portion 12a of the metal layer 12 is not particularly limited, but is usually 10 to 1000 nm.
  • the average particle size of the plurality of portions 12a means the average value of the equivalent circle diameters of the plurality of portions 12a.
  • the equivalent circle diameter of the portion 12a is the diameter of a perfect circle corresponding to the area of the portion 12a. Also, the distance between the portions 12a is not particularly limited, but is usually about 10 to 1000 nm.
  • the electromagnetic wave transmitting metallic luster member 1 may include other layers in addition to the metal layer 12 described above, depending on the application.
  • the continuous layers are likely to crack due to stretching. Therefore, when another layer is provided between the substrate 10 and the metal layer 12, it is preferable that the layer is less likely to cause cracks.
  • optical adjustment layer such as a high refractive material for adjusting appearance such as color
  • a protective layer for improving durability such as scratch resistance layer
  • barrier layer corrosion-resistant layer
  • easy-adhesion layer hard coat layer
  • antireflection layer light extraction layer
  • anti-glare layer and the like.
  • Method for producing an electromagnetic wave transmitting metallic luster member In the method for manufacturing an electromagnetic wave transmitting metallic luster member according to the present embodiment, a layer containing at least an indium element and including a plurality of portions that are at least partially discontinuous with each other (hereinafter simply referred to as discontinuous and a second step of vapor-depositing a metal containing aluminum element on the discontinuous layer. Each step will be described in detail below.
  • a layer containing at least an indium element and including a plurality of portions that are at least partially discontinuous with each other is formed on the substrate 10 .
  • the discontinuous layer can be formed, for example, by evaporating a metal containing indium on the surface of the substrate 10 .
  • vapor deposition methods include physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating, and chemical vapor deposition (CVD) such as plasma CVD, optical CVD, and laser CVD. Physical vapor deposition is preferred, and sputtering is more preferred. Discontinuous layers of uniform thin films can be formed by this method.
  • the discontinuous layer by a sputtering method using a metal target material containing indium element and substantially free of oxygen (1 volume % or less). More preferably, the metal target material does not contain oxygen at all. Since such a metal target material does not contain oxygen, the wettability with the substrate can be reduced, and the formation of a discontinuous layer on the substrate 10 is promoted. For the same reason, when forming a discontinuous layer, it is preferable to perform vapor deposition in an atmosphere that does not substantially contain oxygen (100 volume ppm or less), and vapor deposition is performed in an atmosphere that does not contain oxygen at all. is more preferred.
  • the indium element contained in the metal target material is not particularly limited and may be contained as an indium alloy as well as indium alone. Examples include In--Sn, In--Cr, and In--Zn.
  • the metal target material may contain silver (Ag), chromium (Cr), etc., in addition to the metal containing indium.
  • Sputtering is performed under vacuum.
  • the atmospheric pressure during sputtering is, for example, 1 Pa or less, preferably 0.7 Pa or less, from the viewpoints of suppressing a decrease in sputtering rate, discharge stability, and the like.
  • the power source used in the sputtering method may be, for example, a DC power source, an AC power source, an MF power source, an RF power source, or a combination thereof.
  • sputtering may be performed multiple times by appropriately setting the metal target material, sputtering conditions, and the like.
  • a metal containing an aluminum element is vapor-deposited on the formed discontinuous layer.
  • the same method as in the first step can be adopted.
  • a metal containing an aluminum element is used as the metal target material.
  • the aluminum element may be contained in the metal target material as aluminum alone, as an aluminum compound, or as an aluminum alloy.
  • the metal target material may contain zinc (Zn), lead (Pb), copper (Cu), silver (Ag), etc., in addition to the metal containing aluminum element.
  • a discontinuous metal layer containing aluminum and indium can be formed on the substrate.
  • the metal layer is formed so as to contain more than 90% by mass and 98% by mass or less of the indium element.
  • the aluminum element and the indium element exist in the metal layer without being compatible with each other. That is, the aluminum element and the indium element exist in the metal layer without forming an alloy.
  • the electromagnetic wave transmitting metallic luster member of the present embodiment has electromagnetic wave transmitting properties, it is preferably used for devices, articles, and parts thereof that transmit and receive electromagnetic waves.
  • the electromagnetic wave transmitting metallic luster member of the present embodiment has electromagnetic wave transmitting properties, it is preferably used for devices, articles, and parts thereof that transmit and receive electromagnetic waves.
  • ECU boxes electrical components, engine peripheral parts, drive system/gear peripheral parts, intake/exhaust system parts, cooling system parts, and the like.
  • electronic devices and home appliances include home appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, televisions, clocks, ventilation fans, projectors, speakers, personal computers, and mobile phones.
  • home appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, televisions, clocks, ventilation fans, projectors, speakers, personal computers, and mobile phones.
  • smart phones digital cameras, tablet PCs, portable music players, portable game machines, battery chargers, electronic information devices such as batteries, and the like.
  • Nitto Denko's Luciax CS9861UAS adheresive layer
  • Matsunami Glass Industry's slide glass glass
  • a sample was obtained.
  • a humidification heating test was performed by placing the glass-attached sample in an environment of 65° C. and 90% RH for 120 hours. The following evaluations of radio wave transmittance and brilliance were performed on the glass-attached sample before the humidification heat test and the glass-attached sample after the humidification heat test.
  • Radio wave transmission attenuation at 28 GHz was measured from the substrate surface side using a free space method evaluation jig (Keycom) LAF-26.5A, an antenna WR-28 and a spectrum analyzer (CXA signal Analyzer NA9000A) manufactured by Agilent. There is a correlation between the electromagnetic wave permeability in the millimeter wave radar frequency band (76 to 80 GHz) and the electromagnetic wave permeability in the microwave band (28 GHz). The electromagnetic wave permeability in the band (28 GHz), that is, the microwave electric field transmission attenuation amount was used as an index and judged according to the following criteria. Table 2 shows the measurement results.
  • a total of five points “a” to “e” obtained by dividing each of the center lines A and B of the horizontal sides into quarters were selected as measurement points.
  • a viewing angle region containing approximately five portions 12a was extracted from the cross-sectional image at each of the selected measurement locations. Five portions 12a at each of these five measurement points, that is, the individual thicknesses of 25 (5 ⁇ 5 points) portions 12a are obtained, and the average value thereof is defined as the "maximum thickness". did.
  • [Contents of aluminum element and indium element] The contents of aluminum element and indium element in the metal layer were measured by fluorescent X-ray analysis. As an analyzer, ZSX Primus III+ manufactured by Rigaku was used. The measured fluorescence intensity was converted to the thickness of the sample using a calibration curve obtained from measurements of an indium simple substance film and an aluminum simple substance film having known thicknesses as reference samples. From the thickness of the obtained sample, mass conversion was performed using an aluminum density of 2.70 g/cm 3 and an indium density of 7.31 g/cm 3 to calculate the contents of aluminum element and indium element in the metal layer.
  • Example 1 As a base film, an easy-to-form PET film manufactured by Mitsubishi Chemical Corporation (product number: G931E75, thickness: 50 ⁇ m) was used. First, using an In—Sn alloy target (Sn ratio of 5% by mass): ITM, a layer composed of an In—Sn alloy was formed as a first layer on the base film by DC pulse sputtering (150 kHz). Sputtering was performed in an atmosphere in which oxygen was not supplied. The resulting first layer had a discontinuous structure. Next, an aluminum (Al)-containing layer was formed as a second layer on the first layer by alternating current sputtering (AC: 40 kHz) using an Al target.
  • ITM In—Sn alloy target
  • AC alternating current sputtering
  • the electromagnetic wave transmitting metallic luster member of Example 1 in which the metal layer was formed on the base film, was obtained.
  • Tables 1 and 2 show the results of various evaluations of the obtained electromagnetic wave transmitting metallic luster member of Example 1. Further, elemental analysis was performed using FE-TEM JEM-2800 manufactured by JEOL Ltd. to measure the distribution of Al element and In element.
  • Example 1 It was confirmed that the metal layer obtained in Example 1 had a discontinuous structure. It was also confirmed that the aluminum element was unevenly distributed in the metal layer so as to surround the indium element. Moreover, the distribution regions of the aluminum element and the indium element overlapped in a range of 14 nm or less in depth from the surface of the metal layer. That is, it was found that the aluminum element and the indium element were not compatible with each other (not alloyed) in a range deeper than 14 nm from the surface of the metal layer.
  • Example 2 to 10 Electromagnetic wave-transmitting metallic luster members of Examples 2 to 10 were produced and evaluated in the same manner as in Example 1, except that the contents of the aluminum element and the indium element in the metal layer were changed as shown in Tables 1 and 2. did. In addition, Examples 7 to 10 were evaluated only from the side of the base material. It was also confirmed that the metal layers in Examples 2 to 10 had a discontinuous structure.
  • FIG. 2 shows an electron micrograph (SEM image) of the surface of the electromagnetic wave transmitting metallic luster member in Example 2. As shown in FIG. Further, it was confirmed that the metal layers in Examples 2 to 10 were unevenly distributed in the metal layer so that the aluminum element surrounded the indium element. Only the results of elemental analysis in Example 2 are shown in FIG. Also in Examples 2 to 10, the distribution regions of the aluminum element and the indium element overlapped in a range of 14 nm or less in depth from the surface of the metal layer (only in Example 2, (d )).
  • Comparative example 1 An electromagnetic wave transmitting metallic luster member of Comparative Example 1 was produced and evaluated in the same manner as in Example 1, except that the contents of the aluminum element and the indium element in the metal layer were changed as shown in Tables 1 and 2.
  • Comparative example 2 An electromagnetic wave transmitting metallic luster member of Comparative Example 2 was produced in the same manner as in Example 1, except that the first layer was made of an In—Sn alloy and the metal layer was formed without providing the second layer. made and evaluated.
  • Comparative Example 3 An electromagnetic wave transmitting metallic luster member of Comparative Example 3 was produced and evaluated in the same manner as in Example 1 except that the contents of the aluminum element and the indium element in the metal layer were changed as shown in Tables 1 and 2.
  • Comparative Example 4 In—Sn alloy target (Sn ratio of 5% by mass): Same as Example 1 except that ITM was changed to In and the contents of aluminum element and indium element in the metal layer were changed as shown in Tables 1 and 2. Then, an electromagnetic wave transmitting metallic glossy member of Comparative Example 4 was produced and evaluated.
  • the electromagnetic wave transmitting metallic luster members of Examples 1 to 10 showed good results in both electromagnetic wave transmittance and appearance after the humidification heating test and after the tensile test.
  • Comparative Example 1 the indium element content in the metal layer was as low as 25% by mass, resulting in a high ⁇ E value and poor brightness (appearance).
  • Comparative Example 2 does not contain Al element, the Y value (SCI) in the humidified heating test is low, and the ⁇ E value is high, resulting in poor brightness (appearance).
  • Comparative Example 3 since the orderliness of the island-like shape was low and defects were generated, the ⁇ E value was high and the brilliance (appearance) was poor.
  • the present invention is not limited to the above embodiments, and can be modified and embodied as appropriate without departing from the gist of the invention.
  • the electromagnetic wave permeable metallic luster member according to the present invention can be used for devices, articles, and parts thereof that transmit and receive electromagnetic waves.

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

Abstract

La présente invention concerne un organe métallique brillant émettant les ondes électromagnétiques qui comprend : un corps de base ; et une couche métallique formée sur le corps de base. La couche métallique comporte une pluralité de parties qui sont au moins partiellement discontinues les unes par rapport aux autres. La couche métallique contient des éléments aluminium et des éléments indium, et la quantité des éléments indium contenue dans la couche métallique est supérieure à 90 % en masse mais inférieure ou égale à 98 % en masse.
PCT/JP2022/011028 2021-03-29 2022-03-11 Organe métallique brillant émettant les ondes électromagnétiques et son procédé de production WO2022209779A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009006613A (ja) * 2007-06-28 2009-01-15 Nissha Printing Co Ltd 加飾シート、加飾シートの製造方法および加飾成形品の製造方法
JP2009006612A (ja) * 2007-06-28 2009-01-15 Nissha Printing Co Ltd 加飾シート、加飾シートの製造方法および加飾成形品の製造方法
JP2009286082A (ja) * 2008-05-30 2009-12-10 Toyoda Gosei Co Ltd 電磁波透過性光輝樹脂製品及び製造方法
JP4601262B2 (ja) * 2002-03-25 2010-12-22 日本写真印刷株式会社 金属発色を有するカバーパネル
JP4732147B2 (ja) * 2005-11-21 2011-07-27 豊田合成株式会社 樹脂製品及びその製造方法並びに金属皮膜の成膜方法
JP2019031079A (ja) * 2017-08-04 2019-02-28 積水化学工業株式会社 積層体
WO2020067052A1 (fr) * 2018-09-25 2020-04-02 積水化学工業株式会社 Corps perméable aux ondes radio
US20200299831A1 (en) * 2017-04-07 2020-09-24 Byoung Sam Kim Manufacturing method of radio wave transmittable sensor cover having micro crack and laser hole and radio wave transmittable sensor cover manufactured using the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4601262B2 (ja) * 2002-03-25 2010-12-22 日本写真印刷株式会社 金属発色を有するカバーパネル
JP4732147B2 (ja) * 2005-11-21 2011-07-27 豊田合成株式会社 樹脂製品及びその製造方法並びに金属皮膜の成膜方法
JP2009006613A (ja) * 2007-06-28 2009-01-15 Nissha Printing Co Ltd 加飾シート、加飾シートの製造方法および加飾成形品の製造方法
JP2009006612A (ja) * 2007-06-28 2009-01-15 Nissha Printing Co Ltd 加飾シート、加飾シートの製造方法および加飾成形品の製造方法
JP2009286082A (ja) * 2008-05-30 2009-12-10 Toyoda Gosei Co Ltd 電磁波透過性光輝樹脂製品及び製造方法
US20200299831A1 (en) * 2017-04-07 2020-09-24 Byoung Sam Kim Manufacturing method of radio wave transmittable sensor cover having micro crack and laser hole and radio wave transmittable sensor cover manufactured using the same
JP2019031079A (ja) * 2017-08-04 2019-02-28 積水化学工業株式会社 積層体
WO2020067052A1 (fr) * 2018-09-25 2020-04-02 積水化学工業株式会社 Corps perméable aux ondes radio

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