WO2019208499A1 - Article à perméabilité électromagnétique à brillant métallique - Google Patents

Article à perméabilité électromagnétique à brillant métallique Download PDF

Info

Publication number
WO2019208499A1
WO2019208499A1 PCT/JP2019/017034 JP2019017034W WO2019208499A1 WO 2019208499 A1 WO2019208499 A1 WO 2019208499A1 JP 2019017034 W JP2019017034 W JP 2019017034W WO 2019208499 A1 WO2019208499 A1 WO 2019208499A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal layer
substrate
metallic luster
article
indium oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/017034
Other languages
English (en)
Japanese (ja)
Inventor
太一 渡邉
孝洋 中井
暁雷 陳
秀幸 北井
秀行 米澤
幸大 宮本
将治 有本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to CN201980027688.3A priority Critical patent/CN112004666A/zh
Priority to KR1020207029677A priority patent/KR102680787B1/ko
Priority claimed from JP2019080643A external-priority patent/JP7319081B2/ja
Publication of WO2019208499A1 publication Critical patent/WO2019208499A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/14—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side

Definitions

  • the present invention relates to an electromagnetic wave transparent metallic luster article.
  • members having electromagnetic wave transparency and metallic luster have been suitably used for devices that transmit and receive electromagnetic waves because they have both a high-quality appearance derived from the metallic luster and electromagnetic wave transparency.
  • a metallic luster article that combines both luster and electromagnetic wave transmission, in which a cover member of a millimeter wave radar mounted on the front part of an automobile such as a front grill and an emblem is decorated.
  • Millimeter wave radar transmits millimeter wave electromagnetic waves (frequency: about 77 GHz, wavelength: about 4 mm) to the front of the car, receives reflected waves from the target, and measures and analyzes the reflected waves. The distance, target direction, and size can be measured. The measurement result can be used for inter-vehicle measurement, automatic speed adjustment, automatic brake adjustment, and the like. Since the front part of the automobile in which such a millimeter wave radar is arranged is a so-called automobile face and is a part that gives a large impact to the user, it is preferable to produce a high-class feeling with a metallic glossy front decoration.
  • This kind of metallic luster article is not only a millimeter wave radar but also various devices that require communication, for example, automobile door handles with smart keys, in-vehicle communication devices, mobile phones, electronic devices such as personal computers, etc.
  • the application of is expected.
  • IoT technology application in a wide range of fields such as household appliances such as refrigerators, daily life equipment, etc., which has not been conventionally performed, is expected.
  • Patent Document 1 describes a metal thin film transfer material in which Sn is deposited by vacuum deposition.
  • the glitter is improved by increasing the coverage of the metal film, but it is not sufficient. To increase the coverage, it is necessary to increase the film thickness, and there is a problem in terms of cost.
  • the vacuum vapor deposition method described in Patent Document 1 it is difficult to form a wide, uniform and stable film, and the metal film is likely to be oxidized under a low vacuum. Therefore, an article that is excellent in electromagnetic wave permeability and has both a thin metal layer and high glitter is desired.
  • the present invention was made in order to solve these problems in the prior art, and provides an electromagnetic wave transmissive metallic luster article that is excellent in electromagnetic wave permeability and has both a thin metal layer and high glitter. Objective.
  • the present inventors usually have a discontinuous structure, for example, a metal layer made of other metals such as aluminum (Al) has a discontinuous structure and is glossy. It has been found that the average particle size of a plurality of portions in a discontinuous state and in a specific range is excellent in electromagnetic wave permeability and achieves both a reduction in the thickness of the metal layer and high glitter, and the present invention. It came to be completed.
  • One embodiment of the present invention includes a base and a metal layer formed on the base, and the 20 ° gloss is 900 or more.
  • the metal layer relates to an electromagnetic wave transmissive metallic luster article that includes a plurality of portions that are discontinuous with each other at least partially, and an average particle size of the plurality of portions is 30 nm or more and less than 100 nm.
  • Another aspect of the present invention includes a base and a metal layer formed on the base,
  • the metal layer includes a plurality of portions at least partially discontinuous with each other,
  • the coverage of the substrate with the metal layer is 75% or more and less than 100%
  • the present invention relates to an electromagnetic wave transparent metallic glossy article having an average particle size of the plurality of portions of 30 nm or more and less than 100 nm.
  • an indium oxide-containing layer is further provided between the base and the metal layer.
  • the indium oxide-containing layer is preferably provided in a continuous state.
  • the indium oxide-containing layer is made of either indium oxide (In 2 O 3 ), indium tin oxide (ITO), or indium zinc oxide (IZO). It is preferable to include.
  • the thickness of the indium oxide-containing layer is preferably 1 nm to 1000 nm.
  • the thickness of the metal layer is preferably 15 nm to 100 nm.
  • the ratio of the thickness of the metal layer to the thickness of the indium oxide-containing layer is 0. .02 to 100 may be used.
  • the sheet resistance may be 100 ⁇ / ⁇ or more.
  • the plurality of portions may be formed in an island shape.
  • the metal layer is made of aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag), or an alloy thereof. It is preferable that
  • the substrate is preferably any one of a base film, a resin molded article base, a glass base, or an article to be provided with a metallic luster.
  • an electromagnetic wave transmissive metallic luster article that is excellent in electromagnetic wave transmission properties and has both a thin metal layer and high glitter.
  • FIG. 1 is a schematic cross-sectional view of an electromagnetic wave transmissive metallic luster article according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of an electromagnetic wave transmissive metallic luster article according to an embodiment of the present invention.
  • FIG. 3 is a view showing an electron micrograph of the surface of an electromagnetic wave transparent metallic glossy article according to an embodiment of the present invention.
  • FIG. 4 is a graph showing the relationship between the coverage and glossiness of the electromagnetic wave transmissive metallic luster articles of Examples and Comparative Examples.
  • FIG. 5 is a graph showing the relationship between the film thickness and coverage of the electromagnetic wave transmissive metallic luster articles of Examples and Comparative Examples.
  • FIG. 1 is a schematic cross-sectional view of an electromagnetic wave transmissive metallic luster article according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of an electromagnetic wave transmissive metallic luster article according to an embodiment of the present invention.
  • FIG. 3 is a view showing an electron micrograph
  • FIG. 6 is a diagram showing the relationship between the crystal grains (average particle diameter) and the coverage of the electromagnetic wave transmissive metallic luster articles of Examples and Comparative Examples.
  • FIG. 7 is a view for explaining a method for measuring the thickness of the metal layer of the electromagnetic wave transparent metallic glossy article according to an embodiment of the present invention.
  • FIG. 8 is a diagram showing a transmission electron micrograph (TEM image) of a cross section of a metal layer in one embodiment of the present invention.
  • TEM image transmission electron micrograph
  • An electromagnetic wave-transmissive metallic glossy article includes a base and a metal layer formed on the base, and the 20 ° gloss is 900 or more.
  • the metal layer includes a plurality of portions that are discontinuous with each other at least partially, and the average particle size of the plurality of portions is not less than 30 nm and less than 100 nm.
  • An electromagnetic wave transmissive metallic luster article includes a base and a metal layer formed on the base.
  • the metal layer includes a plurality of portions at least partially discontinuous with each other, The coverage of the substrate with the metal layer is 75% or more and less than 100%, The plurality of portions have an average particle size of 30 nm or more and less than 100 nm.
  • FIG. 1 shows a schematic cross-sectional view of an electromagnetic wave transmissive metallic luster article (hereinafter referred to as “metallic luster article”) 1 according to an embodiment of the present invention
  • FIG. 3 shows a metallic luster article according to an embodiment of the present invention
  • 1 shows an electron micrograph (SEM image) of the surface of No. 1
  • FIG. 8 shows a transmission electron micrograph (TEM image) of a cross-sectional view of the island-shaped metal layer 11 in one embodiment of the present invention.
  • SEM image electron micrograph
  • TEM image transmission electron micrograph
  • the metallic luster article 1 includes a base 10 and a metal layer 12 formed on the base 10.
  • the metal layer 12 is formed on the substrate 10.
  • the metal layer 12 includes a plurality of portions 12a.
  • the plurality of portions 12a in the metal layer 12 are discontinuous from each other at least in part, in other words, at least partially separated by the gap 12b. Since the sheet is separated by the gap 12b, the sheet resistance of the metallic luster article is increased and the interaction with the radio wave is reduced, so that the radio wave can be transmitted.
  • Each of the plurality of portions 12a may be an aggregate of sputtered particles formed by vapor deposition, sputtering, or the like of metal. Note that the “discontinuous state” in the present specification 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.
  • the sheet resistance increases, and the desired electromagnetic wave permeability can be obtained. That is, according to the metal layer 12 formed in a discontinuous state, sufficient glitter can be easily obtained, and electromagnetic wave permeability can be secured.
  • a discontinuous form is not specifically limited, For example, an island-like structure, a crack structure, etc. are contained.
  • the “island-like structure” means that metal particles are independent from each other as shown in FIG. 3, and the particles are spread in a state of being slightly separated or partially in contact with each other. It is the structure which becomes.
  • the crack structure is a structure in which a metal thin film is divided by a 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 it to cause a crack 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 between the base film and the metal thin film layer. .
  • the aspect in which the metal layer 12 is discontinuous is not particularly limited, but an island structure is preferable from the viewpoint of productivity.
  • the 20 ° glossiness of the metallic luster article needs to be 900 or more, preferably 1100 or more, and more preferably 1300 or more. If it is less than 900, there is a problem that the metallic appearance cannot be obtained due to inferior luster.
  • the 20 ° glossiness of a metallic luster article can be measured according to JIS Z 8741 (1997 edition). Specifically, the measurement can be performed using PG-IIM (20 ° gloss measurement, manufactured by Nippon Denshoku Industries Co., Ltd.). In addition, the measurement of 20 degree glossiness is performed with respect to the surface by the side of a metal layer.
  • the electromagnetic wave permeability of the metallic luster article 1 can be evaluated by, for example, the amount of radio wave transmission attenuation. Note that there is a correlation between the radio wave transmission attenuation in the microwave band (5 GHz) and the radio wave transmission attenuation in the millimeter wave radar frequency band (76 to 80 GHz). A metallic luster article excellent in electromagnetic wave transmission in the wave band is also excellent in electromagnetic wave transmission in the frequency band of the millimeter wave radar.
  • the electromagnetic wave permeability in the microwave band is preferably 10 [-dB] or less, more preferably 5 [-dB] or less, and still more preferably 2 [-dB] or less. If it is larger than 10 [-dB], there is a problem that 90% or more of radio waves are blocked.
  • the sheet resistance of the metallic luster article 1 also has a correlation with the electromagnetic wave permeability.
  • the sheet resistance of the metallic luster article 1 is preferably 100 ⁇ / ⁇ or more.
  • the radio wave transmission attenuation in the microwave band (5 GHz) is about 10 to 0.01 [ ⁇ dB].
  • the sheet resistance of the metallic luster article is more preferably 200 ⁇ / ⁇ or more, and further preferably 600 ⁇ / ⁇ or more. Particularly preferably, it is 1000 ⁇ / ⁇ or more.
  • the sheet resistance of the metallic luster article 1 can be measured by an eddy current measurement method according to JIS-Z2316-1: 2014.
  • the radio wave transmission attenuation amount and sheet resistance of the metallic luster article 1 are affected by the material and thickness of the metal layer 12.
  • the metallic luster article 1 includes the indium oxide-containing layer 11, it is also affected by the material and thickness of the indium oxide-containing layer 11.
  • the substrate 10 include resins, glasses, and ceramics from the viewpoint of electromagnetic wave transmission.
  • the substrate 10 may be any of a substrate film, a resin molded substrate, a glass substrate, or an article to which a metallic luster is to be imparted.
  • the base film for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, polycarbonate (PC), cycloolefin polymer (COP), polystyrene
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • COP cycloolefin polymer
  • PP polypropylene
  • PMMA polyurethane
  • ABS acrylic
  • these members do not affect the glitter and electromagnetic wave transmission.
  • it is preferably one that can withstand high temperatures such as vapor deposition and sputtering. Therefore, among the above materials, for example, polyethylene terephthalate, polyethylene naphthalate, Acrylic, polycarbonate, cycloolefin polymer, ABS, polypropylene and polyurethane are preferred. Of these, polyethylene terephthalate, cycloolefin polymer, polycarbonate, and acrylic are preferable because of a good balance between heat resistance and cost.
  • the base film may be a single layer film or a laminated film. From the viewpoint of ease of processing, the thickness is preferably about 6 ⁇ m to 250 ⁇ m, for example.
  • plasma treatment, easy adhesion treatment, or the like may be performed.
  • the metal layer 12 may be provided on at least a part of the base film, may be provided only on one side of the base film, or may be provided on both sides.
  • the base film is only an example of an object (substrate 10) on which the metal layer 12 can be formed.
  • the base 10 includes a resin molded product base, a glass base, and an article itself to which a metallic luster is to be imparted.
  • the resin molding base material and the article to be provided with metallic luster include, for example, vehicle structural parts, vehicle-mounted products, electronic equipment casings, home appliance casings, structural parts, mechanical parts, and various automobiles. Examples include parts, electronic device parts, furniture, kitchenware, and other household goods, medical equipment, building material parts, other structural parts, exterior parts, and the like.
  • the metal layer 12 can be formed on all of these substrates, and may be formed on a part of the surface of the substrate or on the entire surface of the substrate.
  • the substrate 10 to which the metal layer 12 is to be applied preferably satisfies the same materials and conditions as those of the base film.
  • the metallic luster article 1 which concerns on one Embodiment may further be provided with the indium oxide containing layer 11 between the base
  • the indium oxide-containing layer 11 may be provided directly on the surface of the substrate 10 or indirectly through a protective film or the like provided on the surface of the substrate 10.
  • the indium oxide-containing layer 11 is preferably provided in a continuous state on the surface of the substrate 10 to be provided with a metallic luster, in other words, without a gap.
  • the smoothness and corrosion resistance of the indium oxide-containing layer 11, and thus the metal layer 12 and the metallic luster article 1 can be improved, and the indium oxide-containing layer 11 is formed without in-plane variation. It is also easy to do.
  • the indium oxide-containing layer 11 is further provided between the base 10 and the metal layer 12, that is, the indium oxide layer 11 is formed on the base 10 and the metal layer 12 is formed thereon. Accordingly, it is preferable because the metal layer 12 is easily formed in a discontinuous state.
  • the details of the mechanism are not always clear, but when sputtered particles formed by metal deposition or sputtering form a thin film on the substrate, the surface diffusivity of the particles on the substrate affects the shape of the thin film. It is considered that the discontinuous structure is more easily formed when the temperature of the metal layer is higher, the wettability of the metal layer to the substrate is lower, and the melting point of the material of the metal layer is lower.
  • indium oxide-containing layer 11 indium oxide (In 2 O 3 ) itself can be used.
  • a metal-containing material such as indium tin oxide (ITO) or indium zinc oxide (IZO) is used.
  • ITO or IZO containing the second metal is more preferable in terms of high discharge stability in the sputtering process.
  • a film in a continuous state can be formed along the surface of the substrate.
  • a metal layer laminated on the indium oxide-containing layer is For example, it is preferable because an island-like discontinuous structure is easily obtained.
  • Cr chromium
  • indium (In) but also a discontinuous structure is usually difficult to be applied to the metal layer. It becomes easy to include various metals.
  • the content ratio (content ratio (ZnO / (In 2 O 3 + ZnO)) ⁇ 100), which is a mass ratio of zinc oxide (ZnO) contained in IZO, is, for example, 2 wt% to 20 wt%.
  • the thickness of the indium oxide-containing layer 11 is usually preferably 1000 nm or less, more preferably 50 nm or less, and still more preferably 20 nm or less, from the viewpoint of sheet resistance, electromagnetic wave permeability, and productivity.
  • the thickness is preferably 1 nm or more, and in order to easily facilitate the discontinuous state, it is more preferably 2 nm or more, and 5 nm or more. More preferably.
  • the metal layer 12 is formed on the substrate and includes a plurality of portions 12a that are discontinuous with each other at least partially.
  • the average particle size of the plurality of portions 12a is not less than 30 nm and less than 100 nm.
  • the average particle diameter 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 plurality of portions 12a is a diameter of a perfect circle corresponding to the area of the plurality of portions 12a.
  • the average particle diameter of the plurality of portions 12a can be measured by the method described in the column of Examples.
  • the average particle size of the plurality of portions 12a is set to 30 nm or more and less than 100 nm in the present invention.
  • the average particle diameter of the plurality of portions 12a is preferably 40 nm or more, more preferably 50 nm or more, and further preferably 60 nm or more. Further, it is preferably 99 nm or less, more preferably 98 nm or less, and further preferably 95 nm or less.
  • the coverage of the base with the metal layer 12 is the ratio of the total area of the plurality of portions 12a to the surface area of the base in the region where the metal layer 12 is provided.
  • the coverage of the substrate with the metal layer 12 can be measured by the method described in the column of Examples.
  • the coverage of the base with the metal layer 12 is 75% or more and less than 100%.
  • the coverage of the substrate with the metal layer 12 is preferably 80% or more, more preferably 82% or more, still more preferably 84% or more, and still more preferably 86% or more. Further, it is preferably 98% or less, more preferably 96% or less, and further preferably 94% or less.
  • the average particle diameter of the plurality of portions 12a of the metal layer 12 can be set to the above range by adjusting the power applied to the sputtering target.
  • the glitter can be improved while maintaining high electromagnetic wave permeability. This is because by setting the average particle diameter of the plurality of portions 12a within the above range, both a thin film and a high coverage can be achieved, thereby suppressing diffuse reflection and regular reflection in the visible light region, thereby increasing specular reflection. is there.
  • the metal layer 12 when the metal layer 12 is in a continuous state on the substrate, sufficient glitter can be obtained, but the sheet resistance becomes very small, and therefore electromagnetic wave transmission cannot be ensured.
  • the coverage is 75% or more and less than 100%, and the average particle size of the plurality of portions 12a is 30 nm or more and less than 100 nm. It is possible to obtain an electromagnetic wave-transmitting metallic luster article that is excellent in both the thickness of the metal layer and high luster.
  • the details of the mechanism by which the metal layer 12 becomes discontinuous on the substrate are not necessarily clear, but are estimated to be as follows. That is, in the thin film formation process of the metal layer 12, the ease of forming the discontinuous structure is related to the surface diffusion on the substrate to which the metal layer 12 is applied, the temperature of the substrate is high, and the metal layer with respect to the substrate The lower the melting point of the material of the metal layer, the easier it is to form a discontinuous structure. Therefore, for metals other than aluminum (Al) used in particular in the following examples, for metals with relatively low melting points such as zinc (Zn), lead (Pb), copper (Cu), and silver (Ag), It is considered that a discontinuous structure can be formed by a similar method.
  • the metal layer 12 has a relatively low melting point as well as sufficient glitter. This is because the metal layer 12 is preferably formed by thin film growth using sputtering. For this reason, a metal having a melting point of about 1000 ° C. or less is suitable as the metal layer 12. For example, aluminum (Al), zinc (Zn), lead (Pb), copper (Cu), silver (Ag) It is preferable that at least one kind of metal selected from the above and an alloy containing the metal as a main component are included. In particular, Al and alloys thereof are preferable for the reasons such as the luster and stability of the substance and the price. Moreover, when using an aluminum alloy, it is preferable that aluminum content shall be 50 mass% or more.
  • the thickness of the metal layer 12 is usually preferably 10 nm or more so as to exhibit sufficient glitter, and from the viewpoint of productivity, it is usually preferably 100 nm or less.
  • 15 nm to 100 nm is preferable, 15 nm to 80 nm is more preferable, 15 nm to 70 nm is further preferable, 15 nm to 60 nm is still more preferable, 15 nm to 50 nm is particularly preferable, and 15 nm to 40 nm is most preferable.
  • the ratio of the thickness of the metal layer to the thickness of the indium oxide-containing layer is preferably in the range of 0.1 to 100. A range of 3 to 35 is more preferable.
  • the metallic luster article of the present embodiment may include other layers depending on the application.
  • Other layers include an optical adjustment layer (color adjustment layer) such as a highly refractive material for adjusting the appearance such as color, and a protective layer (abrasion resistance) for improving durability such as moisture resistance and scratch resistance.
  • Property layer barrier layer (corrosion prevention layer), easy adhesion layer, hard coat layer, antireflection layer, light extraction layer, antiglare layer and the like.
  • a method such as vacuum deposition or sputtering can be used.
  • the indium oxide-containing layer 11 is formed on the substrate 10, the indium oxide-containing layer 11 is formed by vacuum deposition, sputtering, ion plating or the like prior to the formation of the metal layer 12.
  • sputtering is preferable because the thickness can be strictly controlled even in a large area.
  • indium oxide containing layer 11 between the base
  • the metal thin film according to the present embodiment is a metal thin film formed on the substrate 10, and the metal thin film has a thickness of 15 nm to 100 nm, and is a plurality of discontinuous states at least partially. Including the island-shaped portion, the 20 ° glossiness is 900 or more, and the average particle size of the plurality of island-shaped portions is 30 nm or more and less than 100 nm.
  • the metal layer 12 described above can be formed to a thickness of 15 nm to 100 nm, and only this can be used as a metal thin film.
  • a metal layer 12 is formed by sputtering on an indium oxide-containing layer 11 laminated on a substrate 10 such as a substrate film to obtain a film with a metal thin film.
  • an adhesive is applied onto the substrate to produce a substrate with an adhesive layer.
  • a film with a metal thin film is formed by laminating a film with a metal thin film and a substrate with an adhesive layer so that the metal layer 12 and the adhesive layer are in contact with each other and sufficiently adhering them.
  • the metal layer (metal thin film) 12 present on the outermost surface of the substrate can be transferred to the outermost surface of the substrate with the adhesive layer.
  • the above description can be used as it is for the substrate, metal layer, gloss, coverage, and average particle size of a plurality of portions.
  • metallic luster articles and metal thin films are used for an apparatus and an article that transmit and receive electromagnetic waves, and parts thereof.
  • household goods such as structural parts for vehicles, on-vehicle equipment, housing for electronic equipment, housing for home appliances, structural parts, mechanical parts, various automotive parts, electronic equipment parts, furniture, kitchenware, etc. , Medical equipment, building material parts, other structural parts and exterior parts.
  • ECU boxes electrical components, engine peripheral components, drive system / gear peripheral components, intake / exhaust system components, cooling system components, and the like.
  • electronic devices and home appliances include refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, TVs, clocks, ventilation fans, projectors, speakers, and other home appliances, personal computers, mobile phones
  • Electronic information devices such as smartphones, digital cameras, tablet PCs, portable music players, portable game machines, chargers, and batteries.
  • the total cross-sectional area of the metal layer in the viewing angle region extracted at each of the five measurement positions divided by the lateral width of the viewing angle region is defined as the thickness of the metal layer in each viewing angle region.
  • the average value of the metal layer thickness in each viewing angle region was defined as the metal layer thickness (Al film thickness (nm)).
  • Radio wave transmission attenuation The radio wave transmission attenuation at 5 GHz was measured using a spectrum analyzer MS4644B manufactured by Anritsu Co., Ltd. with a sample sandwiched between rectangular waveguide measurement evaluation jigs WR-187.
  • the sheet resistance as a laminate of the metal layer and the indium oxide-containing layer was measured by an eddy current measurement method using a non-contact type resistance measuring device NC-80MAP manufactured by Napson, in accordance with JIS-Z2316.
  • the sheet resistance is preferably 100 ⁇ / ⁇ or more, more preferably 200 ⁇ / ⁇ or more, and further preferably 600 ⁇ / ⁇ or more. If it is less than 100 ⁇ / ⁇ , there is a problem that sufficient electromagnetic wave permeability cannot be obtained.
  • the resistance value was high and exceeded the measurement upper limit of NC-80MAP, the measurement was performed using Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Corporation.
  • the 20 ° glossiness of metallic glossy articles was measured according to JIS Z 8741 (1997 edition). Specifically, the measurement was performed using PG-IIM (20 ° gloss measurement, manufactured by Nippon Denshoku Industries Co., Ltd.). In addition, the measurement of 20 degree glossiness was performed with respect to the surface by the side of a metal layer.
  • an aluminum (Al) layer was formed on the ITO layer using AC sputtering (AC: 40 kHz, Al target applied power: 3.1 W / cm 2 ) to obtain a metallic luster article (metal thin film).
  • the obtained aluminum layer was a discontinuous layer.
  • the temperature of the base film when forming the Al layer was set to 130 ° C.
  • Example 2 to 5 The metallic glossy members (metals) of Examples 2 to 5 were used in the same manner as in Example 1 except that the time for forming the aluminum (Al) layer on the ITO layer was changed using AC sputtering (AC: 40 kHz). Thin film).
  • Comparative Example 1 A metallic luster article (metal thin film) of Comparative Example 1 was obtained in the same manner as in Example 1 except that the applied power of the Al target in Example 1 was changed to 9.3 W / cm 2 .
  • Comparative Examples 2 to 5 The metallic luster members of Comparative Examples 2 to 5 (metal) are the same as Comparative Example 1 except that the time for forming the aluminum (Al) layer on the ITO layer is changed using AC sputtering (AC: 40 kHz). Thin film).
  • FIG. 4 is a diagram showing the relationship between the coverage by the metal layer of the substrate of the electromagnetically transparent metallic glossy article of Examples and Comparative Examples and the glossiness
  • FIG. 5 is the electromagnetically transparent metallic gloss of Examples and Comparative Examples
  • FIG. 6 is a diagram showing the relationship between the film thickness of the article and the coverage with the metal layer of the substrate, and FIG. 6 is based on the crystal grains (average particle size) of the electromagnetic wave permeable metallic luster articles of Examples and Comparative Examples It is a figure which shows the relationship of a coverage.
  • the metallic glossy articles of Examples 1 to 5 include a plurality of portions 12a formed in a discontinuous state in the aluminum layer. As a result, it was shown that excellent electromagnetic wave permeability was obtained. Further, the metallic luster articles of Examples 1 to 5 had a high coverage even when the metal layer was a thin film, and all had good glitter and an excellent metallic appearance. On the other hand, the metallic luster articles of Comparative Examples 1 to 5 had a large average particle size in the metal layer portion, a small coverage of the metal layer, a small glossiness, inferior luster and inferior metallic appearance.
  • the metallic luster article according to the present invention can be used for devices and articles for transmitting and receiving electromagnetic waves, and parts thereof.
  • applications for household goods such as structural parts for vehicles, vehicle-mounted products, housings for electronic devices, housings for home appliances, structural components, mechanical parts, various automotive parts, electronic device parts, furniture, kitchenware, etc. It can also be used for various applications that require both design and electromagnetic wave transmission properties, such as medical equipment, building material parts, other structural parts and exterior parts.

Landscapes

  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un article à perméabilité électromagnétique avec un brillant métallique (1), pourvu d'un substrat (10) et d'une couche métallique (12) formée sur le substrat (10). Le brillant 0 20° est d'au moins 900. La couche métallique (12) comprend une pluralité de parties (12a) qui sont, au moins en partie, mutuellement discontinues. Le diamètre de grain moyen de la pluralité de parties (12a) est d'au moins 30 nm et de moins de 100 nm. Un autre mode de réalisation de la présente invention concerne un article à perméabilité électromagnétique ayant un brillant métallique (1), pourvu d'un substrat (10) et d'une couche métallique (12) formée sur le substrat (10). La couche métallique comprend une pluralité de parties (12a) qui sont, au moins en partie, mutuellement discontinues. Le rapport de couverture du substrat (10) par la couche métallique (12) est d'au moins 75 % et de moins de 100 %, et le diamètre de grain moyen de la pluralité de parties (12a) est d'au moins 30 nm et de moins de 100 nm.
PCT/JP2019/017034 2018-04-23 2019-04-22 Article à perméabilité électromagnétique à brillant métallique Ceased WO2019208499A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201980027688.3A CN112004666A (zh) 2018-04-23 2019-04-22 电磁波透过性金属光泽物品
KR1020207029677A KR102680787B1 (ko) 2018-04-23 2019-04-22 전자파 투과성 금속 광택 물품

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018-082658 2018-04-23
JP2018082658 2018-04-23
JP2019-080643 2019-04-22
JP2019080643A JP7319081B2 (ja) 2018-04-23 2019-04-22 電磁波透過性金属光沢物品

Publications (1)

Publication Number Publication Date
WO2019208499A1 true WO2019208499A1 (fr) 2019-10-31

Family

ID=68295017

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/017034 Ceased WO2019208499A1 (fr) 2018-04-23 2019-04-22 Article à perméabilité électromagnétique à brillant métallique

Country Status (1)

Country Link
WO (1) WO2019208499A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021132456A1 (fr) * 2019-12-26 2021-07-01 大日本印刷株式会社 Feuille métallique décorative et corps moulé métallique décoratif comportant ladite feuille
JPWO2021132461A1 (fr) * 2019-12-27 2021-07-01
WO2023190612A1 (fr) * 2022-03-30 2023-10-05 日東電工株式会社 Stratifié, dispositif électroluminescent et dispositif de détection

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH066783B2 (ja) * 1986-12-22 1994-01-26 株式会社麗光 包装用蒸着フイルム
JP2008221557A (ja) * 2007-03-12 2008-09-25 Ulvac Japan Ltd 光輝性膜および光輝性膜の製造方法
WO2018079547A1 (fr) * 2016-10-24 2018-05-03 日東電工株式会社 Élément métallique brillant perméable aux ondes électromagnétiques, article utilisant celui-ci et film mince métallique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH066783B2 (ja) * 1986-12-22 1994-01-26 株式会社麗光 包装用蒸着フイルム
JP2008221557A (ja) * 2007-03-12 2008-09-25 Ulvac Japan Ltd 光輝性膜および光輝性膜の製造方法
WO2018079547A1 (fr) * 2016-10-24 2018-05-03 日東電工株式会社 Élément métallique brillant perméable aux ondes électromagnétiques, article utilisant celui-ci et film mince métallique

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021132456A1 (fr) * 2019-12-26 2021-07-01 大日本印刷株式会社 Feuille métallique décorative et corps moulé métallique décoratif comportant ladite feuille
JPWO2021132456A1 (fr) * 2019-12-26 2021-07-01
JP7647582B2 (ja) 2019-12-26 2025-03-18 大日本印刷株式会社 金属調加飾シート及びこれを備える金属調加飾成形体
JPWO2021132461A1 (fr) * 2019-12-27 2021-07-01
WO2021132461A1 (fr) * 2019-12-27 2021-07-01 大日本印刷株式会社 Feuille décorative à fini métallique et corps moulé décoratif à fini métallique comportant une feuille décorative à fini métallique
US12246556B2 (en) 2019-12-27 2025-03-11 Dai Nippon Printing Co., Ltd. Metal tone decorative sheet and metal tone decorative molded body provided with metal tone decorative sheet
JP7647583B2 (ja) 2019-12-27 2025-03-18 大日本印刷株式会社 金属調加飾シート及びこれを備える金属調加飾成形体
WO2023190612A1 (fr) * 2022-03-30 2023-10-05 日東電工株式会社 Stratifié, dispositif électroluminescent et dispositif de détection

Similar Documents

Publication Publication Date Title
US11577491B2 (en) Metallic lustrous member with radio wave transmissibility, article using same, and production method therefor
JP7319077B2 (ja) 電磁波透過性金属光沢物品、及び、金属薄膜
WO2019208504A1 (fr) Article de lustre métallique transparent à ondes électromagnétiques, et couche mince métallique
WO2019208499A1 (fr) Article à perméabilité électromagnétique à brillant métallique
JP7319081B2 (ja) 電磁波透過性金属光沢物品
TWI869564B (zh) 電磁波透過性積層構件、及其製造方法
CN112004664B (zh) 电磁波透过性金属光泽物品
WO2019208488A1 (fr) Article de lustre métallique transmettant des ondes électromagnétiques
JP7670684B2 (ja) 電磁波透過性金属光沢部材
JP7319080B2 (ja) 電磁波透過性金属光沢物品、及び、金属薄膜
WO2019208494A1 (fr) Produit de lustre métallique transmettant des ondes électromagnétiques et film mince métallique
JP7319078B2 (ja) 電磁波透過性金属光沢物品
JP7687894B2 (ja) 積層体、及び加飾部材
WO2019208490A1 (fr) Article métallique brillant perméable aux ondes électromagnétiques et son procédé de fabrication
WO2019208489A1 (fr) Article de lustre métallique transmettant des ondes électromagnétiques

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19792383

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19792383

Country of ref document: EP

Kind code of ref document: A1