WO2021006130A1 - Article de lustre métallique transmettant des ondes électromagnétiques - Google Patents

Article de lustre métallique transmettant des ondes électromagnétiques Download PDF

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Publication number
WO2021006130A1
WO2021006130A1 PCT/JP2020/025735 JP2020025735W WO2021006130A1 WO 2021006130 A1 WO2021006130 A1 WO 2021006130A1 JP 2020025735 W JP2020025735 W JP 2020025735W WO 2021006130 A1 WO2021006130 A1 WO 2021006130A1
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layer
electromagnetic wave
metallic luster
metal layer
metal
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PCT/JP2020/025735
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English (en)
Japanese (ja)
Inventor
秀行 米澤
正義 片桐
孝洋 中井
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日東電工株式会社
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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
    • B32B15/08—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 of synthetic resin

Definitions

  • the present invention relates to an electromagnetic wave transmitting metallic luster article.
  • a member having electromagnetic wave transmission and metallic luster has both a high-class appearance derived from the metallic luster and electromagnetic wave transmission, and is therefore suitably used for an apparatus for transmitting and receiving electromagnetic waves.
  • metal is used for the metallic luster member, the transmission and reception of electromagnetic waves is substantially impossible or disturbed. Therefore, an electromagnetic wave-transmitting metallic luster article having both metallic luster and electromagnetic wave transmission is required so as not to interfere with the transmission and reception of electromagnetic waves and not to impair the design.
  • Such electromagnetic wave-transmitting metallic luster articles are various devices that require communication as devices for transmitting and receiving electromagnetic waves, for example, electronic devices such as automobile door handles provided with smart keys, in-vehicle communication devices, mobile phones, and personal computers. It is expected to be applied to 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 home appliances such as refrigerators and household appliances, which have not been used for communication in the past. From the viewpoint of design, these electromagnetic wave-transmitting metallic luster articles may be required to have a metallic luster with a high degree of luster.
  • Patent Document 1 discloses an electromagnetic wave transmitting metallic luster member using not only chromium (Cr) or indium (In) but also other metals such as aluminum (Al) as a metal layer.
  • This electromagnetically transmissive metallic luster member includes an indium oxide-containing layer provided on the surface of the substrate and a metal layer laminated on the indium oxide-containing layer, and the metal layers are in a discontinuous state with each other at least in part. Includes multiple parts.
  • Patent Document 2 a decoration having a metal coloring portion by a metal thin film layer on a transparent resin molded product as a cover panel in which radio interference does not occur despite having a beautiful design expression of metal coloring.
  • a cover panel having a metal coloration in which the metal thin film layer has a discontinuous film structure is described.
  • the metallic luster member in the prior art has a problem that the reflectance decreases with time and the metallic luster is lost.
  • the metal layer in the metallic luster member is easily deteriorated by oxidation due to moisture in the air or the like, and there is a demand for providing a metallic luster member capable of maintaining the metallic luster for a long period of time.
  • the metallic luster member may be scratched during the manufacturing process or transportation, and it is difficult to provide a member having a metallic appearance, which exhibits excellent electromagnetic wave transmission and is excellent in scratch resistance.
  • the present invention has been made to solve these problems in the prior art, and provides an electromagnetic wave-transmitting metallic luster article having excellent electromagnetic wave transmission, a metallic luster that can be maintained for a long period of time, and excellent scratch resistance. The purpose is to do.
  • the present inventors have made the metal layer a discontinuous structure and provided a protective layer formed on the surface of the metal layer opposite to the substrate side.
  • the present invention has been completed by finding that an electromagnetic wave-transmitting metallic luster article having excellent electromagnetic wave permeability, a metallic luster can be maintained for a long period of time, and an excellent scratch resistance can be obtained. That is, the present invention is as follows.
  • the metal layer is an electromagnetic wave-transmissive metallic luster article containing a plurality of portions that are discontinuous with each other at least in part.
  • the electromagnetic wave-transmitting metallic luster article according to [1] wherein the protective layer includes an adhesive layer.
  • the pressure-sensitive adhesive layer contains a (meth) acrylic polymer as a base polymer.
  • the barrier layer contains at least one selected from the group consisting of at least one oxide of metal and semi-metal, nitride, carbide, oxynitride, carbide, carbide and carbide oxide [6].
  • an electromagnetic wave-transmissive metallic luster article having excellent electromagnetic wave transmission, a metallic luster that can be maintained for a long period of time, and excellent scratch resistance.
  • FIG. 1 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster article according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster article according to an embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster article according to an embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster article according to an embodiment of the present invention.
  • FIG. 5 is a schematic cross-sectional view of an electromagnetic wave transmitting metallic luster article according to an embodiment of the present invention.
  • FIG. 6 is an electron micrograph of the surface of an electromagnetic wave transmitting metallic luster article according to an embodiment of the present invention.
  • FIG. 7 is a diagram for explaining a method for measuring the film thickness of the metal layer of the electromagnetic wave transmitting metallic luster article according to the 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 according to an embodiment of the present invention.
  • TEM image transmission electron micrograph
  • Basic configuration> 1 to 5 show schematic cross-sectional views of an electromagnetic wave transmitting metallic luster article 1 according to an embodiment of the present invention. Further, FIG. 6 shows an electron micrograph (SEM image) of the surface of the metal layer of the electromagnetic wave transmitting metallic luster article in order to explain the discontinuous structure of the metal layer.
  • SEM image electron micrograph
  • the electromagnetic wave-transmitting metallic luster article 1 is formed on the substrate 10, the metal layer 12 formed on the substrate 10, and the surface of the metal layer 12 opposite to the substrate 10 side. Includes a protective layer 13.
  • the electromagnetic wave transmitting metallic luster article 1 may include a substrate 10, a metal layer 12, and an adhesive layer 13b and a protective film 13a as the protective layer 13.
  • the electromagnetic wave transmitting metallic luster article 1 may have a barrier layer 14 on a surface of the metal layer 12 opposite to the substrate 10 side.
  • the electromagnetic wave transmitting metallic luster article 1 may further include an indium oxide-containing layer 15 between the substrate 10 and the metal layer 12.
  • the metal layer 12 is formed on the substrate 10.
  • the metal layer 12 includes a plurality of portions 12a. These plurality of portions 12a in the metal layer 12 are separated from each other by a gap 12b at least in a discontinuous state, that is, in at least a part. Since the plurality of portions 12a are separated by the gap 12b, the sheet resistance of the plurality of portions 12a increases and the interaction with the radio waves decreases, so that the radio waves can be transmitted.
  • Each of these portions 12a may be an aggregate of sputtered particles formed by vapor deposition, sputtering, or the like of a metal.
  • the "discontinuous state” referred to in the present specification means a state in which a plurality of portions 12a are separated from each other by a gap 12b, and as a result, they are electrically insulated from each other. By being electrically insulated, the sheet resistance becomes large, and the desired electromagnetic wave transmission can be obtained. That is, according to the metal layer 12 formed in a discontinuous state, sufficient brilliance can be easily obtained, and electromagnetic wave transmission can be ensured.
  • the discontinuous form is not particularly limited, and includes, for example, an island-like structure, a crack structure, and the like.
  • the “island-like structure” means that the metal particles are independent of each other, and the particles are spread in a state of being slightly separated from each other or partially in contact with each other. Means the structure.
  • the crack structure is a structure in which a metal thin film is divided by cracks.
  • 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 generate 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 elasticity, that is, easily forming cracks by stretching, between the base film and the metal thin film layer. ..
  • the mode in which the metal layer 12 is discontinuous is not particularly limited, but from the viewpoint of productivity, an island-like structure is preferable.
  • the electromagnetic wave transmissive metallic luster article 1 preferably has a reflectance Y of 20% or more in the SCI measurement of the reflected light in the wavelength range of 380 nm to 780 nm.
  • the reflectance Y is more preferably 40% or more, and further preferably 50% or more.
  • the reflectance Y can be measured by a spectrocolorimeter CM-2600d manufactured by Konica Minolta Co., Ltd. using D65 as a standard light source, and can be measured by the method described in Examples.
  • the amount of electromagnetic wave transmission attenuation and the sheet resistance of the electromagnetic wave transmitting metallic luster article 1 are affected by the material and thickness of the metal layer 12 and the like. Further, when the electromagnetic wave transmitting metallic luster article 1 includes the indium oxide-containing layer 15 described later, it is also affected by the material and thickness of the indium oxide-containing layer 15.
  • the layer can withstand high temperatures such as vapor deposition and sputtering. Therefore, among the above materials, for example, polyethylene terephthalate, polyethylene naphthalate, etc. Acrylic, polycarbonate, cycloolefin polymer, ABS, polypropylene and polyurethane are preferred. Of these, polyethylene terephthalate, cycloolefin polymer, polycarbonate, and acrylic are preferable because they have a good balance between heat resistance and cost.
  • the base film is only an example of an object (base 10) on which the metal layer 12 can be formed.
  • the substrate 10 includes, as described above, a resin molded substrate, a glass substrate, and the article itself to which metallic luster should be imparted.
  • the resin molded base material and articles to which metallic luster should be imparted include vehicle structural parts, vehicle-mounted products, electronic device housings, home appliance housings, structural parts, mechanical parts, and various automobiles. Examples include parts for household appliances such as parts for electronic devices, furniture, kitchen utensils, medical devices, parts for building materials, other structural parts and exterior parts.
  • 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. In this case, it is preferable that the substrate 10 to which the metal layer 12 is applied satisfies the same materials and conditions as the above-mentioned substrate film.
  • the metal layer 12 is formed on the substrate and includes a plurality of portions that are discontinuous with each other at least in part. When the metal layer 12 is in a continuous state on the substrate, a sufficient metallic luster can be obtained, but the amount of radio wave transmission attenuation becomes very large, and therefore electromagnetic wave transmission cannot be ensured.
  • the details of the mechanism by which the metal layer 12 becomes discontinuous on the substrate are not always clear, but it is presumed to be roughly as follows. That is, in the thin film forming 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 is formed. The smaller the wettability of the metal layer and the lower the melting point of the metal layer material, the easier it is to form a discontinuous structure. Therefore, for metals other than aluminum (Al), which are particularly used in the following examples, tin (Sn), indium (In), zinc (Zn), lead (Pb), copper (Cu), and silver (Ag) are also used. It is considered that a discontinuous structure can be formed by the same method for metals having a relatively low melting point such as.
  • the metal layer 12 has a relatively low melting point as well as being able to exhibit sufficient brilliance. 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 lower is suitable as the metal layer 12, and for example, aluminum (Al), tin (Sn), indium (In), zinc (Zn), and lead (Pb). ), Copper (Cu), at least one metal selected from silver (Ag), and any of the alloys containing the metal as a main component are preferably contained.
  • Al aluminum
  • Sn tin
  • In indium
  • the aluminum content is preferably 50% by mass or more.
  • the equivalent circle diameter of the portion 12a of the metal layer 12 is not particularly limited, but is usually about 10 to 1000 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 circle-equivalent diameter of the portion 12a is the diameter of a perfect circle corresponding to the area of the portion 12a.
  • the distance between the portions 12a is not particularly limited, but is usually about 10 to 1000 nm.
  • the thickness of the metal layer 12 is usually preferably 10 nm or more so as to exhibit sufficient brilliance, while it is usually preferably 100 nm or less from the viewpoint of productivity.
  • 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 further preferable, 15 nm to 50 nm is particularly preferable, and 15 nm to 40 nm is most preferable.
  • the thickness of the metal layer 12 can be measured by the method described in the column of Examples.
  • the sheet resistance of the metal layer and the indium oxide-containing layer as a laminate is preferably 100 ⁇ / ⁇ or more.
  • the electromagnetic wave transmission property is about 10 to 0.01 [ ⁇ dB] at a wavelength of 5 GHz. More preferably, it is 1000 ⁇ / ⁇ or more.
  • the value of this sheet resistance is greatly affected not only by the material and thickness of the metal layer but also by the material and thickness of the indium oxide-containing layer which is the base layer. Therefore, when the indium oxide-containing layer is provided, it is necessary to consider the relationship with the indium oxide-containing layer.
  • the electromagnetic wave transmitting metallic luster article 1 of the present embodiment includes a protective layer 13.
  • the protective layer 13 can be formed on the metal layer as shown in FIGS. 1 to 5. For example, as shown in FIGS. 1 and 2, it can be formed on the surface of the metal layer 12 opposite to the substrate 10 side.
  • the protective layer 13 is formed on the surface of the barrier layer 14 opposite to the metal layer 12 side, as shown in FIGS. 3 to 5. May be good.
  • the protective layer 13 is preferably a resin layer containing a resin.
  • the protective layer 13 is an optical adjustment layer (color adjustment layer) such as a high-refractive-index material for adjusting the appearance such as color, and a protective film (scratch resistance) for improving durability such as moisture resistance and scratch resistance. It may be a sex layer), an easy-adhesion layer, an adhesive layer, a hard coat layer, an antireflection layer, a light extraction layer, an anti-glare layer, or the like, or a combination thereof. As shown in FIGS. 1 and 3, the protective layer 13 may be an adhesive layer. Further, as shown in FIGS. 2 and 4, the protective layer 13 may include an adhesive layer 13b and a protective film 13a.
  • the protective layer 13 includes the pressure-sensitive adhesive layer 13b and the protective film 13a
  • only the protective film 13a can be peeled off.
  • the electromagnetic wave-transmitting metallic luster article 1 of the present embodiment may be used by being attached to an adherend member via an adhesive layer 13b.
  • the adherend member can be decorated from the inside by attaching the electromagnetic wave transmissive metallic luster article 1 to the transparent adherend member via the pressure-sensitive adhesive layer 13b.
  • the electromagnetic wave-transmitting metallic luster article 1 is interposed via the adhesive layer 13b with respect to the surface of the transparent adherend member on the side opposite to the visible side (hereinafter, also referred to as the outside) (hereinafter, also referred to as the inside).
  • the pressure-sensitive adhesive layer 13b and the metal layer 12 are visually recognized through the adherend member. Since the pressure-sensitive adhesive layer 13b suppresses or prevents deterioration of the metal layer 12 due to moisture in the air, an electromagnetic wave-transmissive metallic luster article capable of maintaining metallic luster for a long period of time and having excellent scratch resistance can be obtained.
  • the transparent adherend member for example, a member made of glass or plastic can be used, but the transparent member is not limited to this.
  • the protective layer 13 when the protective layer 13 includes the pressure-sensitive adhesive layer 13b and the protective film 13a, the pressure-sensitive adhesive layer 13b is peeled off from the metal layer 12 together with the protective film 13a, and the substrate 10 and the metal layer are separated.
  • It can also be a laminate containing at least 12 and. That is, the electromagnetic wave-transmitting metallic luster article 1 suppresses or prevents deterioration of the metal layer 12 by protecting the metal layer 12 with the protective layer 13 until the metal layer 12 is further decorated or the like, depending on the intended use. It can retain metallic luster for a long period of time. In addition, it is possible to prevent scratches caused by the manufacturing process, transportation, and the like. After the protective layer 13 is peeled off, the laminated body can be decorated or the like on the metal layer 12.
  • the peeling force between the laminate and the protective layer 13 is, for example, 5.00 N / mm or less, preferably 2.00 N / mm or less, and for example, 0.001 N / 50 mm or more, preferably 0.01 N. / Mm or more.
  • the protective layer 13 can be easily peeled from the barrier layer 14 when the peeling force is equal to or less than the above upper limit, and the electromagnetic wave. Damage to the transparent metallic luster article 1 can be suppressed. Further, when the peeling force is equal to or more than the above lower limit, it is possible to suppress bonding bubbles at the time of bonding the protective layer.
  • the peeling force can be measured by the method described in Examples.
  • the thickness of the protective layer is preferably 5 to 300 ⁇ m, more preferably 5 to 250 ⁇ m, further preferably 50 to 250 ⁇ m, even more preferably 100 to 200 ⁇ m, and more than 100 ⁇ m to 200 ⁇ m. The following is particularly preferable.
  • the thickness of the protective layer is 5 ⁇ m or more, it is preferable from the viewpoint of ensuring scratch resistance. Further, the thickness of the protective layer is 250 ⁇ m or less, which is preferable in terms of transportability.
  • the thickness of the protective layer can be measured with a dial gauge or the like.
  • the protective layer 13 is preferably a layer that does not easily permeate or absorb water. For example, by making the protective layer 13 a layer that does not easily permeate or absorb moisture, deterioration of the metal layer 12 due to moisture in the air can be suppressed or prevented, and the metallic luster can be maintained for a long period of time. Further, the protective layer 13 is preferably a transparent layer. Since the protective layer has transparency, it can be an electromagnetic wave-transmitting metallic luster article having excellent metallic luster.
  • the pressure-sensitive adhesive layer is preferably formed of a pressure-sensitive adhesive composition containing a base polymer.
  • a base polymer a known polymer used for the pressure-sensitive adhesive can be used.
  • the base polymer refers to the main component of the polymer contained in the pressure-sensitive adhesive composition.
  • the “main component” refers to a component contained in an amount of more than 50% by mass, unless otherwise specified.
  • the adhesive composition preferably contains a (meth) acrylic polymer as a base polymer.
  • (meth) acrylate means acrylate and / or methacrylate.
  • the (meth) acrylic polymer in the embodiment of the present invention preferably contains an alkyl (meth) acrylate and a hydroxyl group-containing monomer as monomer units.
  • the method for introducing a hydroxyl group is not particularly limited, but for example, a method for copolymerizing a hydroxyl group-containing monomer can be easily performed.
  • the (meth) acrylic polymer in the embodiment of the present invention refers to an acrylic polymer and / or a methacrylic polymer
  • (meth) acrylate refers to an acrylate and / or methacrylate
  • an alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Can be given. These compounds may be used alone or in combination of two or more.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl ( Meta) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, Examples thereof include vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. These monomers may be used alone or in combination of two or more.
  • the hydroxyl group-containing monomer may be used alone or in combination of two or more, but the total content is 1 to 1 to 100 parts by mass of the (meth) acrylic polymer. It is preferably 10 parts by mass, and more preferably 2 to 6 parts by mass.
  • a reaction point by cross-linking or the like is imparted.
  • the (meth) acrylic polymer used in the embodiment of the present invention preferably has a weight average molecular weight of about 300,000 to 2.5 million. When the weight average molecular weight is less than 300,000, the cohesive force of the pressure-sensitive adhesive composition is reduced, which tends to cause adhesive residue.
  • the weight average molecular weight is obtained by measuring by GPC (gel permeation chromatography).
  • the glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ° C. or lower (usually -100 ° C. or higher), preferably ⁇ 10 ° C. or lower.
  • the glass transition temperature (Tg) of the (meth) acrylic polymer can be adjusted within the above range by appropriately changing the monomer component and composition ratio used.
  • a polymerizable monomer for adjusting the glass transition point and the peelability of the (meth) acrylic polymer may be used as long as the effect of the present invention is not impaired. it can.
  • polymerizable monomers used in the (meth) acrylic polymer include, for example, cohesive power and heat resistance of a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, a cyano group-containing monomer, a vinyl ester monomer, an aromatic vinyl monomer, and the like. It has a property-improving component, an acid anhydride group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, an epoxy group-containing monomer, N-acryloylmorpholine, a vinyl ether monomer, and other functional groups that act as adhesion bases and cross-linking base points. Ingredients can be used as appropriate. These monomer compounds may be used alone or in combination of two or more.
  • the pressure-sensitive adhesive composition according to the present embodiment does not contain an acidic group-containing monomer as a constituent monomer component in order to prevent corrosion of the metal layer and to make it difficult for the pressure-sensitive adhesive layer to absorb or permeate water. It is preferable that the monomer is substantially not contained, and particularly preferably the carboxyl group-containing monomer is not contained or substantially not contained. With such a configuration, it is possible to suppress or prevent the acidic groups contained in the pressure-sensitive adhesive layer from being oxidized by moisture in the air and chemically acting on the metal layer to deteriorate the metal layer, thereby achieving metallic luster. It is preferable for long-term retention.
  • Examples of the cyanide-containing monomer include acrylonitrile and methacrylonitrile.
  • vinyl ester monomer examples include vinyl acetate, vinyl propionate, vinyl laurate and the like.
  • aromatic vinyl monomer examples include styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene and the like.
  • amide group-containing monomer examples include acrylamide and diethyl acrylamide.
  • amino group-containing monomer examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N- (meth) acryloyl morpholine, and alkylaminoalkyl (meth) acrylate. Examples include ester.
  • epoxy group-containing monomer examples include glycidyl (meth) acrylate and allyl glycidyl ether.
  • vinyl ether monomer examples include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and the like.
  • the other polymerizable monomers may be used alone or in combination of two or more, but the total content is the (meth) acrylic polymer 100. It is preferably 0 to 300 parts by mass, and more preferably 0 to 150 parts by mass with respect to parts by mass.
  • the polymerization method of the (meth) acrylic polymer is not particularly limited, and known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and UV polymerization can be adopted. Further, the obtained copolymer may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
  • an isocyanate-based cross-linking agent as the cross-linking agent.
  • Isocyanate-based cross-linking agents are used to impart adhesion and cohesiveness.
  • isocyanate-based cross-linking agent a polyfunctional isocyanate compound is used, and various compounds having two or more isocyanate groups in the molecule are included.
  • isocyanate compound examples include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, and 2,4-tolylene diisocyanate.
  • lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate
  • alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate
  • 2,4-tolylene diisocyanate examples include 2,4-tolylene diisocyanate.
  • Aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene Examples thereof include isocyanate adducts such as diisocyanate trimeric adduct (trade name Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.) and isocyanurates of hexamethylene diisocyanate (trade name Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.).
  • those having an isocyanurate ring are particularly preferable, and for example, a polyisocyanate having a long-chain alkylenediol-modified isocyanurate ring (Bernock DN-995 manufactured by Dainippon Ink and Chemicals, Inc.) and an isocyanurate compound of hexamethylene diisocyanate. (Product name Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like. These compounds may be used alone or in combination.
  • the content of the cross-linking agent used in the embodiment of the present invention may be blended to such an extent that it does not affect the adhesive physical characteristics, but is usually 0.2 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. It is contained, preferably 0.5 to 8 parts by mass, and more preferably 1 to 6 parts by mass.
  • the acrylic pressure-sensitive adhesive includes powders of cross-linking agents (polyamine compounds, melamine resins, aziridine derivatives, urea resins), antistatic agents, plasticizers, silane coupling agents, colorants, pigments and the like other than those exemplified above.
  • cross-linking agents polyamine compounds, melamine resins, aziridine derivatives, urea resins
  • antistatic agents plasticizers, silane coupling agents, colorants, pigments and the like other than those exemplified above.
  • Dyes, surfactants, surface lubricants, leveling agents, softeners, antioxidants, antistatic agents, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders , Particle-like, foil-like material, etc. can also be appropriately used. These components may be used alone or in combination of two or more.
  • the adhesive layer includes, for example, the surface of the metal layer in the laminate including at least the substrate and the metal layer, which is opposite to the substrate side, and the adhesive layer and the protective film. It can be formed by laminating the adhesive surfaces of the laminated body of.
  • the electromagnetic wave-transmitting metallic luster article is, for example, a laminate including a substrate, a metal layer, a barrier layer, and a protective layer in this order, the surface of the barrier layer opposite to the metal layer, the adhesive layer, and the protection It can be formed by laminating the pressure-sensitive adhesive surfaces of the laminate with the film.
  • the pressure-sensitive adhesive layer can also be formed, for example, by applying the pressure-sensitive adhesive composition on a metal layer and drying and removing a solvent or the like.
  • one or more solvents may be added as appropriate.
  • the thickness of the pressure-sensitive adhesive layer is preferably 1 to 300 ⁇ m, more preferably 2 to 250 ⁇ m, further preferably 3 to 250 ⁇ m, and even more preferably 5 to 200 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer can be measured with a dial gauge.
  • Various methods are used as the method for applying the pressure-sensitive adhesive composition. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples include a method such as an extrusion coating method.
  • the heating and drying temperature is preferably about 30 ° C. to 200 ° C., more preferably 40 ° C. to 180 ° C., and even more preferably 80 ° C. to 160 ° C. By setting the heating temperature in the above range, an adhesive layer having excellent adhesive properties can be obtained.
  • As the drying time an appropriate time can be adopted as appropriate. The drying time is preferably about 5 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and even more preferably 1 minute to 8 minutes.
  • a pressure-sensitive adhesive layer can be formed by irradiating with active energy rays such as ultraviolet rays.
  • active energy rays such as ultraviolet rays.
  • a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a chemical light lamp, or the like can be used for ultraviolet irradiation.
  • the material for forming the protective film of the present embodiment is not particularly limited, and for example, a polyolefin-based film such as polyethylene, polypropylene, or an ethylene / propylene copolymer; a polyester-based film such as polyethylene terephthalate; a plastic film such as polyvinyl chloride. Papers such as kraft paper and Japanese paper; cloths such as cotton cloth and sufu cloth; cloth woven cloth such as polyester non-woven fabric and vinylon cloth woven cloth; metal foil. Further, the thickness of the protective film is not particularly limited.
  • the plastic films may be non-stretched films or stretched (uniaxially stretched or biaxially stretched) films. Further, the surface of the protective film on which the pressure-sensitive adhesive layer is provided may be subjected to surface treatment such as application of an undercoat agent or corona discharge treatment.
  • constituent material of the separator examples include porous materials such as plastic film, paper, cloth, and non-woven fabric, nets, foam sheets, metal foils, and appropriate thin leaves such as laminates thereof.
  • a plastic film is preferably used because of its excellent surface smoothness.
  • plastic film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
  • -Vinyl acetate copolymer film and the like can be mentioned.
  • the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • the separator may be used for mold release and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based mold release agent, silica powder, etc., as well as a coating type, a kneading type, and a vapor deposition type. It is also possible to carry out antistatic treatment such as.
  • the peelability from the pressure-sensitive adhesive layer can be further enhanced by appropriately performing a peeling treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the separator.
  • the electromagnetic wave transmitting metallic luster article 1 may have a barrier layer 14 on a surface of the metal layer 12 opposite to the substrate 10 side.
  • the barrier layer 14 may be laminated on the metal layer 12, and the gap 12b does not necessarily have to be completely filled.
  • the barrier layer is a layer for suppressing oxidation (corrosion) of the metal layer 12.
  • the barrier layer preferably contains at least one selected from the group consisting of at least one oxide of metal and metalloid, nitrides, carbides, oxynitrides, carbides, carbides and carbides.
  • the metal for example, aluminum, titanium, indium, magnesium and the like
  • the metalloid for example, silicon, bismuth, germanium and the like
  • ZnO + Al 2 O 3 AZO
  • IZO indium zinc oxide
  • ITO indium tin oxide
  • SiOCN silicon nitride nitride film
  • SiON silicon nitride film
  • SiN silicon nitride film
  • the barrier layer does not easily allow water vapor to permeate.
  • the degree of water vapor permeation in the barrier layer can be evaluated by various methods, and for example, the degree of water vapor permeation can be used for evaluation.
  • the water vapor permeation amount is less than 3g / m 2 ⁇ day, more preferably at most 1g / m 2 ⁇ day, 0.5g / m 2 ⁇ day or less Is more preferable.
  • the amount of water vapor permeation of the barrier layer can be measured using, for example, a water vapor permeation measuring device PERMATRAN-W Model 3/33 manufactured by MOCON.
  • the thickness of the barrier layer 14 is not particularly limited, but is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 20 nm or more in order to improve the barrier property. Further, in order to improve the electromagnetic wave transmission and the metallic luster of the appearance, 100 nm or less is preferable, 70 nm or less is more preferable, and 50 nm or less is further preferable.
  • the thickness of the barrier layer can be measured by the method described in Examples.
  • the barrier layer may be further provided between the metal layer and the substrate.
  • the electromagnetic wave transmissive metal glossy article 1 includes an indium oxide-containing layer
  • a barrier layer may be provided between the indium oxide-containing layer and the metal layer, and the barrier layer may be provided on the side opposite to the metal layer of the indium oxide-containing layer. It may be provided.
  • the electromagnetic wave transmitting metallic luster article may be provided with other layers depending on the application, in addition to the above-mentioned metal layer, protective layer, indium oxide-containing layer, and barrier layer.
  • Other layers include an optical adjustment layer (color adjustment layer) such as a high-refractive material for adjusting the appearance such as color, an easy-adhesion layer, a hard coat layer, an antireflection layer, a light extraction layer, an anti-glare layer, and the like. Can be mentioned.
  • an indium oxide-containing layer 15 may be further provided between the substrate 10 and the metal layer 12, as shown in FIG.
  • the indium oxide-containing layer 15 may be provided directly on the surface of the substrate 10, or may be indirectly provided via a protective film or the like provided on the surface of the substrate 10.
  • the indium oxide-containing layer 15 is preferably provided continuously on the surface of the substrate 10 to be imparted metallic luster, in other words, without gaps.
  • the smoothness and corrosion resistance of the indium oxide-containing layer 15, the metal layer 12, and the electromagnetic wave-transmissive metallic luster article 1 can be improved, and the indium oxide-containing layer 15 can be provided without in-plane variation. It also becomes easy to form a film.
  • the indium oxide-containing layer 15 is further provided between the substrate 10 and the metal layer 12, that is, the indium oxide-containing layer 15 is formed on the substrate 10 and the metal layer 12 is formed on the indium oxide-containing layer 15.
  • the metal layer 12 is easily formed in a discontinuous state, which is preferable.
  • the details of the mechanism are not always clear, but when sputtered particles 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, and the substrate It is considered that the higher the temperature, the smaller the wettability of the metal layer with respect to the substrate, and the lower the melting point of the material of the metal layer, the easier it is to form a discontinuous structure. Then, it is considered that by providing the indium oxide-containing layer on the substrate, the surface diffusivity of the metal particles on the surface thereof is promoted, and the metal layer can be easily grown in a discontinuous state.
  • indium oxide-containing layer 15 indium oxide (In 2 O 3 ) itself can be used, or a metal-containing substance such as indium tin oxide (ITO) or indium zinc oxide (IZO) is used. You can also do it. However, ITO and IZO containing a second metal are more preferable because they have high discharge stability in the sputtering process.
  • ITO and IZO containing a second metal are more preferable because they have high discharge stability in the sputtering process.
  • a continuous film can be formed along the surface of the substrate, and in this case, a metal layer laminated on the indium oxide-containing layer can be formed. For example, it is preferable because it tends to have an island-like discontinuous structure.
  • chromium (Cr) or indium (In) but also aluminum or the like which is usually difficult to have a discontinuous structure and is difficult to apply to this application, is used in the metal layer. It becomes easier to include various metals.
  • the thickness of the indium oxide-containing layer 15 is usually preferably 1000 nm or less, more preferably 50 nm or less, still more preferably 20 nm or less, from the viewpoint of sheet resistance, electromagnetic wave transmission, and productivity.
  • it is preferably 1 nm or more, and in order to ensure the discontinuous state, it is more preferably 2 nm or more, and 5 nm or more. Is more preferable.
  • a method such as vacuum deposition or sputtering can be used.
  • the indium oxide-containing layer 15 is formed on the substrate 10, the indium oxide-containing layer 15 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.
  • the indium oxide-containing layer 15 is provided between the substrate 10 and the metal layer 12, it is preferable that the indium oxide-containing layer 15 and the metal layer 12 are in direct contact with each other without interposing another layer.
  • electromagnetic wave transmissive metallic luster articles Since the electromagnetic wave-transmitting metallic luster article of the present embodiment has electromagnetic wave transmission property, it is preferable to use it for an apparatus or article for transmitting and receiving electromagnetic waves and its parts.
  • applications for household goods such as structural parts for vehicles, vehicle-mounted products, housings for electronic devices, housings for home appliances, structural parts, mechanical parts, various automobile parts, electronic device parts, furniture, kitchen supplies, etc. , Medical equipment, building material parts, other structural parts, exterior parts, etc. More specifically, in the vehicle industry, instrument panels, console boxes, doorknobs, door trims, shift levers, pedals, glove boxes, bumpers, bonnets, fenders, trunks, doors, roofs, pillars, seats, steering wheels.
  • ECU box electrical parts, engine peripheral parts, drive system / gear peripheral parts, intake / exhaust system parts, cooling system parts and the like.
  • home appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, TVs, watches, ventilation fans, projectors, speakers, personal computers, mobile phones , Smartphones, digital cameras, tablet PCs, portable music players, portable game machines, chargers, electronic information devices such as batteries, and the like.
  • Example 1 ⁇ Creation of a laminate of base film, indium oxide-containing layer, and metal layer> First, using DC magnetron sputtering, a base film on a 50 ⁇ m PET film coated with a hard coat layer on one side and an anti-blocking layer on one side so that the thickness after drying is 2 ⁇ m is prepared, and the hard coat layer is prepared. An ITO layer was directly formed on the top so as to have a thickness of 5 nm. The temperature of the base film when forming the ITO layer was set to 130 ° C. ITO contains 10% by mass of SnO 2 with respect to In 2 O 3 .
  • an island-shaped aluminum (Al) layer having a thickness of 30 nm is formed on the ITO layer, and a laminate of a base film, an indium oxide-containing layer, and a metal layer is formed.
  • laminated body 1a was obtained.
  • the temperature of the base film when forming the Al layer was set to 130 ° C.
  • a 0.02 [-dB] when measuring the sheet resistance was 10 4 Omega more.
  • ⁇ Preparation of barrier layer> An aluminum oxide film having a thickness of 10 nm was formed as a barrier layer on the island-shaped aluminum layer of the laminated body 1a by a sputtering method to obtain a laminated body 1b.
  • ⁇ Creation of protective film with adhesive layer> 100 parts by mass of 2-ethylhexyl acrylate and 4 parts by mass of 2-hydroxyethyl acrylate were blended and copolymerized so as to be 35% by mass on a monomer basis, and contained an acrylic polymer having a weight average molecular weight of 600,000. A solution was obtained. To this solution, 4 parts by mass of an isocyanate-based cross-linking agent having an isocyanurate ring (Coronate HX manufactured by Nippon Polyurethane Industry Co., Ltd.) is added to 100 parts by mass of an acrylic polymer (dry mass), and ethyl acetate is further added to solidify the solution.
  • an isocyanate-based cross-linking agent having an isocyanurate ring Coronate HX manufactured by Nippon Polyurethane Industry Co., Ltd.
  • a pressure-sensitive adhesive solution (material A) having a component concentration adjusted to 20% was prepared.
  • the pressure-sensitive adhesive solution (material A) is applied onto an untreated polyethylene terephthalate film (PET) (manufactured by Mitsubishi Chemical Polyester Co., Ltd., Diafoil T100 # 38) having a thickness of 38 ⁇ m so that the film thickness after drying is 20 ⁇ m. Then, it was dried at 140 ° C. for 2 minutes to form an adhesive layer, and a protective film with an adhesive layer was obtained.
  • PET polyethylene terephthalate film
  • Example 2 An electromagnetic wave-transmitting metallic luster article was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive layer of the protective film with the pressure-sensitive adhesive layer of Example 1 was changed as follows to obtain a protective film. 95 parts by mass of butyl acrylate and 5 parts by mass of acrylic acid were copolymerized in ethyl acetate so as to be 30% by mass on a monomer basis to obtain a solution containing an acrylic polymer having a weight average molecular weight of 600,000.
  • the acrylic polymer solution (30% by mass) was diluted with ethyl acetate to 20% by mass, and an epoxy-based cross-linking agent (Mitsubishi Gas Chemicals (Mitsubishi Gas Chemicals Co., Ltd.) was used as a cross-linking agent for 100 parts by mass (solid content) of the acrylic polymer in this solution.
  • 5 parts by mass of TETRAD-C) manufactured by Co., Ltd. was added, and the mixture was kept at around 25 ° C. and mixed and stirred for about 1 minute to prepare an adhesive solution (material B).
  • the pressure-sensitive adhesive solution (material B) is applied onto an untreated polyethylene terephthalate film having a thickness of 38 ⁇ m so that the film thickness after drying is 5 ⁇ m, and dried at 150 ° C. for 90 seconds to form a pressure-sensitive adhesive layer. Then, a protective film with an adhesive layer was obtained.
  • Example 3 An electromagnetic wave-transmissive metallic luster article was obtained in the same manner as in Example 1 except that the adhesive layer of the protective film with the adhesive layer of Example 1 was obtained as described below. 90 parts by mass of butyl acrylate and 10 parts by mass of acrylic acid were copolymerized in ethyl acetate so as to be 30% by mass on a monomer basis to obtain a solution containing an acrylic polymer having a weight average molecular weight of 750,000.
  • the acrylic polymer solution (30% by mass) was diluted with ethyl acetate to 20% by mass, and an epoxy-based cross-linking agent (Mitsubishi Gas Chemicals (Mitsubishi Gas Chemicals Co., Ltd.) was used as a cross-linking agent for 100 parts by mass (solid content) of the acrylic polymer in this solution. 12 parts by mass of TETRAD-C) manufactured by Co., Ltd. was added, and the mixture was kept at about 25 ° C. and mixed and stirred for about 1 minute to prepare a pressure-sensitive adhesive solution (material C).
  • an epoxy-based cross-linking agent Mitsubishi Gas Chemicals (Mitsubishi Gas Chemicals Co., Ltd.) was used as a cross-linking agent for 100 parts by mass (solid content) of the acrylic polymer in this solution.
  • 12 parts by mass of TETRAD-C) manufactured by Co., Ltd. was added, and the mixture was kept at about 25 ° C. and mixed and stirred for about 1 minute to prepare a pressure-sensitive adhesive solution (material
  • the pressure-sensitive adhesive solution (material C) is applied onto an untreated polyethylene terephthalate film having a thickness of 125 ⁇ m so that the film thickness after drying is 20 ⁇ m, and dried at 150 ° C. for 90 seconds to form a pressure-sensitive adhesive layer. Then, a protective film with an adhesive layer was obtained.
  • Example 4 An electromagnetic wave-transmitting metallic luster article was obtained in the same manner as in Example 1 except that the barrier layer in the laminated body 1b of Example 1 was changed as follows to obtain a laminated body. As a barrier layer on top of the island-shaped aluminum layer of the laminate 1a, to obtain a Al 2 O 3 -ZnO film (AZO film) was formed so that the 30nm laminate by sputtering.
  • AZO film Al 2 O 3 -ZnO film
  • Example 5 Using the protective film with an adhesive layer as a protective layer, peel off the separator on one side of a transparent optical adhesive sheet (manufactured by Nitto Denko Co., Ltd., CS9861UAS (adhesive layer thickness: 25 ⁇ m, separator (polyethylene terephthalate film) thickness: 38 ⁇ m)).
  • a transparent optical adhesive sheet manufactured by Nitto Denko Co., Ltd., CS9861UAS (adhesive layer thickness: 25 ⁇ m, separator (polyethylene terephthalate film) thickness: 38 ⁇ m
  • An electromagnetic wave-transmitting metallic glossy article was obtained in the same manner as in Example 1 except that the film was changed to a new one (base material: PET sepa) and bonded to the surface of the barrier layer of the laminated body 1b.
  • the pressure-sensitive adhesive layer of the optical transparent pressure-sensitive adhesive sheet is an acrylic pressure-sensitive adhesive (material D).
  • the reflection characteristics (reflectance), protective film peeling force, and scratch resistance were evaluated for the electromagnetic wave-transmitting metallic luster articles obtained in Examples and Comparative Examples.
  • the details of the evaluation method are as follows.
  • ⁇ Humidification durability test method> The produced electromagnetic wave-transmitting metallic luster article was subjected to 65 ° C. H. After the humidification durability test, the electromagnetic wave-transmitting metallic luster article prepared from the constant temperature and humidity chamber was taken out and the protective film (protective layer) with the adhesive layer was peeled off. It was used as a sample.
  • a light-shielding film (manufactured by Mitsubishi Chemical Co., Ltd., B100-100) having an absorbance of about 5-6 was attached to the anti-blocking surface of the PET substrate with respect to the radio wave transmitting metallic luster article before and after the humidification durability test.
  • the surface from which the protective film (protective layer) with an adhesive layer was peeled off and the glass were laminated with an optical transparent adhesive sheet (CS9861UAS, manufactured by Nitto Denko KK).
  • the radio wave transmitting metallic luster article of Comparative Example 1 the surface on the barrier layer side and the glass were bonded with an optical transparent adhesive sheet (manufactured by Nitto Denko KK, CS9861UAS).
  • the peeled surface from which the separator of the transparent adhesive sheet for optics was peeled off was bonded with glass.
  • the reflectance Y (%) was measured for visible light having a wavelength in the range of 380 nm to 780 nm using a spectrocolorimeter CM-2600d manufactured by Konica Minolta. As the measurement data, the value of SCI indicating total reflection was used.
  • D65 was used as a standard light source, and the visible light was incident on the side where the metal layer was provided on the surface of the electromagnetic wave transmitting metallic luster article (the side where the glass was bonded). Further, the difference in reflectance before and after the humidification durability test (reflectance after the humidification durability test-initial reflectance) was defined as the amount of change ( ⁇ Y (%)).
  • the total cross-sectional area of the metal layer in the viewing angle region extracted at each of the five measurement points divided by the width of the viewing angle region is defined as the film thickness of the metal layer in each viewing angle region.
  • the average value of the film thickness of the metal layer in each viewing angle region was taken as the thickness (nm) of the metal layer.
  • TEM image transmission electron microscope photograph
  • the barrier layer was obtained from the obtained TEM image.
  • the included viewing angle region was extracted.
  • the total cross-sectional area of the barrier layer in the viewing angle region extracted at each of the five measurement points divided by the width of the viewing angle region is defined as the film thickness of the barrier layer in each viewing angle region.
  • the average value of the film thickness of the barrier layer in each viewing angle region was taken as the thickness (nm) of the barrier layer.
  • 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 square waveguide measurement evaluation jigs WR-187.

Landscapes

  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un article de lustre métallique transmettant des ondes électromagnétiques comprenant : un corps de base; une couche métallique formée sur le corps de base; et une couche protectrice formée sur une surface de la couche métallique opposée au corps de base, la couche métallique comprenant une pluralité de parties qui sont discontinues l'une par rapport à l'autre dans au moins une zone de celle-ci.
PCT/JP2020/025735 2019-07-11 2020-06-30 Article de lustre métallique transmettant des ondes électromagnétiques WO2021006130A1 (fr)

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WO2023190612A1 (fr) * 2022-03-30 2023-10-05 日東電工株式会社 Stratifié, dispositif électroluminescent et dispositif de détection

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WO2022181528A1 (fr) * 2021-02-24 2022-09-01 日東電工株式会社 Élément à perméabilité électromagnétique avec brillant métallique, et élément décoratif

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JPH03755U (fr) * 1989-05-24 1991-01-08
JP2018192808A (ja) * 2016-10-24 2018-12-06 日東電工株式会社 電磁波透過性金属光沢部材、これを用いた物品、及び、金属薄膜
JP2019086510A (ja) * 2017-11-07 2019-06-06 三恵技研工業株式会社 車載レーダー装置用レドーム及びその製造方法

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JPH03755U (fr) * 1989-05-24 1991-01-08
JP2018192808A (ja) * 2016-10-24 2018-12-06 日東電工株式会社 電磁波透過性金属光沢部材、これを用いた物品、及び、金属薄膜
JP2019086510A (ja) * 2017-11-07 2019-06-06 三恵技研工業株式会社 車載レーダー装置用レドーム及びその製造方法

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Publication number Priority date Publication date Assignee Title
WO2023190612A1 (fr) * 2022-03-30 2023-10-05 日東電工株式会社 Stratifié, dispositif électroluminescent et dispositif de détection

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