WO2021132456A1 - Feuille métallique décorative et corps moulé métallique décoratif comportant ladite feuille - Google Patents

Feuille métallique décorative et corps moulé métallique décoratif comportant ladite feuille Download PDF

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Publication number
WO2021132456A1
WO2021132456A1 PCT/JP2020/048427 JP2020048427W WO2021132456A1 WO 2021132456 A1 WO2021132456 A1 WO 2021132456A1 JP 2020048427 W JP2020048427 W JP 2020048427W WO 2021132456 A1 WO2021132456 A1 WO 2021132456A1
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Prior art keywords
layer
metal
decorative sheet
metallic
sea
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PCT/JP2020/048427
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English (en)
Japanese (ja)
Inventor
剛 天野
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大日本印刷株式会社
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Priority to JP2021567607A priority Critical patent/JPWO2021132456A1/ja
Publication of WO2021132456A1 publication Critical patent/WO2021132456A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon

Definitions

  • the present invention relates to a metal-like decorative sheet and a metal-like decorative molded body provided with the same.
  • An object of the present invention is to provide a metallic decorative sheet having an excellent metallic luster and a metallic decorative molded body having the decorative sheet and having an excellent metallic luster.
  • a metal-like decorative sheet having a metal layer on a base material layer, wherein the metal layer has a plurality of island portions containing metal and a sea portion located between the island portions, and the metal.
  • the area ratio of the sea part when the layer is viewed in a plan view is X (%) and the reflectance of the metallic decorative sheet at a wavelength of 550 nm is Y (%), the following conditional equations (1) to (3) Metallic decorative sheet that meets the requirements.
  • FIG. It is a graph showing the region satisfying the conditional equations (1) to (3) when the horizontal axis is the area ratio (%) of the sea part and the vertical axis is the reflectance (%) of the metallic decorative sheet at a wavelength of 550 nm. .. It is a figure explaining the thin line model used in Example 1.
  • FIG. It is a graph which shows the relationship between the area ratio of the sea part and the reflectance by Example 1.
  • FIG. It is a scanning electron micrograph of a metal layer in the metal-like decorative sheet of Example 2.
  • FIG. It is a scanning electron micrograph of a metal layer in the metal-like decorative sheet of Example 3.
  • FIG. It is a scanning electron micrograph of a metal layer in the metal-like decorative sheet of Example 4.
  • FIG. It is a scanning electron micrograph of a metal layer in the metal-like decorative sheet of Example 5.
  • the metallic decorative sheet of the present invention is a metallic decorative sheet having a metal layer on a base material layer, and the metal layer is a plurality of islands containing metal and a sea portion located between the islands.
  • X the area ratio of the sea part when the metal layer is viewed in a plan view
  • Y the reflectance of the metal-like decorative sheet at a wavelength of 550 nm
  • the metal layer in the metallic decorative sheet of the present invention has a "sea island structure" having a plurality of islands containing metal and a sea portion located between the islands.
  • the structure is shown in FIGS. 4 to 7, and a plurality of islands are densely packed, and the islands are separated by a sea part.
  • the structures shown in FIGS. 4 to 7 can be seen when the metal layer of the metallic decorative sheet is observed with a scanning electron microscope. Since the metal layer has a sea-island structure, it is possible to obtain a metallic decorative sheet that transmits electromagnetic waves in the radar wavelength region while having a metallic luster.
  • the area ratio X (%) of the sea part can be obtained by the following method. First, the surface of the metal layer is observed with an electron microscope under the following conditions, and an image is acquired. Equipment: Scanning electron microscope Observation conditions Acceleration voltage: 5 kV Emission current: 10 ⁇ A Pixel size: 9.5 to 10.0 nm Working distance: 15mm Observation magnification: 10,000 times Gradation: 8 bits
  • the cut out image is binarized based on Otsu's method.
  • the ratio of the area of the sea area to the entire cut-out image is defined as the area ratio (%) of the sea area of the relevant part.
  • the work was performed at 20 points in the image, and the average value of the 20 points was defined as the area ratio X (%) of the sea part of the metal layer.
  • the reflectance Y (%) in the present invention is a value when light having a wavelength of 550 nm is incident from the base material layer side, and can be obtained by using a spectrophotometer. In the present invention, the reflectance Y (%) is a value when the incident angle is 5 degrees.
  • the metallic decorative sheet of the present invention is required to satisfy the above-mentioned conditional expressions (1) to (3).
  • the conditional expression (1) is a regulation of the area ratio of the sea area.
  • the small area ratio of the sea area means that the adjacent island areas are close to each other.
  • the area ratio of the sea area is set to 10% or more (that is, X ⁇ 10).
  • the area ratio of the sea area is preferably 14% or more, more preferably 16% or more.
  • the larger the area ratio of the sea part the smaller the area ratio of the island part (metal part). That is, if the area ratio of the sea portion is too large, the reflectance of the metallic decorative sheet decreases, and it becomes difficult to obtain a metallic luster.
  • the area ratio X of the sea area is preferably 32% or less, and more preferably 30% or less.
  • Conditional expression (2) is a regulation of reflectance. From the viewpoint of obtaining a metallic decorative sheet having a metallic luster and excellent design, the reflectance is set to 60% or more (that is, Y ⁇ 60). Y is preferably 61% or more, and more preferably 62% or more. The larger the area ratio of the sea area, the lower the reflectance tends to be. From the viewpoint of facilitating the satisfaction of the conditional expression (1), Y is preferably 69.2% or less, more preferably 68.1% or less, and more preferably 66.5% or less. , 65.5% or less is more preferable.
  • Conditional formula (3) is a regulation that takes into consideration the decrease in reflectance due to the increase in the area of the sea area.
  • the absorption of visible light by the island portion containing metal is suppressed, so that the reflectance can be increased.
  • the area ratio of the sea part becomes large, even if the size of the island part is increased to eliminate the influence of absorption, the amount of transmitted light becomes large and the reflectance decreases.
  • the island portion is too large, diffused light from the edge of the island portion may be visually recognized even if the area ratio of the sea portion is adjusted, resulting in a rough metallic luster.
  • the present invention requires that the area ratio of the sea area and the reflectance satisfy the condition (3).
  • conditional expression (4) is a regulation that takes into consideration the decrease in reflectance and the suppression of the occurrence of whitening. Specifically, as the size of the islands decreases, the reflectance tends to decrease. In particular, when the size of the island is small (for example, the size of the island is 75 nm or less), the change in reflectance due to the fluctuation of the size of the island and the area ratio of the sea tends to be remarkable.
  • the conditional expression (4) even if the size of the island part and the area ratio of the sea part change due to the fluctuation of the manufacturing conditions of the metal-like decorative sheet, the fluctuation range of the reflectance of the obtained metal-like decorative sheet can be changed. It can be made smaller.
  • the small area ratio of the sea part means that the islands are densely formed, so that the islands are likely to come into contact with each other during molding.
  • Example of layer structure of metallic decorative sheet Specific examples of the metallic decorative sheet include the following configurations (1) to (8). In addition, "/" means the boundary of each layer.
  • Base material layer / Metal layer / Adhesive layer (2) Base material layer / Metal layer / Adhesive layer / Peeling layer (3) Base material layer / Primer layer / Metal layer / Adhesive layer (4) Base material layer / Primer Layer / Metal layer / Adhesive layer / Peeling layer (5) Base material layer / Metal layer / Adhesive layer / Backer layer (6) Base material layer / Primer layer / Metal layer / Adhesive layer / Backer layer (7) Base material layer / Metal layer / adhesive layer / backer layer / adhesive layer (8) Base material layer / primer layer / metal layer / adhesive layer / backer layer / adhesive layer The configuration of each layer will be described in detail below.
  • the base material layer serves as a support for the metallic decorative sheet. Further, it is preferable that the base material layer is arranged on the outermost layer side when the decorative molded product is formed. Therefore, the base material layer has a role of imparting scratch resistance to the metal-like decorative sheet and the metal-like decorative molded body. In this case, the base material layer is preferably transparent from the viewpoint that the metal layer can be visually recognized.
  • polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, vinyl resins such as ethylene-vinyl alcohol copolymer, polyethylene terephthalate, and the like.
  • polyester resins such as polyethylene naphthalate and polybutylene terephthalate, acrylic resins such as methyl poly (meth) acrylate and ethyl poly (meth) acrylate, styrene resins such as polystyrene, nylon 6 or nylon 66, etc.
  • a plastic film containing a resin such as a polyamide resin or an ABS resin (acrylonitrile-styrene-butadiene copolymer resin).
  • a resin such as a polyamide resin or an ABS resin (acrylonitrile-styrene-butadiene copolymer resin).
  • it has excellent weather resistance and moldability, and also has excellent transparency due to its low refractive index.
  • an acrylic resin film in which scratches are inconspicuous is preferable.
  • the resin component forming the base material layer only one type may be used, or two or more types may be mixed and used. Further, the base material layer may be formed of a single-layer film of these resins, or may be formed of a multi-layer film made of the same or different resins, but is preferably formed of a single-layer film. .. In the present invention, "(meth) acrylic” is a general term for "acrylic” and “methacryl”, and other similar substances with (meth) have the same meaning.
  • the base material layer is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one or both sides, if necessary, in order to improve the adhesion to the metal layer, the primer layer described later, and the like. May be.
  • the oxidation method performed as the surface treatment of the base material layer include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment method and the like.
  • examples of the unevenness method performed as the surface treatment of the base material layer include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of resin component constituting the base material layer, and from the viewpoint of effect, operability, and the like, a corona discharge treatment method is preferable.
  • the base layer has a haze of JIS K7136: 2000 of preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less. Further, the base material layer preferably has a visible light transmittance of JIS K7361-1: 1997 of 85% or more, and more preferably 90% or more.
  • the thickness of the base material layer is appropriately set according to the use of the metallic decorative sheet, and is usually about 50 to 250 ⁇ m, preferably about 60 to 150 ⁇ m, and more preferably about 70 to 125 ⁇ m.
  • the metal-like decorative sheet can be provided with even better three-dimensional moldability, designability, and the like.
  • the metal layer is a layer provided on the base material layer to impart metallic luster to the metallic decorative sheet.
  • the metal layer of the present invention has a sea-island structure having a plurality of islands containing metal and a sea portion located between the islands.
  • the metal layer of the present invention preferably has electromagnetic wave transmission property for transmitting electromagnetic waves having a radar wavelength.
  • the transmittance of electromagnetic waves having a frequency of 76.5 GHz is preferably 90% or more, and more preferably 93% or more.
  • the transmittance of electromagnetic waves having a frequency of 100 kHz is preferably 93% or more, and more preferably 95% or more.
  • the metal layer preferably contains indium, tin, gold, and at least one of these alloys, from the viewpoint that the formation of a metal layer by vapor deposition facilitates the formation of a sea-island structure.
  • the metal layer more preferably contains a metal having a melting point of 240 ° C. or lower, and the metal layer more preferably contains indium or tin.
  • indium tends to have a sea-island structure because it has a low melting point.
  • the metal layer made of indium is also preferable in that it has excellent metallic luster and good weather resistance.
  • the metal layer containing indium or tin tends to form a sea-island structure.
  • a metal having a relatively low melting point is formed by a vapor deposition method or the like, it takes a relatively long time for the metal reaching the surface of the base material to solidify.
  • the higher the substrate temperature during vapor deposition the longer the time to solidification. Therefore, it is considered that the metal before becoming a solid moves on the surface of the base material, collides with other metals, and coalesces to form an island portion.
  • the sea-island structure is formed by taking in the metal that reaches the surface of the base material and growing the island part while repeating collision and coalescence.
  • indium and tin have extremely low melting points of 156 ° C. and 232 ° C., respectively. Therefore, the solidification rate on the surface of the base material is slow, and the above-mentioned collisions and coalescences occur frequently, so that it is considered that the sea-island structure is more easily formed.
  • a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, plasma CVD using plasma, or contact heat of a material gas using a heating catalyst is used.
  • PVD physical vapor deposition method
  • Examples thereof include a chemical vapor deposition method (CVD) such as a catalytic chemical vapor deposition method (Cat-CVD) for decomposition.
  • CVD chemical vapor deposition method
  • Cat-CVD catalytic chemical vapor deposition method
  • the vacuum vapor deposition method which can process any material, is preferable. That is, as the metal layer, a physical vapor deposition film is preferable, and among them, a vacuum deposition film is preferable.
  • the thickness of each island is preferably 30 to 100 nm, more preferably 40 to 80 nm.
  • the thickness per island can be adjusted, for example, by the time of vapor deposition. That is, if the vapor deposition time is lengthened, the thickness of each island can be increased.
  • the size of the islands is 75 nm when the average value of the diameters calculated from the area of each island is defined as the "size of the islands". It is preferably 400 nm or more and 400 nm or less.
  • the size of the island portion determined by the above definition is 75 nm or more, a high reflectance (60% or more) can be obtained when the area ratio X of the sea portion is 10% or more. As a result, a metallic decorative sheet having excellent metallic luster can be obtained.
  • the size of the island portion is preferably 350 nm or less, and more preferably 300 nm or less.
  • the area per island can be calculated by the following method. First, an electron microscope image of the surface of the metal layer is acquired under the same conditions as when calculating the area ratio of the sea part, and the image is binarized.
  • a square frame containing 50 or more and 100 or less islands is superimposed on the photograph taken.
  • L represents the actual size on the sample, and can be calculated based on, for example, the pixel size or scale bar of the SEM photograph.
  • the number of islands including the whole in the frame (n 1 ) the number of islands in which it is recognized that 1/2 or more and less than 1 of the area of the island is present in the frame (n 2 ), the said.
  • n represented by the following formula (i) is fictitious as the number of islands existing in the frame.
  • n n 1 + (3n 2 + n 3 ) / 4 (i)
  • S [nm 2 ] the total area of the islands in the frame is calculated, and the total area is set to "S [nm 2 ]".
  • a S / n (ii)
  • the islands have an amorphous shape. Therefore, in calculating the island size in the present specification, it is assumed that each island is circular.
  • the diameter of the island, which is assumed to be circular, is defined as the "size of the island”.
  • the area ratio of the sea part and the size of the island part can be adjusted by the vapor deposition time, the substrate temperature at the time of deposition, the material of the substrate layer, the material of the primer layer described later, and the like. Specifically, when the vapor deposition time is lengthened, the size of the island portion can be increased, while the area ratio of the sea portion can be reduced. The higher the substrate temperature at the time of vapor deposition, the smaller the island size and the larger the area ratio of the sea area.
  • the metallic decorative sheet of the present invention may have an adhesive layer in order to bond the base material layer on which the metal layer is formed to the adherend.
  • the adhesive layer is provided on the surface of the metal layer opposite to the base material.
  • the adhesive layer is preferably composed of a heat-sensitive or pressure-sensitive resin.
  • the adhesive layer is preferably a so-called heat-sensitive adhesive layer or pressure-sensitive adhesive layer.
  • the resin used for the adhesive layer a general-purpose acrylic resin, urethane resin, polyester resin, silicone resin, vinyl chloride resin or vinyl acetate resin, or a mixture or copolymer of two or more of these is used. It is preferable to use it. From the viewpoint of adhesive strength, an acrylic resin is more preferable.
  • the thickness is preferably 0.5 to 3 ⁇ m, more preferably 0.5 to 1.5 ⁇ m. Further, in the case of a pressure-sensitive adhesive, the thickness is preferably 20 to 100 ⁇ m, more preferably 30 to 60 ⁇ m.
  • the glass transition temperature Tg of the adhesive layer is preferably 0 to 30 ° C., more preferably 5 to 28 ° C., and even more preferably 10 to 26 ° C.
  • resistance to chipping (chipping resistance) can be easily improved, heat resistance is improved, and deterioration of the surface smoothness of the decorative molded product is suppressed. It will be easier to do.
  • by setting the glass transition temperature to 30 ° C. or lower it becomes easy to suppress a decrease in chipping resistance due to a decrease in adhesion. Further, when the glass transition temperature is 0 to 30 ° C., it becomes easy to balance the chipping resistance of the decorative molded product with the smoothness of the surface of the metallic decorative sheet at a high temperature.
  • the primer layer improves the adhesion between the metal layer and the layer adjacent to the metal layer (for example, the base material layer), suppresses deterioration of the metal layer due to components (for example, chlorine component) contained in the layer adjacent to the metal layer, and It is a layer provided as needed for the purpose of a base or the like when a metal layer is formed by vapor deposition.
  • the material of the primer layer is not particularly limited, but it is preferably formed of a material having a small difference in refractive index from the base material layer from the viewpoint of reducing the influence on the reflectance.
  • the material of the primer layer include resins such as acrylic resin, polyurethane resin, acrylic-urethane copolymer resin, and polyester resin.
  • the primer layer preferably contains an acrylic resin in order to improve the adhesion with the metal layer.
  • the primer layer is preferably a layer containing an acrylic polyol and an isocyanate from the viewpoint that the sea-island structure is affected by the primer layer.
  • the primer layer may contain additives such as an ultraviolet absorber and a light stabilizer.
  • the thickness of the primer layer is not particularly limited, but is usually about 0.5 to 2.5 ⁇ m, preferably about 1 to 2 ⁇ m.
  • the metallic decorative sheet may have a release layer on the surface opposite to the base material of the adhesive layer for the purpose of protecting the adhesive layer.
  • the peeling layer can be easily peeled from the adhesive layer when the decorative molded product is manufactured by the vacuum forming method.
  • the release layer preferably contains a release agent in order to improve the release property.
  • the release layer can be a layer containing a release agent and a binder resin.
  • the release agent include a melamine resin release agent, a silicone release agent, a fluorine resin release agent, a cellulose resin release agent, a urea resin release agent, a polyolefin resin release agent, and a paraffin release agent.
  • Mold release agents such as mold agents, acrylic resin-based mold release agents, and composite mold release agents thereof are preferable. Of these, a silicone-based release agent is particularly preferable.
  • a thermoplastic resin is preferably used, for example, an acrylic resin, a polyester resin, a cellulose derivative resin, a polyvinyl acetal resin, a polyvinyl butyral resin, a vinyl chloride-vinyl acetate copolymer, and a chlorinated polyolefin resin. And so on.
  • the release layer is an ink prepared by dissolving or dispersing the above-mentioned mold release agent and binder resin with necessary additives in an appropriate solvent, using a gravure coating method, a roll coating method, a comma coating method, or gravure printing. It can be formed by coating and drying by a known means such as a method, a screen printing method, and a gravure reverse roll coating method.
  • a release film in which a release layer containing the above-mentioned release agent is provided on one side of a known resin film such as a polyester film may be used.
  • the metal-like decorative sheet may have a backer layer on the inner layer side of the metal layer (the side opposite to the base material layer with the metal layer interposed therebetween).
  • the backer layer has a role of improving the strength of the metal-like decorative sheet and maintaining the shape of the metal-like decorative molded body formed from the metal-like decorative sheet.
  • the thickness of the backer layer is not particularly limited, and may be appropriately selected in the range of, for example, 0.1 to 10 mm.
  • a plurality of backer layers may be laminated on the inner layer side of the metal layer.
  • the backer layer may be transparent, but in order to suppress surface reflection of the backer layer, it is preferably an achromatic color (gray, black) excluding white, and more preferably black.
  • the backer layer preferably contains a pigment for making it achromatic.
  • the backer layer pigment may be a black pigment alone or a mixture of a black pigment and another pigment (white pigment or the like).
  • the binder resin of the backer layer is a polyolefin resin such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefin-based thermoplastic elastomer, ABS (acrylonitrile-butadiene-).
  • a polyolefin resin such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefin-based thermoplastic elastomer, ABS (acrylonitrile-butadiene-).
  • ABS acrylonitrile-butadiene-
  • binder resins it is preferable to contain ABS resin from the viewpoint of suppressing cracks during molding.
  • the ratio of the ABS resin to the total binder resin in the backer layer is preferably 50% by mass or more, more preferably 70% by mass or more,
  • any additive such as a light stabilizer such as an ultraviolet absorber, a plasticizer, a filler, an antioxidant, a lubricant, and an antistatic agent can be added to the backer layer.
  • a light stabilizer such as an ultraviolet absorber, a plasticizer, a filler, an antioxidant, a lubricant, and an antistatic agent.
  • the backer layer preferably has a heat shrinkage rate of 1.0% or less, more preferably 0.5% or less, and further preferably 0.1% or less when heated at 75 ° C. for 30 minutes. preferable.
  • the metallic decorative sheet may have a layer other than those exemplified above as long as it does not significantly affect the reflectance.
  • the metallic decorative molded body of the present invention is formed by integrating an adherend with the metallic decorative sheet of the present invention.
  • the adhesive layer is located on the adherend side.
  • the adherend used for the metal-like decorative molded body of the metal-like decorative sheet of the present invention is not particularly limited, and examples thereof include a molded body made of glass, ceramics, resin, or the like.
  • the adherend may be one that has been molded into the shape of the molded body in advance, or may be the shape of the molded body at the time of decorative molding such as vacuum forming or insert molding.
  • the thickness of the adherend is not particularly limited, but is usually 1 mm or more, preferably 1 to 10 mm.
  • a metal-like decorative molded body can be manufactured by vacuum forming having the following steps (y1) to (y2).
  • (Y1) A laminated body is produced in which the surface of the metallic decorative sheet on the adhesive layer side and the adherend are adhered to each other.
  • (Y2) The surface of the laminated body on the adherend side is arranged toward the mold and vacuum formed.
  • Example 1 For the thin line model shown in FIG. 2, a metal-like decorative sheet at a wavelength of 550 nm when the size of the island part of the metal layer and the area ratio of the sea part are changed based on the strict coupling wave analysis (RCWA) method. It was calculated by simulating the reflectance (%) of.
  • RCWA strict coupling wave analysis
  • the sea island structure was simplified to one dimension.
  • the layer structure of the metal-like decorative sheet was a base material layer (PMMA) / metal layer (indium-deposited film).
  • the light emitting surface was arranged on the base material layer side, and it was set that the light was vertically incident on the base material layer (incident angle 5 °).
  • the length of the metal layer portion in the direction perpendicular to the light incident direction (reference numeral Lm in FIG. 2) was defined.
  • the ratio of the sea part in the thin line model was considered to correspond to the area ratio X (%) of the sea part when the metal-like decorative sheet (metal layer) was viewed in a plan view.
  • Metal layer thickness 50 nm Island size: 50nm-400nm
  • FIG. 3 is a graph showing the relationship between the area ratio of the sea area and the reflectance obtained in the above simulation.
  • the horizontal axis is the area ratio of the sea area
  • the vertical axis is the reflectance.
  • the areas represented by the conditional expressions (1) to (3) are shown by a thick frame and shading.
  • the reflectance tends to decrease as the area ratio of the sea portion increases.
  • the island size of the metal layer indium-deposited film
  • the reflectance was 60% or more by setting the area ratio of the predetermined sea area. That is, from FIG.
  • Example 2 An indium vapor deposition film was formed on a PMMA substrate (manufactured by Escarbo Sheet Co., Ltd., trade name "Technoloy Film S001G", width 1 m, thickness 125 ⁇ m) under the vapor deposition conditions shown in Table 1, and the metallic finish of Example 2 was formed. I got a decorative sheet.
  • the vapor deposition was carried out using a resistance heating vapor deposition type vapor deposition apparatus (EX-200, manufactured by ULVAC, Inc.). The pressure in the chamber at the start of vapor deposition was 1.0 ⁇ 10 -3 Pa.
  • Examples 3 and 5 An indium vapor deposition film was formed under the same conditions as in Example 2 except that the vapor deposition conditions shown in Table 1 were used to obtain metallic decorative sheets of Examples 3 and 5.
  • Example 4 One surface of the same PPMA base material as in Example 2 was subjected to corona treatment.
  • the corona treatment was carried out using a corona treatment device with a take-up / winding device under the conditions of an output of 100 W, a base-to-electrode distance of 1.5 mm, and a substrate transfer speed of 20 m / min.
  • an indium-deposited film was formed on the corona-treated surface of the base material under the same conditions as in Example 2 except that the conditions shown in Table 1 were applied, and the metallic decorative sheet of Example 4 was applied. Obtained.
  • Example 6 A coating liquid 1 for forming a primer layer having the following formulation was prepared. On the same PPMA base material as in Example 2, the primer layer forming coating liquid 1 was applied and dried to form a primer layer having a thickness of 2 ⁇ m. An indium-deposited film was formed on the formed primer layer under the same conditions as in Example 2 except that the conditions shown in Table 1 were used to obtain a metallic decorative sheet of Example 6.
  • Example 1 An indium vapor deposition film was formed under the same conditions as in Example 2 except that the vapor deposition conditions shown in Table 1 were used to obtain a metallic decorative sheet of Comparative Example 1.
  • Reflectance measurement A sample was cut out from the metal-like decorative sheets of Examples 2 to 6 and Comparative Example 1, and a spectral reflectance measuring device (spectral photometric meter) (manufactured by JASCO Corporation, trade name: V-670) was used. The measurement light was incident on the sample at an incident angle of 5 degrees from the substrate layer (PMMA) side, and the reflectance of the sample at a wavelength of 550 nm was measured. The reflectance (wavelength 550 nm) was measured for each of the samples cut out from 10 points, and the average value was taken as the reflectance Y (%) of the metal-like decorative sheet of Examples 2 to 6 and Comparative Example 1. The results are shown in Table 1.
  • a metal-like decorative molded body was obtained by injection molding.
  • a methacrylic resin was used as the injection resin.
  • the shape of the molded body was a flat plate of 10 cm ⁇ 15 cm.
  • the resin temperature at the time of injection was 240 ° C.
  • the surface of the obtained metallic decorative molded product was visually observed, and the whitening of the metallic decorative sheet was evaluated according to the following criteria. The results are shown in Table 1. A: No whitening was seen B: Slight whitening was seen C: Whitening was confirmed overall
  • FIG. 3 displays plots of Examples 2 to 6 and Comparative Example 1. It can be seen that all the examples fall within the region represented by the conditional expressions (1) to (3).
  • the plot of Example 2 is close to the graph for the simulated island size of 250 nm.
  • Example 4 is located between the graph obtained by the simulation when the island size is 100 nm and the graph when the island size is 150 nm. In this way, there was a strong correlation between the results of the simulation with the one-dimensional thin line model and the sample, which was almost the same as the simulation results.

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

Abstract

L'invention concerne une feuille métallique décorative ayant un excellent éclat métallique et un corps moulé métallique décoratif comportant la feuille décorative. La feuille métallique décorative présente une couche métallique sur une couche de matériau de base, la couche métallique ayant une pluralité de parties îlots contenant un métal et une partie mer positionnée entre les parties îlots, et les expressions conditionnelles (1) à (3) suivantes étant satisfaites, où X(%) est le rapport de surface de la partie mer dans une vue en plan de la couche métallique et Y(%) est la réflectance de la feuille métallique décorative à une longueur d'onde de 550 nm. (1) : X ≧ 10 (2) : Y ≧ 60 (3) : Y ≦ -0,4182X + 73,382
PCT/JP2020/048427 2019-12-26 2020-12-24 Feuille métallique décorative et corps moulé métallique décoratif comportant ladite feuille WO2021132456A1 (fr)

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WO2019208493A1 (fr) * 2018-04-23 2019-10-31 日東電工株式会社 Article perméable au rayonnement électromagnétique ayant un lustre métallique, et élément décoratif
WO2019208499A1 (fr) * 2018-04-23 2019-10-31 日東電工株式会社 Article à perméabilité électromagnétique à brillant métallique
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WO2020153137A1 (fr) * 2019-01-25 2020-07-30 ソニー株式会社 Structure, film décoratif, procédé de fabrication de structure et procédé de fabrication de film décoratif
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WO2009110090A1 (fr) * 2008-03-07 2009-09-11 三菱電機株式会社 Pièce décorative
JP2010251899A (ja) * 2009-04-13 2010-11-04 Sankei Giken Kogyo Co Ltd 電磁波透過性の金属複合材料及びその製造方法
JP2011027434A (ja) * 2009-07-21 2011-02-10 Toyota Motor Corp 樹脂基材表面への装飾皮膜の形成方法とその装飾皮膜を有する外装装飾部材
JP2018069462A (ja) * 2016-10-24 2018-05-10 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
JP2018154878A (ja) * 2017-03-17 2018-10-04 株式会社Ｊｃｕ 電磁波透過用金属被膜、電磁波透過用金属被膜の形成方法及び車載用レーダー装置
WO2019208493A1 (fr) * 2018-04-23 2019-10-31 日東電工株式会社 Article perméable au rayonnement électromagnétique ayant un lustre métallique, et élément décoratif
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JP2019209550A (ja) * 2018-06-01 2019-12-12 大日本印刷株式会社 金属調加飾用部材及びそれを用いた金属調加飾成形体
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