WO2021132456A1 - Metallic decorative sheet and metallic decorative molded body provided with same - Google Patents

Metallic decorative sheet and metallic decorative molded body provided with same 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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French (fr)
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/en

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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 form; Layered products 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 form; Layered products 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 form; Layered products 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.

Abstract

Provided are a metallic decorative sheet having an excellent metallic luster, and a metallic decorative molded body provided with the decorative sheet. The metallic decorative sheet has a metallic layer on a base material layer, wherein the metallic layer has a plurality of island parts containing a metal, and a sea part positioned between the island parts, and wherein the following conditional expressions (1) to (3) are satisfied, where X(%) is the area ratio of the sea part in a plan view of the metallic layer, and Y(%) is the reflectance of the metallic decorative sheet at a wavelength of 550 nm. (1): X ≧ 10 (2): Y ≧ 60 (3): Y ≦ -0.4182X + 73.382

Description

金属調加飾シート及びこれを備える金属調加飾成形体Metal-like decorative sheet and metal-like decorative molded body equipped with it
　本発明は、金属調加飾シート及びこれを備える金属調加飾成形体に関する。 The present invention relates to a metal-like decorative sheet and a metal-like decorative molded body provided with the same.
　従来より、成形体の意匠性を高めるために、成形体の表面に金属光沢を付与することが行われている。金属光沢を付与する手段として、金属光沢を有する加飾シートを金型内に配置し、その金型内に樹脂を射出成型することにより、成形体に金属蒸着シートを接着させる手段が知られている（例えば特許文献１）。 Conventionally, in order to enhance the design of the molded product, metallic luster has been imparted to the surface of the molded product. As a means for imparting metallic luster, a means for adhering a metal vapor deposition sheet to a molded body by arranging a decorative sheet having metallic luster in a mold and injection molding a resin in the mold is known. (For example, Patent Document 1).
特許５８０９７６８号公報Japanese Patent No. 5809768
　しかしながら、上述した金属光沢を有する金属蒸着シートを用いて成形体を形成した場合、成形体表面が白っぽく見え、期待した金属光沢が得られないことが頻発した。 However, when the molded body was formed using the metal vapor deposition sheet having the metallic luster described above, the surface of the molded body looked whitish and the expected metallic luster was not obtained frequently.
　本発明は、金属光沢感に優れる金属調加飾シート、及び、該加飾シートを備え、金属光沢感に優れる金属調加飾成形体を提供することを目的とする。 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.
　本願発明者が検討した結果、複数の島部と該島部間の海部とを有するいわゆる「海島構造」を有する金属層を形成した金属調加飾シートにおいて、海部の面積比率が小さい場合に、成型体を作製した際に白化が起こりやすいことを見出した。更に、海部の面積比率によって、金属調加飾シートの反射率が変化することを見出した。すなわち、金属光沢に優れ、成形時の白化を抑制することができる金属調加飾シートを得るためには、海部の面積比率及び反射率に適切な範囲があり、これらを適切に制御する必要があることが分かった。 As a result of examination by the inventor of the present application, in a metal-like decorative sheet having a metal layer having a so-called "sea island structure" having a plurality of islands and a sea between the islands, when the area ratio of the sea is small. It was found that whitening is likely to occur when the molded body is produced. Furthermore, it was found that the reflectance of the metallic decorative sheet changes depending on the area ratio of the sea area. That is, in order to obtain a metallic decorative sheet having excellent metallic luster and capable of suppressing whitening during molding, there is an appropriate range in the area ratio and reflectance of the sea part, and it is necessary to appropriately control these. It turned out that there was.
　すなわち、上記課題を解決するために、本発明は、以下の［１］～［４］を提供する。
［１］基材層上に金属層を有する金属調加飾シートであって、前記金属層は金属を含む複数の島部と、前記島部の間に位置する海部とを有し、前記金属層を平面視したときの前記海部の面積比率をＸ（％）、波長５５０ｎｍにおける前記金属調加飾シートの反射率をＹ（％）としたときに、下記条件式（１）～（３）を満たす金属調加飾シート。
　Ｘ≧１０　…（１）
　Ｙ≧６０　…（２）
　Ｙ≦－０．４１８２Ｘ＋７３.３８２　…（３）
［２］前記島部の各々を円形と仮定し、前記島部１個あたりの面積から算出した直径の平均値を、前記島部のサイズと定義した場合に、前記サイズが７５ｎｍ以上４００ｎｍ以下である、［１］に記載の金属調加飾シート。
［３］前記金属層は、インジウム又はスズを含む、［１］または［２］に記載の金属調加飾シート。
［４］［１］～［３］の何れかに記載の金属調加飾シートと、被着体とを有する金属調加飾成形体。 That is, in order to solve the above problems, the present invention provides the following [1] to [4].
[1] 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. When 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.
X ≧ 10… (1)
Y ≧ 60… (2)
Y ≦ −0.4182X + 73.382… (3)
[2] When each of the islands is assumed to be circular and the average value of the diameters calculated from the area per island is defined as the size of the islands, the size is 75 nm or more and 400 nm or less. A metal-like decorative sheet according to [1].
[3] The metal-like decorative sheet according to [1] or [2], wherein the metal layer contains indium or tin.
[4] A metal-like decorative molded body having the metal-like decorative sheet according to any one of [1] to [3] and an adherend.
　本発明に依れば、金属光沢感に優れる金属調加飾シート、及び、該加飾シートを備える金属調加飾成形体を得ることができる。 According to the present invention, it is possible to obtain a metallic decorative sheet having an excellent metallic luster and a metallic decorative molded body provided with the decorative sheet.
横軸を海部の面積比率（％）、縦軸を波長５５０ｎｍにおける金属調加飾シートの反射率（％）とした場合に、条件式（１）～（３）を満たす領域を表すグラフである。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. .. 実施例１で用いた細線モデルを説明する図である。It is a figure explaining the thin line model used in Example 1. FIG. 実施例１による海部の面積比率と反射率との関係を示すグラフである。It is a graph which shows the relationship between the area ratio of the sea part and the reflectance by Example 1. FIG. 実施例２の金属調加飾シートにおける金属層の走査型電子顕微鏡写真である。It is a scanning electron micrograph of a metal layer in the metal-like decorative sheet of Example 2. FIG. 実施例３の金属調加飾シートにおける金属層の走査型電子顕微鏡写真である。It is a scanning electron micrograph of a metal layer in the metal-like decorative sheet of Example 3. FIG. 実施例４の金属調加飾シートにおける金属層の走査型電子顕微鏡写真である。It is a scanning electron micrograph of a metal layer in the metal-like decorative sheet of Example 4. FIG. 実施例５の金属調加飾シートにおける金属層の走査型電子顕微鏡写真である。It is a scanning electron micrograph of a metal layer in the metal-like decorative sheet of Example 5. FIG.
　以下、本発明の金属調加飾シート及び金属調加飾成形体について、詳細に説明する。なお、本明細書中の「ＡＡ～ＢＢ」との数値範囲の表記は、「ＡＡ以上ＢＢ以下」であることを意味する。 Hereinafter, the metal-like decorative sheet and the metal-like decorative molded body of the present invention will be described in detail. The notation of the numerical range of "AA to BB" in this specification means "AA or more and BB or less".
［金属調加飾シート］
　本発明の金属調加飾シートは、基材層上に金属層を有する金属調加飾シートであって、前記金属層は金属を含む複数の島部と、前記島部の間に位置する海部とを有し、前記金属層を平面視したときの前記海部の面積比率をＸ（％）、波長５５０ｎｍにおける前記金属調加飾シートの反射率をＹ（％）としたときに、下記条件式（１）～（３）を満たす金属調加飾シートである。
　　Ｘ≧１０　…（１）
　　Ｙ≧６０　…（２）
　　Ｙ≦－０．４１８２Ｘ＋７３.３８２　…（３） [Metallic decoration sheet]
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. When the area ratio of the sea part when the metal layer is viewed in a plan view is X (%) and the reflectance of the metal-like decorative sheet at a wavelength of 550 nm is Y (%), the following conditional expression is used. It is a metallic decorative sheet satisfying (1) to (3).
X ≧ 10… (1)
Y ≧ 60… (2)
Y ≦ −0.4182X + 73.382… (3)
　本発明の金属調加飾シートにおける金属層は、金属を含む複数の島部と、島部の間に位置する海部とを有する「海島構造」を有する。例示的には、図４～７に示す構造であり、複数の島部が密集し、島部間は海部で隔てられている。図４～７に示す構造は、金属調加飾シートの金属層を走査型電子顕微鏡で観察した際に見られる。金属層が海島構造を有することにより、金属調の光沢感を有しつつ、レーダー波長領域の電磁波を透過する金属調加飾シートとすることができる。 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. Illustratively, 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.
〔海部の面積比率〕
　本発明において、海部の面積比率Ｘ（％）は、以下の方法で求めることができる。
　まず、下記の条件で金属層表面の電子顕微鏡観察を行い、画像を取得する。
　　装置：走査型電子顕微鏡
　　観察条件
　　　加速電圧：５ｋＶ
　　　エミッションカレント：１０μＡ
　　　ピクセルサイズ：９．５～１０．０ｎｍ
　　　ワーキングディスタンス：１５ｍｍ
　　　観察倍率：１０，０００倍
　　　階調：８ビット [Area ratio of sea area]
In the present invention, 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 μA
Pixel size: 9.5 to 10.0 nm
Working distance: 15mm
Observation magnification: 10,000 times Gradation: 8 bits
　上記条件での観察で得られた画像から８０～９０万画素分を切り出す。切り出した画像をＯｔｓｕ’ｓ　ｍｅｔｈｏｄに基づいて２値化処理する。切り出した画像全体に対する海部の面積の割合を、当該箇所の海部の面積比率（％）とする。当該作業を画像の２０箇所で行い、２０箇所の平均値を金属層の海部の面積比率Ｘ（％）とした。 Cut out 800,000 to 900,000 pixels from the image obtained by observation under the above conditions. 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.
〔金属調加飾シートの反射率〕
　本発明における反射率Ｙ（％）は、基材層側から波長５５０ｎｍの光を入射したときの値であり、分光光度計を用いて取得することができる。なお本発明において、反射率Ｙ（％）は、入射角５度としたときの値である。 [Reflectance of metallic decorative sheet]
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.
〔条件式（１）～（３）〕
　本発明の金属調加飾シートは、上述した条件式（１）～（３）を満たすことを要件とする。
　条件式（１）は、海部の面積比率の規定である。海部の面積比率が小さいことは、隣り合う島部が近接していることを意味する。射出成形により金属調加飾シートを接着させたり、金属調加飾シートを成型体に貼着したりして金属調加飾成形体を製造する際に、三次元曲面への金属調加飾シートの追従による変形や熱による金属調加飾シートの収縮などが起こる場合がある。海部の面積比率が小さく島部が近接していると、島部同士が接触して、金属調加飾シートが白化する虞がある。白化の発生を抑制するとの観点から、海部の面積比率は１０％以上（すなわち、Ｘ≧１０）とする。確実に白化の発生を抑制するために、海部の面積比率は１４％以上が好ましく、１６％以上がより好ましい。
　なお、海部の面積比率が大きくなることは、島部（金属部分）の面積比率が小さくなることを意味する。すなわち、海部の面積比率が大きすぎると、金属調加飾シートの反射率が低下し、金属光沢感を得ることが難しくなる。この観点から、海部の面積比率Ｘは、３２％以下であることが好ましく、３０％以下であることがより好ましい。 [Conditional expressions (1) to (3)]
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. When a metal-like decorative sheet is adhered by injection molding or a metal-like decorative sheet is attached to a molded body to manufacture a metal-like decorative molded body, the metal-like decorative sheet on a three-dimensional curved surface is formed. Deformation due to the follow-up of the metal and shrinkage of the metallic decorative sheet due to heat may occur. If the area ratio of the sea area is small and the islands are close to each other, the islands may come into contact with each other and the metallic decorative sheet may be whitened. From the viewpoint of suppressing the occurrence of bleaching, the area ratio of the sea area is set to 10% or more (that is, X ≧ 10). In order to surely suppress the occurrence of bleaching, 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. From this point of view, the area ratio X of the sea area is preferably 32% or less, and more preferably 30% or less.
　条件式（２）は、反射率の規定である。金属光沢感のある優れた意匠性を有する金属調加飾シートを得る観点から、反射率は６０％以上（すなわち、Ｙ≧６０）とする。Ｙは６１％以上であることが好ましく、６２％以上であることがより好ましい。なお、海部の面積比率が大きいほど、反射率が低くなる傾向がある。条件式（１）を満たしやすくするとの観点から、Ｙは、６９．２％以下であることが好ましく、６８．１％以下であることがより好ましく、６６．５％以下であることがより好ましく、６５．５％以下であることが更に好ましいい。 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.
　条件式（３）は、海部の面積が増加することによる反射率の低下を考慮した規定である。島部を大きくすることにより、金属を含む島部による可視光の吸収が抑制されるため、反射率を高くすることができる。一方で、海部の面積比率が大きくなると、島部のサイズを大きくして吸収の影響を排除したとしても、透過光量が大きくなるため、反射率が低下してしまう。また、島部が大きすぎる場合には、海部の面積比率を調整しても島部のエッジからの拡散光が視認され、ざらついた金属光沢となる虞がある。これらを考慮して、本発明では、海部の面積比率と反射率とが条件（３）を満たすことを要件とする。 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. By enlarging the island portion, the absorption of visible light by the island portion containing metal is suppressed, so that the reflectance can be increased. On the other hand, when 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. Further, if 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. In consideration of these, the present invention requires that the area ratio of the sea area and the reflectance satisfy the condition (3).
　海部の面積比率Ｘ（％）をｘ軸、反射率Ｙ（％）をｙ軸としたときに、条件式（１）～（３）を満たす領域は、図１の太枠及び網掛けで示される領域に相当する。 When the area ratio X (%) of the sea area is on the x-axis and the reflectance Y (%) is on the y-axis, the regions satisfying the conditional expressions (1) to (3) are shown by the thick frame and shading in FIG. Corresponds to the area to be
　本発明の金属調加飾シートは更に、下記条件式（４）を満たすことが好ましい。
　　Ｙ≧－０.７５Ｘ＋７０.５　…（４）
　条件式（４）は、反射率の低下及び白化の発生の抑制を考慮した規定である。具体的に、島部のサイズが小さくなると、反射率が低下する傾向がある。特に島部のサイズが小さい場合（例えば島部のサイズが７５ｎｍ以下）では、島部のサイズ及び海部の面積比率の変動による反射率の変化が顕著となる傾向がある。条件式（４）を満たすことにより、金属調加飾シートの製造条件のブレにより島部のサイズ及び海部の面積比率が変化した場合でも、得られる金属調加飾シートの反射率の変動幅を小さくすることができる。また、海部の面積比率が小さいことは島部が密に形成されていることであるため、成形時に島部同士が接触しやすくなる。条件式（４）を満たすことにより、成形時の白化の発生を確実に抑制することができる。 It is preferable that the metallic decorative sheet of the present invention further satisfies the following conditional expression (4).
Y ≧ −0.75X + 70.5… (4)
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. By satisfying 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. In addition, 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. By satisfying the conditional expression (4), the occurrence of whitening during molding can be reliably suppressed.
〔金属調加飾シートの層構成の例〕
　金属調加飾シートの具体例としては、例えば、下記（１）～（８）の構成が挙げられる。なお、「／」は各層の境界を意味する。
（１）基材層／金属層／接着層
（２）基材層／金属層／接着層／剥離層
（３）基材層／プライマー層／金属層／接着層
（４）基材層／プライマー層／金属層／接着層／剥離層
（５）基材層／金属層／接着層／バッカー層
（６）基材層／プライマー層／金属層／接着層／バッカー層
（７）基材層／金属層／接着層／バッカー層／接着層
（８）基材層／プライマー層／金属層／接着層／バッカー層／接着層
　以下、各層の構成について詳細に説明する。 [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.
(1) 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.
＜基材層＞
　基材層は、金属調加飾シートの支持体としての役割を有する。また、基材層は、加飾成形体となった場合に、最も外層側に配置されることが好ましい。このため、基材層は、金属調加飾シート及び金属調加飾成形体に耐擦傷性を付与する役割を有する。この場合、金属層を視認できるとの観点から、基材層は透明性を有することが好ましい。 <Base layer>
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.
　基材層としては、ポリエチレン、ポリプロピレンなどのポリオレフィン系樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、エチレン―酢酸ビニル共重合体、エチレン―ビニルアルコール共重合体などのビニル系樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレートなどのポリエステル系樹脂、ポリ（メタ）アクリル酸メチル、ポリ（メタ）アクリル酸エチルなどのアクリル系樹脂、ポリスチレン等のスチレン系樹脂、ナイロン６又はナイロン６６などで代表されるポリアミド系樹脂、ＡＢＳ樹脂（アクリロニトリル―スチレン―ブタジエン共重合体樹脂）などの樹脂を含むプラスチックフィルムを用いることが好ましい。
　これらの中でも、耐候性、成形性に優れるとともに、屈折率が低いため透明性に優れ、
かつ傷が目立ちにくい、アクリル系樹脂フィルムが好適である。 As the base material layer, 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. Represented by 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. It is preferable to use a plastic film containing a resin such as a polyamide resin or an ABS resin (acrylonitrile-styrene-butadiene copolymer resin).
Among these, it has excellent weather resistance and moldability, and also has excellent transparency due to its low refractive index.
Moreover, an acrylic resin film in which scratches are inconspicuous is preferable.
　基材層を形成する樹脂成分としては、１種類のみを用いてもよいし、２種類以上を混合して用いてもよい。また、基材層は、これら樹脂の単層フィルムで形成されていてもよく、また同種又は異種樹脂による複層フィルムで形成されていてもよいが、単層フィルムで形成されていることが好ましい。
　なお、本発明において、「（メタ）アクリル」とは「アクリル」及び「メタクリル」の総称であり、（メタ）の付く他の類似するものも同様の意である。 As 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.
　基材層は、金属層、後述するプライマー層などとの密着性を向上させるために、必要に応じて、片面又は両面に酸化法や凹凸化法等の物理的又は化学的表面処理が施されていてもよい。基材層の表面処理として行われる酸化法としては、例えば、コロナ放電処理、プラズマ処理、クロム酸化処理、火炎処理、熱風処理、オゾン紫外線処理法等が挙げられる。また、基材層の表面処理として行われる凹凸化法としては、例えばサンドブラスト法、溶剤処理法等が挙げられる。これらの表面処理は、基材層を構成する樹脂成分の種類に応じて適宜選択されるが、効果及び操作性等の観点から、好ましくはコロナ放電処理法が挙げられる。 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. Examples of 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. Further, 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.
　基材層は、ＪＩＳ　Ｋ７１３６：２０００のヘイズが５％以下であることが好ましく、３％以下であることがより好ましく、１％以下であることがさらに好ましい。
　また、基材層は、ＪＩＳ　Ｋ７３６１－１：１９９７の可視光線透過率が８５％以上であることが好ましく、９０％以上であることがより好ましい。 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.
　基材層の厚みは、金属調加飾シートの用途等に応じて適宜設定されるが、通常５０～２５０μｍ程度、好ましくは６０～１５０μｍ程度、さらに好ましくは７０～１２５μｍ程度が挙げられる。基材層の厚みが上記範囲内であると、金属調加飾シートに対してより一層優れた三次元成形性、意匠性などを備えさせることができる。 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 μm, preferably about 60 to 150 μm, and more preferably about 70 to 125 μm. When the thickness of the base material layer is within the above range, the metal-like decorative sheet can be provided with even better three-dimensional moldability, designability, and the like.
＜金属層＞
　金属層は、基材層の上に設けられ、金属調加飾シートに金属光沢を付与する層である。本発明の金属層は、図４～７に例示されるように、金属を含む複数の島部と、島部の間に位置する海部とを有する、海島構造を有する。
　本発明の金属層は、レーダー波長の電磁波を透過する電磁波透過性を有していることが好ましい。具体的に、周波数７６．５ＧＨｚの電磁波の透過率が９０％以上であることが好ましく、９３％以上であることがより好ましい。また、周波数１００ｋＨｚの電磁波の透過率が９３％以上であることが好ましく、９５％以上であることがより好ましい。 <Metal layer>
The metal layer is a layer provided on the base material layer to impart metallic luster to the metallic decorative sheet. As illustrated in FIGS. 4 to 7, 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. Specifically, the transmittance of electromagnetic waves having a frequency of 76.5 GHz is preferably 90% or more, and more preferably 93% or more. Further, the transmittance of electromagnetic waves having a frequency of 100 kHz is preferably 93% or more, and more preferably 95% or more.
　本発明では、蒸着による金属層形成で海島構造をとりやすいとの観点から、金属層はインジウム、スズ、金、及びこれらの合金のうち少なくとも１種を含むことが好ましい。金属層は、融点が２４０℃以下の金属を含むことがより好ましく、金属層がインジウム又はスズを含むことがより好ましい。中でも、インジウムは融点が低いために、海島構造となりやすい傾向がある。また、インジウムからなる金属層は、金属光沢に優れ、耐候性が良好である点でも好適である。 In the present invention, 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. Among them, indium tends to have a sea-island structure because it has a low melting point. Further, the metal layer made of indium is also preferable in that it has excellent metallic luster and good weather resistance.
　インジウムまたはスズを含む金属層が海島構造を形成しやすい理由は以下のように推測される。
　比較的融点の低い金属を蒸着法等により成膜する場合、基材表面に到達した金属が凝固するまでに比較的時間を要する。蒸着時の基材温度が高い程、凝固までの時間が長くなる。このため、固体になる前の金属が基材表面を移動して他の金属と衝突し、合体することによって、島部が形成されると考えられる。その後、衝突及び合体を繰り返しながら、基材表面に到達する金属を取り込んで島部が成長することで、海島構造が形成されると考えられる。特に、インジウム及びスズは、それぞれ融点が１５６℃、２３２℃と極めて低い。このため、基材表面での凝固速度が遅く、上述の衝突及び合体の発生頻度が高いため、海島構造をより形成しやすいと考えられる。 The reason why the metal layer containing indium or tin tends to form a sea-island structure is presumed as follows.
When 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. After that, it is considered that 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. In particular, 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.
　金属層の形成方法としては、真空蒸着法、スパッタリング法、イオンプレーティング法等の物理的気相蒸着法（ＰＶＤ）や、プラズマを利用したプラズマＣＶＤ、加熱触媒体を用いて材料ガスを接触熱分解する触媒化学気相成長法（Ｃａｔ－ＣＶＤ）等の化学的気相蒸着法（ＣＶＤ）が挙げられる。これらの中でも、あらゆる素材に処理可能である真空蒸着法が好ましい。すなわち、金属層としては物理的気相蒸着膜が好ましく、その中でも真空蒸着膜が好ましい。 As a method for forming the metal layer, a physical vapor deposition method (PVD) 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. Examples thereof include a chemical vapor deposition method (CVD) such as a catalytic chemical vapor deposition method (Cat-CVD) for decomposition. Among these, 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.
　金属光沢感及び成形性等の観点から、島部１個あたりの厚みが３０～１００ｎｍとなるように形成するものとすることが好ましく、４０～８０ｎｍであることがより好ましい。
　島部１個あたりの厚みは、例えば、蒸着の時間で調整することができる。すなわち、蒸着時間を長くすると、島部１個あたりの厚みを増大させることができる。 From the viewpoint of metallic luster and moldability, 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.
　本発明における金属層は、島部の各々を円形と仮定し、島部１個あたりの面積から算出した直径の平均値を「島部のサイズ」と定義した場合に、島部のサイズが７５ｎｍ以上４００ｎｍ以下であることが好ましい。
　上記定義で求めた島部のサイズが７５ｎｍ以上であると、海部の面積比率Ｘが１０％以上としたときに、高い反射率（６０％以上）を得ることができる。この結果、金属光沢に優れる金属調加飾シートを得ることができる。更に、島部のサイズを１６０ｎｍ以上、より望ましくは２００ｎｍ以上とすることにより、より高反射率の金属層が形成された金属調加飾シートを得やすくなる。
　一方、島部のサイズが大きくなるほど、島部が占める面積が大きくなるため、相対的に海部の面積比率が下がる傾向がある。この場合、成形時の島部同士の接触による金属調加飾シートの白化が発生する虞がある。また、成形時に金属調加飾シートが延伸された場合に、島部が割れることにより金属光沢感が低下する虞がある。さらに、島部のサイズが大きすぎると、海部の幅（すなわち、島部の間隔）が大きくなり、島部のエッジからの拡散光が視認される場合がある。この結果、ざらついた金属光沢となり、所望の美観を得ることができない虞がある。これらを抑制するとの観点から、島部のサイズを３５０ｎｍ以下とすることが好ましく、３００ｎｍ以下とすることがより好ましい。 In the metal layer in the present invention, assuming that each of the islands is circular, 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.
When 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. Further, by setting the size of the island portion to 160 nm or more, more preferably 200 nm or more, it becomes easy to obtain a metal-like decorative sheet on which a metal layer having a higher reflectance is formed.
On the other hand, as the size of the islands increases, the area occupied by the islands increases, so the area ratio of the seas tends to decrease relatively. In this case, whitening of the metallic decorative sheet may occur due to contact between the islands during molding. Further, when the metallic decorative sheet is stretched during molding, the island portion may be cracked to reduce the metallic luster. Furthermore, if the size of the islands is too large, the width of the sea (that is, the distance between the islands) becomes large, and diffused light from the edges of the islands may be visually recognized. As a result, the metallic luster becomes rough, and there is a possibility that a desired aesthetic appearance cannot be obtained. From the viewpoint of suppressing these, the size of the island portion is preferably 350 nm or less, and more preferably 300 nm or less.
　島部１個あたりの面積は、下記の手法で算出することができる。
　まず、海部の面積比率を算出する場合と同じ条件で、金属層表面の電子顕微鏡画像を取得し、画像を２値化処理する。 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.
　次いで、撮影した写真上に、島部が５０個以上１００個以下入る正方形の枠を重ねる。該枠の一辺の長さをＬ［ｎｍ］とする。「Ｌ」はサンプル上の実サイズを表し、例えば、ＳＥＭ写真のピクセルサイズ又はスケールバーを基準として算出することができる。
　次いで、該枠内に全体が含まれる島部の数（ｎ１）、該枠内にその島部の面積の１／２以上１未満が存在すると認められる島部の数（ｎ２）、該枠内にその島部の面積の１／２未満が存在すると認められる島部の数（ｎ３）をカウントする。カウントしたｎ１、ｎ２及びｎ３に基づいて下記式（ｉ）で示される「ｎ」を、該枠内に存在する島部の個数と擬制する。
　　ｎ＝ｎ１＋（３ｎ２＋ｎ３）／４　（ｉ）
　次いで、該枠における島部の合計面積を算出し、該合計面積を「Ｓ［ｎｍ２］」とする。
　そして、Ｓ［ｎｍ２］及び式（ｉ）で算出した該枠内の島部の数（ｎ）に基づいて下記式（ｉｉ）で示される「ａ」を、該枠内における島部１個あたりの面積［ｎｍ２］と擬制する。
　　ａ＝Ｓ／ｎ　（ｉｉ） Next, a square frame containing 50 or more and 100 or less islands is superimposed on the photograph taken. Let the length of one side of the frame be L [nm]. “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.
Next, 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. Count the number of islands (n 3 ) where less than half of the area of the island is found to exist within the frame. Based on the counted n 1 , n 2 and n 3 , "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)
Next, the total area of the islands in the frame is calculated, and the total area is set to "S [nm 2 ]".
Then, based on S [nm 2 ] and the number of islands (n) in the frame calculated by the formula (i), "a" represented by the following formula (ii) is added to one island in the frame. It is assumed to be the area around [nm 2].
a = S / n (ii)
　図４～７の電子顕微鏡写真のように、島部は不定形を有する。このため、本明細書において島部サイズを算出するにあたって、各島部を円形と仮定する。円形と仮定した島部の直径を「島部のサイズ」と定義する。
　本明細書では、２０箇所における島部１個あたりの面積ａ［ｎｍ２］から、島部のサイズｄ［ｎｍ］を式（ｉｉｉ）から算出する。そして、２０箇所の「ｄ」の平均値を、本明細書における島部のサイズＤ［ｎｍ］とする。
　　ｄ＝（４ａ／π）１／２　（ｉｉｉ） As shown in the electron micrographs of FIGS. 4 to 7, 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".
In the present specification, the size d [nm] of the island portion is calculated from the formula (iii) from the area a [nm 2 ] per island portion at 20 locations. Then, the average value of "d" at 20 points is defined as the island size D [nm] in the present specification.
d = (4a / π) 1/2 (iii)
　海部の面積比率は及び島部のサイズは、蒸着時間、蒸着時の基材温度、基材層の材質、後述するプライマー層の材質などで調整することができる。具体的に、蒸着時間を長くすると、島部のサイズを増加させることができる一方で、海部の面積割合を小さくすることができる。蒸着時の基材温度が高い方が、島部サイズが小さく、海部の面積割合が大きくなる傾向がある。 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.
＜接着層＞
　本発明の金属調加飾シートは、金属層を形成した基材層を被着体に接着するために、接着層を有していても良い。この場合、接着層は、金属層の基材と反対側の面に設けられる。
　接着層は、感熱性又は感圧性の樹脂から構成することが好ましい。言い換えると、接着層は、いわゆる感熱性接着層や感圧性接着層であることが好ましい。 <Adhesive layer>
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. In this case, 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. In other words, the adhesive layer is preferably a so-called heat-sensitive adhesive layer or pressure-sensitive adhesive layer.
　接着層に用いられる樹脂としては、汎用のアクリル系樹脂、ウレタン系樹脂、ポリエステル系樹脂、シリコーン系樹脂、塩化ビニル系樹脂若しくは酢酸ビニル系樹脂、又はこれらの２種以上の混合物若しくは共重合体を用いることが好ましい。粘着強度の観点から、アクリル系樹脂がさらに好ましい。
　感熱性接着層の場合、厚みは０．５～３μｍであることが好ましく、０.５～１.５μｍであることがより好ましい。また、感圧性接着剤の場合、厚みは２０～１００μｍであることが好ましく、３０～６０μｍであることがより好ましい。 As 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.
In the case of the heat-sensitive adhesive layer, the thickness is preferably 0.5 to 3 μm, more preferably 0.5 to 1.5 μm. Further, in the case of a pressure-sensitive adhesive, the thickness is preferably 20 to 100 μm, more preferably 30 to 60 μm.
　接着層のガラス転移温度Ｔｇは、０～３０℃であることが好ましく、５～２８℃であることがより好ましく、１０～２６℃であることがさらに好ましい。
　ガラス転移温度を０℃以上とすることにより、チッピングへの耐性（耐チッピング性）を良好にしやすきでき、また、耐熱性が良好となり、加飾成形体の表面の平滑性が低下することを抑制しやすくなる。また、ガラス転移温度を３０℃以下とすることにより、密着性の低下により耐チッピング性が低下することを抑制しやすくなる。さらに、ガラス転移温度が０～３０℃であると、加飾成形体の耐チッピング性と金属調加飾シートの高温での表面の平滑性とのバランスがとりやすくなる。 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.
By setting the glass transition temperature to 0 ° C. or higher, 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. Further, 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.
＜プライマー層＞
　プライマー層は、金属層と金属層に隣接する層（例えば、基材層）との密着性向上、金属層に隣接する層に含まれる成分（例えば塩素成分など）による金属層の劣化の抑制、金属層を蒸着で形成する場合の下地などを目的として、必要に応じて設けられる層である。
　プライマー層の材質は特に限定されないが、反射率に与える影響を小さくする観点から、基材層と屈折率差が小さい材質で形成されることが好ましい。プライマー層の材質としては、アクリル系樹脂、ポリウレタン系樹脂、アクリル－ウレタン共重合体樹脂、ポリエステル系樹脂などの樹脂が挙げられる。基材層がアクリル系樹脂を含む場合、金属層との密着性を向上させるために、プライマー層はアクリル系樹脂を含むことが好ましい。また、基材層、プライマー層及び金属層がこの順に直接接している場合、海島構造がプライマー層の影響を受ける観点から、プライマー層はアクリルポリオール及びイソシアネートを含む層であることが好ましい。
　プライマー層中には、紫外線吸収剤、光安定剤等の添加剤を含有してもよい。 <Primer layer>
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. Examples of the material of the primer layer include resins such as acrylic resin, polyurethane resin, acrylic-urethane copolymer resin, and polyester resin. When the base material layer contains an acrylic resin, the primer layer preferably contains an acrylic resin in order to improve the adhesion with the metal layer. When the base material layer, the primer layer and the metal layer are in direct contact with each other in this order, 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.
　プライマー層の厚みは、特に限定されないが、通常０．５～２．５μｍ程度、好ましくは１～２μｍ程度である。 The thickness of the primer layer is not particularly limited, but is usually about 0.5 to 2.5 μm, preferably about 1 to 2 μm.
＜剥離層＞
　金属調加飾シートは、接着層を保護する目的で、接着層の基材と反対側の表面に剥離層を有していても良い。剥離層は、加飾成形品を真空成形法により製造する際には、接着層から容易に剥離可能なものである。
　剥離層は、剥離性を向上させるために、離型剤を含むことが好ましい。例えば、剥離層は、離型剤及びバインダー樹脂を含む層とすることができる。離型剤としては、メラミン樹脂系離型剤、シリコーン系離型剤、フッ素樹脂系離型剤、セルロース樹脂系離型剤、尿素樹脂系離型剤、ポリオレフィン樹脂系離型剤、パラフィン系離型剤、アクリル樹脂系離型剤、及び、これらの複合型離型剤等の離型剤が好ましい。これらのなかで、シリコーン系離型剤が特に好ましい。バインダー樹脂としては、熱可塑性樹脂を用いるのがよく、例えば、アクリル系樹脂、ポリエステル系樹脂、セルロース誘導体樹脂、ポリビニルアセタール樹脂、ポリビニルブチラール樹脂、塩化ビニル－酢酸ビニル共重合体、および塩素化ポリオレフィン樹脂等が挙げられる。
　剥離層は、上記の離型剤およびバインダー樹脂に必要な添加剤を加えたものを適当な溶剤に溶解または分散させて調製したインキを、グラビアコート法、ロールコート法、コンマコート法、グラビア印刷法、スクリーン印刷法、およびグラビアリバースロールコーティング法等の公知の手段により塗布・乾燥させて形成することができる。 <Peeling layer>
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. For example, the release layer can be a layer containing a release agent and a binder resin. Examples of 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. As the binder resin, 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.
　あるいは、剥離層として、ポリエステルフィルム等の公知の樹脂フィルムの片面に、上記の離型剤を含む離型層を設けた剥離フィルムを用いてもよい。 Alternatively, as the release layer, 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.
＜バッカー層＞
　金属調加飾シートは、金属層の内層側（金属層を挟んで基材層と反対側）にバッカー層を有していても良い。バッカー層は、金属調加飾シートの強度を向上させたり、金属調加飾シートから形成した金属調加飾成形体の形状を保持したりする役割を有する。 <Backer layer>
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.
　バッカー層の厚みは特に制限されず、例えば、０．１～１０ｍｍの範囲で適宜選択すればよい。なお、金属層の内層側には、複数枚のバッカー層が積層されていてもよい。 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.
　バッカー層は透明であってもよいが、バッカー層の表面反射を抑制するために、白を除く無彩色（灰色、黒色）であることが好ましく、黒色であることがより好ましい。
　バッカー層は、無彩色とするための顔料を含むことが好ましい。バッカー層の顔料としては、黒色顔料の単独でもよいし、黒色顔料と他の顔料（白色顔料等）との混合であってもよい。 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).
　バッカー層のバインダー樹脂は、ポリエチレン、ポリプロピレン、ポリブテン、ポリメチルペンテン、エチレン－プロピレン共重合体、エチレン－プロピレン－ブテン共重合体、オレフィン系熱可塑性エラストマー等のポリオレフィン系樹脂、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン共重合体）樹脂、スチレン樹脂、塩化ビニル樹脂、アクリル系樹脂、ポリカーボネート樹脂等が挙げられる。これらのバインダー樹脂の中でも成形時のクラックを抑制する観点から、ＡＢＳ樹脂を含むことが好ましい。バッカー層の全バインダー樹脂に対するＡＢＳ樹脂の割合は、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。 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-). Examples thereof include styrene copolymer) resin, styrene resin, vinyl chloride resin, acrylic resin, and polypropylene resin. Among these 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, and further preferably 90% by mass or more.
　バッカー層には、必要に応じて、例えば、紫外線吸収剤等の光安定剤、可塑剤、充填剤、酸化防止剤、滑剤、帯電防止剤等の任意の添加剤を添加することができる。 If necessary, 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.
　バッカー層は、７５℃で３０分加熱した際の熱収縮率が１．０％以下であることが好ましく、０．５％以下であることがより好ましく、０．１％以下であることがさらに好ましい。バッカー層の熱収縮率を低くすることにより、バッカー層を起因とする金属光沢の低下を抑制しやすくできる。 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. By lowering the heat shrinkage rate of the backer layer, it is possible to easily suppress the decrease in metallic luster caused by the backer layer.
＜その他の層＞
　金属調加飾シートは、反射率に大きな影響を与えない範囲で、上記に例示した以外の層を有していてもよい。 <Other layers>
The metallic decorative sheet may have a layer other than those exemplified above as long as it does not significantly affect the reflectance.
［金属調加飾成形体］
　本発明の金属調加飾成形体は、本発明の金属調加飾シートに被着体を一体化させることにより成形されてなるものである。金属調加飾シートが接着層を有する場合、接着層は被着体側に位置する。 [Metallic decorative molded body]
The metallic decorative molded body of the present invention is formed by integrating an adherend with the metallic decorative sheet of the present invention. When the metallic decorative sheet has an adhesive layer, the adhesive layer is located on the adherend side.
＜被着体＞
　本発明の金属調加飾シートの金属調加飾成形体に用いられる被着体としては、特に限定されることなく、ガラス、セラミックス、樹脂等からなる成形体が挙げられる。
　なお、被着体は、あらかじめ成形体の形状に成形されたものを用いてもよいし、真空成形やインサート成形などによる加飾成形時に成形体の形状としてもよい。
　被着体の厚みは特に限定されないが、通常、１ｍｍ以上であり、１～１０ｍｍであることが好ましい。 <Subject>
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.
［金属調加飾成形体の製造方法］
　例えば、下記（ｙ１）～（ｙ２）の工程を有する真空成形により、金属調加飾成形体を製造することができる。
（ｙ１）金属調加飾シートの接着層側の面と、被着体とを貼着させた積層体を作製する。
（ｙ２）上記積層体の被着体側の面を型に向けて配置して真空成形する。 [Manufacturing method of metallic decorative molded article]
For example, 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.
　次に、本発明を実施例により、さらに詳細に説明するが、本発明は、この例によってなんら限定されるものではない。 Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.
［実施例１］
　図２に示す細線モデルについて、厳密結合波解析（RCWA,　Rigorous　Coupled　Wave　Analysis）法に基づいて、金属層の島部のサイズ及び海部の面積比率を変えた場合の波長５５０ｎｍにおける金属調加飾シートの反射率（％）のシミュレーションにより計算した。 [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.
　上記シミュレーションでは、海島構造を一次元に単純化して行った。また、上記シミュレーションでは、金属調加飾シートの層構成は、基材層（ＰＭＭＡ）／金属層（インジウム蒸着膜）とした。基材層側に発光面が配置され、基材層に光が垂直入射（入射角５°）すると設定した。 In the above simulation, the sea island structure was simplified to one dimension. Further, in the above simulation, 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 °).
　金属層部分の光入射方向に垂直な方向の長さ（図２中、符号Ｌｍ）と規定した。図２の細線モデルにおいて、海部の比率ｘ（％）は、基材層部分の光入射方向に垂直な方向の長さ（図２中、符号Ｌｓ）とした場合に、ｘ＝（Ｌｓ－Ｌｍ）／Ｌｓ×１００と規定した。細線モデルにおける海部の比率は、金属調加飾シート（金属層）を平面視したときの海部の面積比率Ｘ（％）に相当すると見做した。 The length of the metal layer portion in the direction perpendicular to the light incident direction (reference numeral Lm in FIG. 2) was defined. In the thin line model of FIG. 2, the ratio x (%) of the sea portion is x = (Ls-Lm) when the length of the base material layer portion is perpendicular to the light incident direction (reference numeral Ls in FIG. 2). ) / Ls × 100. 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.
　計算に用いたパラメータを下記に示す。
　　基材層の光学定数：ｎ＝１．４９、ｋ＝０
　　基材層の厚さ：１．０μｍ
　　金属層の光学定数：ｎ＝１．０５５６、ｋ＝４．９５２４
　　金属層の厚さ：５０ｎｍ
　　島部のサイズ：５０ｎｍ～４００ｎｍ
　　海部の面積比率：０～３１％ The parameters used in the calculation are shown below.
Optical constants of substrate layer: n = 1.49, k = 0
Base material layer thickness: 1.0 μm
Optical constants of metal layer: n = 1.0556, k = 4.9524
Metal layer thickness: 50 nm
Island size: 50nm-400nm
Area ratio of sea area: 0-31%
　図３は、上記シミュレーションで得た海部の面積比率と反射率との関係を示すグラフである。横軸は海部の面積比率、縦軸は反射率である。図３中に、条件式（１）～（３）で表される領域を太枠及び網掛けで示した。
　図３によると、基材層上に海島構造を有する金属層を形成した金属調加飾シートでは、海部の面積比率が大きくなるに従い、反射率が低下する傾向がある。金属層（インジウム蒸着膜）の島サイズが７５ｎｍ以上である場合はいずれも、所定の海部の面積比率とすることにより、反射率６０％以上となった。すなわち、図３から、金属層（インジウム蒸着膜）の島サイズが７５ｎｍ～４００ｎｍである場合、海部の面積比率を適切に調整することにより、６０％以上の高い反射率を有する金属調加飾シートが得られることが確認できた。 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, and the vertical axis is the reflectance. In FIG. 3, the areas represented by the conditional expressions (1) to (3) are shown by a thick frame and shading.
According to FIG. 3, in a metal-like decorative sheet in which a metal layer having a sea-island structure is formed on a base material layer, the reflectance tends to decrease as the area ratio of the sea portion increases. When the island size of the metal layer (indium-deposited film) was 75 nm or more, the reflectance was 60% or more by setting the area ratio of the predetermined sea area. That is, from FIG. 3, when the island size of the metal layer (indium-deposited film) is 75 nm to 400 nm, a metal-like decorative sheet having a high reflectance of 60% or more is obtained by appropriately adjusting the area ratio of the sea part. Was confirmed to be obtained.
［実施例２］
　ＰＭＭＡ基材（エスカーボシート株式会社製、商品名「テクノロイフィルム　Ｓ００１Ｇ」、幅１ｍ、厚さ１２５μｍ）上に、表１に示す蒸着条件でインジウム蒸着膜を形成し、実施例２の金属調加飾シートを得た。蒸着は、抵抗加熱蒸着方式の蒸着装置（（株）アルバック製、ＥＸ－２００）を用いて行った。蒸着開始時のチャンバ内圧力は、１．０×１０－３Ｐａであった。 [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 μm) 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.
［実施例３，５］
　表１に示す蒸着条件にしたこと以外は実施例２と同様の条件でインジウム蒸着膜を形成し、実施例３及び実施例５の金属調加飾シートを得た。 [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.
［実施例４］
　実施例２と同じＰＰＭＡ基材の一方の面に、コロナ処理を施した。コロナ処理は、操出・巻取装置付コロナ処理装置を用い、出力１００Ｗ、基材－電極間距離１．５ｍｍ、基板搬送速度２０ｍ／分の条件で行った。
　次いで、上記基材のコロナ処理が施された面に、表１に示す条件としたこと以外は実施例２と同様の条件でインジウム蒸着膜を形成し、実施例４の金属調加飾シートを得た。 [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.
Next, 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.
［実施例６］
　下記処方のプライマー層形成用塗布液１を作製した。
　実施例２と同じＰＰＭＡ基材上に、プライマー層形成用塗布液１を塗布し、乾燥させ、厚み２μｍのプライマー層を形成した。形成したプライマー層上に、表１に示す条件としたこと以外は実施例２と同様の条件でインジウム蒸着膜を形成し、実施例６の金属調加飾シートを得た。
＜プライマー層形成用塗布液１＞
　・ポリエステル系樹脂（昭和インク工業社製、商品名ＳＩＶＭ用ＨＳ）　　１００質量部
　・イソシアネート系化合物（昭和インク工業社製、商品名ＯＰ　Ｎｏ．８１）　　５．０質量部
　・溶剤（株式会社昭和インク工業所製、商品名：化Ｘ－ＮＴ溶剤）　　適量 [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 μm. 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.
<Coating liquid for forming primer layer 1>
-Polyester resin (manufactured by Showa Ink Kogyo Co., Ltd., trade name HS for SIVM) 100 parts by mass-Isocyanate compound (manufactured by Showa Ink Kogyo Co., Ltd., trade name OP No. 81) 5.0 parts by mass-Solvent (Showa Ink Co., Ltd.) Manufactured by Kogyosho, trade name: Chemical X-NT solvent) Appropriate amount
［比較例１］
　表１に示す蒸着条件にしたこと以外は実施例２と同様の条件でインジウム蒸着膜を形成し、比較例１の金属調加飾シートを得た。 [Comparative 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.
１．電子顕微鏡観察
　実施例２～６及び比較例１の金属調加飾シートからサンプルを切り出し、インジウム蒸着膜表面を電子顕微鏡で観察し画像を取得した。観察条件を以下に記載する。
　　装置：走査型電子顕微鏡（日立ハイテクノロジーズ社製、ＳＵ８０４０）
　　観察条件
　　　加速電圧：５ｋＶ
　　　エミッションカレント：１０μＡ
　　　ピクセルサイズ：９．５～１０．０ｎｍ
　　　ワーキングディスタンス：１５ｍｍ
　　　観察倍率：１０，０００倍
　　　階調：８ビット
　実施例２～５の金属層の電子顕微鏡画像を、それぞれ図４～７に示す。 1. 1. Observation with an electron microscope A sample was cut out from the metal-like decorative sheets of Examples 2 to 6 and Comparative Example 1, and the surface of the indium-deposited film was observed with an electron microscope to obtain an image. The observation conditions are described below.
Equipment: Scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, SU8040)
Observation conditions Acceleration voltage: 5 kV
Emission current: 10 μA
Pixel size: 9.5 to 10.0 nm
Working distance: 15mm
Observation magnification: 10,000 times Gradation: 8 bits The electron microscope images of the metal layers of Examples 2 to 5 are shown in FIGS. 4 to 7, respectively.
２．海部の面積比率の算出
　上記１．に記載した条件で得た実施例２～６及び比較例１の金属調加飾シートの電子顕微鏡画像から、８０万画素分を切り出した。切り出した画像をＯｔｓｕ’ｓ　ｍｅｔｈｏｄに基づいて２値化処理し、海部の面積比率Ｘ（％）を算出した。なお、当該作業を画像の２０箇所で行い、２０箇所の平均値を、実施例２～６及び比較例１の金属層の海部の面積比率Ｘ（％）とした。結果を表１に示す。 2. Calculation of the area ratio of the sea area Above 1. 800,000 pixels were cut out from the electron microscope images of the metal-like decorative sheets of Examples 2 to 6 and Comparative Example 1 obtained under the conditions described in 1. The cut-out image was binarized based on Otsu's method, and the area ratio X (%) of the sea area was calculated. The work was performed at 20 locations in the image, and the average value of the 20 locations was defined as the area ratio X (%) of the sea portion of the metal layer of Examples 2 to 6 and Comparative Example 1. The results are shown in Table 1.
３．島部サイズの計測
　上記２．で得た２値化画像から、上述した方法に従い、島部のサイズＤ［ｎｍ］を算出した。結果を表１に示す。 3. 3. Measurement of island size 2. The size D [nm] of the island portion was calculated from the binarized image obtained in the above method according to the above method. The results are shown in Table 1.
４．反射率計測
　実施例２～６及び比較例１の金属調加飾シートからサンプルを切り出し、分光反射率測定器（分光光度計）（日本分光株式会社製、商品名：Ｖ－６７０）を用いて、基材層（ＰＭＭＡ）側から測定光を入射角５度でサンプルに入射させ、サンプルの波長５５０ｎｍにおける反射率を測定した。
　各々１０箇所から切り出したサンプルについて反射率（波長５５０ｎｍ）を測定し、その平均値を実施例２～６及び比較例１の金属調加飾シートの反射率Ｙ（％）とした。結果を表１に示す。 4. 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.
５．成形時の白化の観察
　実施例２～６及び比較例１の金属調加飾シートを用い、射出成形により金属調加飾成形体を得た。射出樹脂としてメタクリル樹脂を用いた。成形体の形状は、１０ｃｍ×１５ｃｍの平板とした。射出時の樹脂温度は２４０℃とした。
　得られた金属調加飾成形体の表面を目視で観察し、下記の基準で金属調加飾シートの白化を評価した。結果を表１に示す。
　Ａ：白化が全く見られなかったもの
　Ｂ：白化がわずかに見られたもの
　Ｃ：全体的に白化が確認できたもの 5. Observation of whitening during molding Using the metal-like decorative sheets of Examples 2 to 6 and Comparative Example 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
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　図３に、実施例２～６及び比較例１のプロットを表示する。いずれの実施例も、条件式（１）～（３）で表される領域内に入ることが分かる。
　実施例２（島サイズ：２４６ｎｍ）のプロットは、シミュレーションで得た島サイズ２５０ｎｍの場合のグラフに近接している。また、例えば、実施例４（島サイズ：１２２ｎｍ）は、シミュレーションで得た島サイズ１００ｎｍの場合のグラフと島サイズ１５０ｎｍの場合のグラフとの間に位置する。このように、一次元の細線モデルでシミュレーションした結果とサンプルとの間に強い相関があり、シミュレーション結果とほぼ一致した。 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 (island size: 246 nm) is close to the graph for the simulated island size of 250 nm. Further, for example, Example 4 (island size: 122 nm) 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.
　表１に示すように、実施例２～６の金属調加飾シートを用いることにより、成形時の白化が抑制されることが確認できた。
  As shown in Table 1, it was confirmed that whitening during molding was suppressed by using the metal-like decorative sheets of Examples 2 to 6.

Claims (4)

  1. 　基材層上に金属層を有する金属調加飾シートであって、
    　前記金属層は金属を含む複数の島部と、前記島部の間に位置する海部とを有し、
    　前記金属層を平面視したときの前記海部の面積比率をＸ（％）、波長５５０ｎｍにおける前記金属調加飾シートの反射率をＹ（％）としたときに、下記条件式（１）～（３）を満たす金属調加飾シート。
    　Ｘ≧１０　…（１）
    　Ｙ≧６０　…（２）
    　Ｙ≦－０．４１８２Ｘ＋７３.３８２　…（３）     A metallic decorative sheet having a metal layer on a base material layer.
    The metal layer has a plurality of islands containing metal and a sea portion located between the islands.
    When the area ratio of the sea portion when the metal layer is viewed in a plan view is X (%) and the reflectance of the metal-like decorative sheet at a wavelength of 550 nm is Y (%), the following conditional equations (1) to (1) to ( A metallic decorative sheet that satisfies 3).
    X ≧ 10… (1)
    Y ≧ 60… (2)
    Y ≦ −0.4182X + 73.382… (3)
  2. 　前記島部の各々を円形と仮定し、前記島部１個あたりの面積から算出した直径の平均値を、前記島部のサイズと定義した場合に、前記サイズが７５ｎｍ以上４００ｎｍ以下である、請求項１に記載の金属調加飾シート。 Claim that the size is 75 nm or more and 400 nm or less when the average value of the diameters calculated from the area per island is defined as the size of the islands, assuming that each of the islands is circular. Item 2. The metallic decorative sheet according to item 1.
  3. 　前記金属層は、インジウム又はスズを含む、請求項１または請求項２に記載の金属調加飾シート。 The metal-like decorative sheet according to claim 1 or 2, wherein the metal layer contains indium or tin.
  4. 　請求項１～３の何れか１項に記載の金属調加飾シートと、被着体とを有する金属調加飾成形体。

          A metal-like decorative molded body having the metal-like decorative sheet according to any one of claims 1 to 3 and an adherend.
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009110090A1 (en) * 2008-03-07 2009-09-11 三菱電機株式会社 Decorative part
JP2010251899A (en) * 2009-04-13 2010-11-04 Sankei Giken Kogyo Co Ltd Metal composite material of electromagnetic wave transparency and method for manufacturing the same
JP2011027434A (en) * 2009-07-21 2011-02-10 Toyota Motor Corp Method of forming decorative coating on surface of resin base material and exterior decoration member having the decorative coating
JP2018069462A (en) * 2016-10-24 2018-05-10 日東電工株式会社 Electromagnetic wave transmissive metallic sheen member, article using the same and thin metallic film
JP2018154878A (en) * 2017-03-17 2018-10-04 株式会社Ｊｃｕ Metal film for electromagnetic wave transmission, formation method of metal film for electromagnetic wave transmission, and on-vehicle radar device
WO2019208499A1 (en) * 2018-04-23 2019-10-31 日東電工株式会社 Electromagnetically permeable article with metallic gloss
WO2019208493A1 (en) * 2018-04-23 2019-10-31 日東電工株式会社 Electromagnetic-wave-permeable metallic-luster article, and decorative member
WO2019230955A1 (en) * 2018-06-01 2019-12-05 大日本印刷株式会社 Metallic decorative member, and metallic decorative molded body using same
JP2019209550A (en) * 2018-06-01 2019-12-12 大日本印刷株式会社 Member for metallic decoration and metallic decorative molded body using the same
WO2020153137A1 (en) * 2019-01-25 2020-07-30 ソニー株式会社 Structure, decorative film, method for manufacturing structure, and method for manufacturing decorative film
JP2021024251A (en) * 2019-08-08 2021-02-22 日東電工株式会社 Electromagnetic wave transmissible laminate

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009110090A1 (en) * 2008-03-07 2009-09-11 三菱電機株式会社 Decorative part
JP2010251899A (en) * 2009-04-13 2010-11-04 Sankei Giken Kogyo Co Ltd Metal composite material of electromagnetic wave transparency and method for manufacturing the same
JP2011027434A (en) * 2009-07-21 2011-02-10 Toyota Motor Corp Method of forming decorative coating on surface of resin base material and exterior decoration member having the decorative coating
JP2018069462A (en) * 2016-10-24 2018-05-10 日東電工株式会社 Electromagnetic wave transmissive metallic sheen member, article using the same and thin metallic film
JP2018154878A (en) * 2017-03-17 2018-10-04 株式会社Ｊｃｕ Metal film for electromagnetic wave transmission, formation method of metal film for electromagnetic wave transmission, and on-vehicle radar device
WO2019208499A1 (en) * 2018-04-23 2019-10-31 日東電工株式会社 Electromagnetically permeable article with metallic gloss
WO2019208493A1 (en) * 2018-04-23 2019-10-31 日東電工株式会社 Electromagnetic-wave-permeable metallic-luster article, and decorative member
WO2019230955A1 (en) * 2018-06-01 2019-12-05 大日本印刷株式会社 Metallic decorative member, and metallic decorative molded body using same
JP2019209550A (en) * 2018-06-01 2019-12-12 大日本印刷株式会社 Member for metallic decoration and metallic decorative molded body using the same
WO2020153137A1 (en) * 2019-01-25 2020-07-30 ソニー株式会社 Structure, decorative film, method for manufacturing structure, and method for manufacturing decorative film
JP2021024251A (en) * 2019-08-08 2021-02-22 日東電工株式会社 Electromagnetic wave transmissible laminate

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