WO2023037789A1 - Metallic-tone decorative film and metallic-tone product - Google Patents

Metallic-tone decorative film and metallic-tone product Download PDF

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Publication number
WO2023037789A1
WO2023037789A1 PCT/JP2022/029154 JP2022029154W WO2023037789A1 WO 2023037789 A1 WO2023037789 A1 WO 2023037789A1 JP 2022029154 W JP2022029154 W JP 2022029154W WO 2023037789 A1 WO2023037789 A1 WO 2023037789A1
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Prior art keywords
decorative film
layer
metallic
indium
metal
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PCT/JP2022/029154
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French (fr)
Japanese (ja)
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義広 赤座
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尾池工業株式会社
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Publication of WO2023037789A1 publication Critical patent/WO2023037789A1/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

Definitions

  • the present invention relates to a metal-like decorative film and a metal-like product. More specifically, the present invention provides a metallic decorative film that exhibits excellent metallic luster with suppressed clouding, and provides sufficient shade/highlight properties when, for example, it is out-molded into a three-dimensional structure. , relating to metal preparations.
  • Patent Document 1 Conventionally, decorative sheets with three-dimensional formability have been developed (for example, Patent Document 1).
  • the decorative sheet described in Patent Document 1 discloses that pigments, dyes, and the like, for example, can be used as coloring agents added in the primer layer.
  • the decorative sheet described in Patent Document 1 when indium is used as the metal vapor deposition layer and a general pigment is used as the colorant, the pigment enters between the islands of the sea-island structure of the indium vapor deposition layer. Hateful. Moreover, unless black is selected as the coloring agent for the primer layer, the decorative sheet cannot absorb the light scattered around the indium islands, and the reflected light has a scattering property. As a result, the decorative sheet has a dull metallic luster. When such a decorative sheet is out-molded into a three-dimensional structure, it is difficult to obtain shade/highlight properties.
  • the present invention has been made in view of such conventional inventions, and exhibits excellent metallic luster with suppressed clouding, for example, when it is out-molded into a three-dimensional structure, it has sufficient shade and high.
  • An object of the present invention is to provide a metal-like decorative film and a metal-like product that can obtain light characteristics.
  • the present inventors have found that by using indium as the metal vapor deposition layer and blending black dye as the primer layer, a resin to which the black dye is added between the islands of the sea-island structure of the indium vapor deposition layer. As a result, the inventors have found that the scattering effect due to the scattered indium islands can be suppressed, and excellent metallic luster with suppressed cloudiness can be exhibited, and the present invention has been completed.
  • a metallic decorative film according to one embodiment of the present invention for solving the above problems has a substrate, an anchor layer, an indium deposition layer, and a primer layer in this order, and the primer layer contains a black dye.
  • the ratio (GS60°/L*45) between the specular glossiness (GS60°) at an incident angle of 60° and the L* value (L*45) at an incident angle and a light receiving angle of 45° is 75 or more It is a metallic decorative film.
  • a metal preparation according to one embodiment of the present invention for solving the above problems is a metal preparation using the metal-like decorative film.
  • FIG. 1 is a schematic diagram of a sample in which neither black dye nor black pigment is added to the primer layer.
  • FIG. 2 is a schematic diagram of a sample in which a black dye is added to the primer layer.
  • FIG. 3 is a schematic diagram of a sample in which a black pigment is added to the primer layer.
  • FIG. 4 is a schematic diagram for explaining the definition of the angle of the L* value.
  • FIG. 5 is an appearance photograph of a metal-like product using the metal-like decorative films of Comparative Example 5 and Example 8.
  • FIG. FIG. 6 is an appearance photograph of a metal tone product using the metal tone decorative films of Comparative Example 5 and Example 8.
  • FIG. 5 is an appearance photograph of a metal-like product using the metal-like decorative films of Comparative Example 5 and Example 8.
  • a metallic decorative film of one embodiment of the present invention has a base material, an anchor layer, an indium deposition layer, and a primer layer in this order.
  • the primer layer contains a black dye.
  • the ratio (GS60°/L*45) between the specular glossiness (GS60°) at an incident angle of 60° and the L* value (L*45) at an incident angle and a light receiving angle of 45° is 75 or more.
  • the metallic decorative film of the present embodiment can exhibit excellent metallic luster with suppressed fogging. Such a metallic decorative film can provide sufficient shade/highlight properties when it is out-molded into a three-dimensional structure, for example.
  • the shade/highlight characteristic refers to a characteristic in which a specular reflection component is strong and a diffuse reflection component is weak. As a result, the specular reflection portion becomes brighter and the other shadow portion becomes darker, thereby realizing an excellent shadow decoration effect.
  • the base material is not particularly limited.
  • the substrate may be poly(meth)acrylic acid ester such as polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate, polyethylene-2,6-naphthalate, polyvinyl fluoride (PVF), polyfluoride.
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • PC polyethylene terephthalate
  • PVF polyvinyl fluoride
  • PVF polyfluoride
  • PVDF Vinylidene chloride
  • PTFE polytetrafluoroethylene
  • PCTFE polychlorotrifluoroethylene
  • ETFE ethylene-tetrafluoroethylene copolymer
  • ECTFE ethylene-chlorotrifluoroethylene copolymer
  • PFA ethylene-perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • the thickness of the base material is not particularly limited.
  • the thickness of the substrate is preferably 1.0 to 300 ⁇ m.
  • the metallic decorative film has excellent scratch resistance and abrasion resistance.
  • the base material may be one that has undergone desired surface processing.
  • Surface treatment is not particularly limited. Examples of surface finishing include matte finishing, satin finishing, embossing, and hairline finishing.
  • the surface of the base material (the surface opposite to the surface on which the anchor layer is formed) may be subjected to surface processing such as various coatings (fluorine processing, hard coating processing, etc.) and transfer. Thereby, various design properties and functionality can be imparted to the surface of the substrate.
  • anchor layer The anchor layer is provided to improve the adhesion between the substrate and the indium deposition layer.
  • the anchor layer is not particularly limited.
  • the anchor layer may be made of any raw material that has good adhesion to the substrate and good receptivity for indium constituting the indium vapor deposition layer. , polyester resins, styrene-maleic acid resins, chlorinated PP resins, and the like.
  • the anchor layer may be formed by adding an isocyanate compound as a curing agent to a polyol resin as a main agent.
  • the thickness of the anchor layer is not particularly limited.
  • the thickness of the anchor layer is preferably 0.1 to 3 ⁇ m.
  • the metallic decorative film has excellent adhesion between the base material and the indium deposited layer.
  • the anchor layer may be given designability by adding a coloring agent or a metal pigment. For example, by blending a yellow pigment as a coloring agent, the metallic decorative film can express a golden appearance. The type and content of the coloring agent can be appropriately adjusted according to the desired metallic appearance. Further, the anchor layer may be provided with functionality such as an antistatic effect by blending an antistatic agent or the like.
  • the anchor layer may contain dyes or pigments.
  • the dye or pigment is preferably a black, gray or chromatic dye or pigment.
  • the metallic decorative film can achieve a color metallic of any color.
  • the dye is not particularly limited.
  • dyes include azo (monoazo, disazo, etc.) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketoneimine dyes, fluorone dyes, nitro dyes, xanthene dyes, acenaphthene dyes, quinophthalone dyes, aminoketone dyes, methine Dyes, perylene dyes, coumarin dyes, perinone dyes, triphenyl dyes, triallylmethane dyes, phthalocyanine dyes, incrophenol dyes, azine dyes, pyrazolone dyes and mixtures thereof.
  • azo monoazo, disazo, etc.
  • azo-methine dyes anthraquinone dyes
  • quinoline dyes ketoneimine dyes
  • fluorone dyes nitro dyes
  • xanthene dyes acenaphthene dyes
  • the pigment is not particularly limited.
  • pigments include bright pigments such as interference mica pigments, white mica pigments, and graphite pigments; inorganic coloring pigments such as yellow lead, yellow iron oxide, red iron oxide, carbon black, manganese ferrite, and titanium dioxide; , silica, zinc oxide, calcium carbonate, precipitated barium sulfate, and other extender pigments;
  • the content of the dye or pigment is not particularly limited.
  • the dye or pigment content in the anchor layer is preferably 2.0% by mass or more, more preferably 4.0% by mass or more.
  • the content of the dye or pigment in the anchor layer is preferably 15.0% by mass or less, more preferably 10.0% by mass or less.
  • the metallic decorative film can easily achieve a color metallic color of any desired color.
  • the indium vapor deposition layer WHEREIN Indium may be contained as an oxide and a nitride.
  • the metal-deposited layer is an indium-deposited layer, appearance defects such as whitening are less likely to occur during molding, and molding processability is excellent. As a result, the metallic decorative film can be easily processed into various three-dimensional shapes.
  • the indium deposition layer may contain various non-metals, metals, metal oxides and metal nitrides.
  • Non-metals, metals and the like are not particularly limited.
  • non-metals are amorphous carbon (DLC) and their composites
  • metals are metals such as gold, silver, platinum, tin, chromium, silicon, titanium, zinc, aluminum and magnesium, oxides thereof, It is the nitride.
  • the content of indium in the indium deposition layer is not particularly limited.
  • the content of indium in the indium deposition layer is preferably 95% by mass or more, more preferably 98% by mass or more.
  • the indium content may be 100% by mass.
  • the indium deposited layer may contain impurities other than indium which is unavoidably contained.
  • the indium deposition layer of this embodiment has a sea-island structure (so-called discontinuous structure).
  • the indium vapor deposition layer for example, compared to other general metal vapor deposition layers such as an aluminum vapor deposition layer, can obtain an excellent metallic luster even if it is three-dimensionally stretched by a molding process or the like.
  • the sea-island structure the island portion is a region where indium exists, and the sea portion is a region where indium does not exist.
  • a resin containing a black dye in the primer layer which will be described later, enters between the islands of the sea-island structure of the indium vapor-deposited layer.
  • the metallic decorative film can suppress the scattering effect caused by scattered indium islands, and can exhibit excellent metallic luster with suppressed haze.
  • the thickness of the indium deposition layer is not particularly limited.
  • the thickness of the indium deposition layer is preferably 10 nm or more, more preferably 15 nm or more.
  • the thickness of the indium deposition layer is preferably 80 nm or less, more preferably 60 nm or less.
  • the thickness of the indium vapor deposition layer is the same as the cross-sectional area of the indium vapor deposition layer having an island structure (the area of the substantially fan-shaped cross section), assuming a rectangle having the same width and area. You can think of it as It should be noted that the thickness of the indium deposited layer in this embodiment is a value determined by quantitative analysis using X-ray fluorescence spectroscopy (XRF).
  • XRF X-ray fluorescence spectroscopy
  • the primer layer imparts excellent three-dimensional formability to the metallic decorative film of the present embodiment, and is intended to provide a metallic decorative film that can sufficiently follow the shape of a metallic preparation having a complicated surface shape. be provided.
  • the primer layer preferably contains a cured resin with a glass transition point of -20°C to 100°C in order to further enhance the three-dimensional formability of the metallic decorative film.
  • the glass transition point (Tg) can be measured by differential scanning calorimetry (DSC) based on JIS K 7121-1987.
  • the content of the resin having a glass transition point (Tg) of -20°C to 100°C is preferably 50% by mass or more, more preferably 70% by mass or more, in the resin constituting the primer layer.
  • the resin forming the primer layer may be only a resin having a glass transition point (Tg) of -20°C to 100°C.
  • the resin with a glass transition point (Tg) of -20°C to 100°C is not particularly limited.
  • resins having a glass transition point (Tg) of -20°C to 100°C include thermosetting resins, thermoplastic resins, polyester resins, polyurethane resins, polyacrylic resins, and polyolefin resins. etc., and more preferably a polyester-based resin.
  • Polyester-based resins include polyester polyols.
  • Polyurethane-based resins include polyester urethane polyols, acrylic urethane polyols, and the like.
  • the polyacrylic resin is acrylic polyol or the like.
  • Polyolefin resins include polyethylene polyol, polypropylene polyol, polybutadiene polyol, polyisoprene polyol, and the like.
  • the primer layer is preferably formed of a cured product of the above resin having a glass transition point (Tg) of -20°C to 100°C and a curing agent, and a glass transition point (Tg) of -20°C to 100°C. More preferably, it is made of a reaction-curing urethane resin obtained from a polyol resin and a curing agent such as an isocyanate compound.
  • the polyol resin having a glass transition point (Tg) of ⁇ 20° C. to 100° C. includes the above-mentioned polyols, which are polyester-based resins, polyurethane-based resins, polyacrylic-based resins, or polyolefin-based resins.
  • the isocyanate compound is not particularly limited.
  • isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4′-diphenylmethane diisocyanate, 2 ,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, polymethylene polyphenylene polyisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4 ,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p
  • the content of the curing agent is not particularly limited.
  • the content of the curing agent is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, with respect to 100 parts by mass of the resin forming the primer layer.
  • the primer layer of this embodiment contains a black dye.
  • Black dyes are not particularly limited. Examples of black dyes include azo (monoazo, disazo, etc.) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketoneimine dyes, fluorone dyes, nitro dyes, xanthene dyes, acenaphthene dyes, quinophthalone dyes, aminoketone dyes, methine dyes, perylene dyes, coumarin dyes, perinone dyes, triphenyl dyes, triallylmethane dyes, phthalocyanine dyes, incrophenol dyes, azine dyes and mixtures thereof.
  • azo monoazo, disazo, etc.
  • azo-methine dyes anthraquinone dyes
  • quinoline dyes ketoneimine dyes
  • fluorone dyes nitro dyes
  • xanthene dyes acen
  • the content of the black dye is not particularly limited.
  • the black dye content in the primer layer is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more.
  • the content of the black dye is preferably 75% by mass or less in the primer layer.
  • the black dye sufficiently penetrates between the islands of the sea-island structure of the indium vapor-deposited layer in the metal-tone decorative film, and the metal-tone decorative film becomes more cloudy. It can exhibit excellent metallic luster under control. Also, the metallic decorative film has excellent formability.
  • FIG. 1 is a schematic diagram of a sample in which neither black dye nor black pigment is added to the primer layer.
  • FIG. 2 is a schematic diagram of a sample in which a black dye is added to the primer layer.
  • FIG. 3 is a schematic diagram of a sample in which a black pigment is added to the primer layer. 1 to 3, only the anchor layer 1, the indium deposited layer 2, and the primer layer 3 are shown for clarity of explanation.
  • the indium deposition layer 2 is provided on the anchor layer 1 by, for example, a vacuum deposition method. Therefore, it is considered that the projecting portion of the indium island structure (island portion 2a) is formed on the primer layer 3 side. Then, the incident light (incident light L1) incident from the substrate side is specularly reflected (specularly reflected light L2) at the bottom portion of the indium island portion 2a (near the interface between the anchor layer 1 and the indium deposition layer 2).
  • the protruding portion of the indium island portion 2a (portion with a substantially fan-shaped cross section) is also considered to be diffusely reflected (diffuse reflected light L3).
  • the protruding portion of the adjacent indium island portions 2a Part of this diffusely reflected light is also thought to be diffusely reflected by the protruding portions of the adjacent indium island portions 2a, causing so-called multiple diffuse reflection. This is presumed to be the deterioration of the shade/highlight characteristics, that is, the shade (shadow) portion is not sufficiently darkened and is visually recognized as cloudy. In the final product, the product is observed from the substrate side.
  • the black dye-added resin R sufficiently wraps around the projecting portion of the indium island portion 2a.
  • diffuse reflection is less likely to occur at the projecting portion of the indium island portion 2a (because the diffusely reflected light is absorbed by the resin to which the black dye is added), and the shade (shadow) portion becomes sufficiently dark. ⁇ Highlight characteristics are presumed to be excellent.
  • the particle size of the general pigment is 40 nm to 50 nm at the smallest. Therefore, the black pigment P1 cannot sufficiently enter between the indium island structures (island portions 2a). As a result, diffuse reflection occurs, and the shade/highlight characteristics are degraded, that is, the shade (shadow) portion is not sufficiently darkened and is visually recognized as cloudiness.
  • the primer layer may further contain a coloring agent for the purpose of adjusting the color of the metallic decorative film and improving the design.
  • coloring agents include, for example, various pigments, dyes, etc., and inorganic pigments such as titanium white (titanium oxide), antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, cobalt blue, quinacridone red. , isoindolinone yellow, phthalocyanine blue, and other organic pigments or dyes; metal pigments consisting of scale-like foils such as aluminum and brass; titanium dioxide-coated mica; ) pigments and the like.
  • the thickness of the primer layer is not particularly limited.
  • the thickness of the primer layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more.
  • the thickness of the primer layer is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less.
  • the adhesive layer is provided for bonding the metallic decorative film to the adherend. Also, the adhesion layer is a layer that can be provided on the surface of the primer layer opposite to the surface on which the indium deposition layer is formed.
  • the adhesive layer is optional. That is, the adhesive layer may be provided on the primer layer described above, or may be omitted when the primer layer also functions as the adhesive layer. Since the metallic decorative film of the present embodiment is provided with an adhesive layer, it can be used by being attached to various substrates, and a metallic luster can be imparted by a simpler and safer method than painting. can. On the other hand, when the adhesive layer is omitted because the primer layer also functions as the adhesive layer, the cost of the metallic decorative film can be reduced.
  • the adhesive layer is not particularly limited.
  • the adhesive layer consists of various adhesives, adhesives, pressure sensitive adhesives (PSA: Pressure Sensitive Adhesive), and the like.
  • the adhesive is not particularly limited.
  • adhesives include acrylic resins, urethane resins, urethane-modified polyester resins, polyester resins, epoxy resins, ethylene-vinyl acetate copolymer (EVA), vinyl resins (vinyl chloride, vinegar vinyl chloride-vinyl acetate copolymer resin), styrene-ethylene-butylene copolymer resin system, polyvinyl alcohol resin system, polyacrylamide resin system, polyacrylamide resin system, isobutylene rubber, isoprene rubber, natural rubber, SBR, NBR, It is made of resin such as silicone rubber. These resins may be appropriately dissolved in a solvent and used, or may be used without a solvent.
  • the thickness of the adhesive layer is not particularly limited.
  • the thickness of the adhesive layer is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more.
  • the thickness of the adhesive layer is preferably 60 ⁇ m or less, more preferably 55 ⁇ m or less.
  • the adhesive layer may be imparted with a design property by being imparted with a metallic pigment in addition to the above-mentioned coloring agent. Further, the adhesive layer may be provided with functionality such as an antistatic effect by blending an antistatic agent or the like. Thereby, the adhesive layer can be improved in bonding aptitude.
  • the metallic decorative film of the present embodiment has a specular glossiness (GS60°) at an incident angle of 60° and an L* value ( L*45) (GS60°/L*45) should be 75 or more, preferably 82 or more, and more preferably 85 or more.
  • L*45 L*45
  • a metallic decorative film exhibiting such a ratio (GS60°/L*45) can exhibit excellent metallic luster with more suppressed fogging.
  • the specular glossiness (GS60°) at an incident angle of 60° was measured using an appearance analyzer (Rhopoint IQ-S, manufactured by Rhopoint) with respect to the metallic decorative film surface at an incident angle of 60°.
  • the L* value (L*45) at an incident angle and a light receiving angle of 45° was measured using a multi-angle spectrophotometer (MA-T6, manufactured by X-Rite) with respect to the surface of the metallic decorative film.
  • the light from the light source is incident at an incident angle of 45°
  • the light receiving angle of the light receiver is set at 45°
  • the reflected light from the surface of the metal-like decorative film is received by the light receiver to calculate the L* value.
  • the light-receiving angle of 45° means that the surface of the metallic decorative film has an inclination angle of 45° from the normal direction.
  • the incident angle of 45° means a direction inclined by 45° toward the normal to the surface of the metal-like decorative film with respect to the direction of the light-receiving angle of 45°, that is, the direction of the normal to the surface of the metal-like decorative film. means.
  • the method for adjusting the specular glossiness is not particularly limited.
  • the specular glossiness (GS60°) can be adjusted by changing the thickness of the indium deposition layer in the indium deposition layer.
  • the thickness of the indium deposition layer is thin, the ratio of the bottom portion of the island structure of indium in the vicinity of the interface between the anchor layer and the indium deposition layer decreases, the specular reflection component decreases, and the specular glossiness (GS60 °) tends to shift downward.
  • the thickness of the indium vapor deposition layer is thick, the ratio of the bottom portion of the indium island structure increases near the interface between the anchor layer and the indium vapor deposition layer, and the specular reflection component becomes relatively large. (GS60°) tends to shift upwards.
  • the method of adjusting the L* value (L*45) within the above range is not particularly limited.
  • the L* value (L*45) can be adjusted by changing the concentration of black dye added in the primer layer. If the concentration of the black dye is low, the proportion of diffusely reflected light absorbed by the protruding portion of the indium island structure protruding toward the primer layer decreases, resulting in deterioration of the shade/highlight characteristics, that is, the shade (shadow). There is a tendency to shift in the direction where the part is not dark enough and is perceived as cloudy. In this case, the L* value (L*45) will be large.
  • the specular glossiness (GS60°) correlates with the intensity of the regular reflection component
  • the L* value (L*45) correlates with the intensity of the diffuse reflection component.
  • the value of GS60°/L*45 which is the ratio of the two, indicates that the intensity of the specular reflection component is strong (the value of GS60° is large) and/or the intensity of the diffuse reflection component is weak (the value of L*45 is smaller) and larger.
  • the value of GS60°/L*45 is small when the intensity of the specular reflection component is low (the value of GS60° is small) and/or when the intensity of the diffuse reflection component is high (the value of L*45 is large).
  • the value of GS60°/L*45 can be an index of shade/highlight characteristics. There is a correlation between this value and the visibility of shades and highlights when visually observed.
  • the excellent shade/highlight feeling means that cloudiness is hardly felt when exposed to external light.
  • an excellent shade/highlight feeling means that the shade (shadow) is darker and the highlight (specular reflection) is brighter, showing a sharp appearance.
  • the resin to which the black dye is added enters between the islands of the sea-island structure of the vapor-deposited indium layer.
  • the metallic decorative film can suppress the scattering effect due to the scattered indium islands, and can exhibit excellent metallic luster with suppressed haze.
  • Such a metallic decorative film can provide sufficient shade/highlight properties when it is out-molded into a three-dimensional structure, for example.
  • the metal-tone decorative film includes a step of forming an anchor layer on the substrate (anchor layer forming step), a step of forming an indium vapor deposition layer on the anchor layer (vapor deposition step), and a primer on the indium vapor deposition layer. It mainly includes a step of forming a layer (primer layer forming step) and a step of forming an adhesive layer on the primer layer (adhesive layer forming step). When the primer layer also serves as the adhesive layer, the adhesive layer forming step may be omitted.
  • an anchor layer is formed on a prepared base material.
  • a method for forming the anchor layer is not particularly limited.
  • the anchor layer may be gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, foiler coat, dip coat, solid coat by silk screen, wire bar coat, flow coat, It can be formed by applying it to the substrate layer by a normal coating method such as comma coating, pouring coating, brush coating, spray coating, or a transfer coating method.
  • an indium deposition layer is formed on the anchor layer.
  • a method for forming the indium deposition layer is not particularly limited.
  • a conventionally known physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a chemical vapor deposition method can be appropriately adopted.
  • the vapor deposition conditions conventionally known conditions can be suitably adopted based on the desired thickness of the indium vapor deposition layer.
  • the metal material preferably contains few impurities and has a purity of 99% by mass or more, more preferably 99.5% by mass or more. Moreover, the metal material is preferably processed into a granular, rod-shaped, tablet-shaped, wire-shaped, or crucible-shaped shape to be used.
  • Heating methods for evaporating metal materials include a method in which the metal material is placed in a crucible and subjected to resistance heating or high-frequency heating, a method in which electron beam heating is performed, and a method in which the metal material is placed directly in a ceramic board such as boron nitride. A well-known method such as a method of performing resistance heating can be used.
  • a crucible used for vacuum deposition is desirably made of carbon, and may be a crucible made of alumina, magnesia, titania, or beryllia.
  • the primer layer is coated with a primer composition containing the above resin by gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, foiler coating, dip coating, and silk screen. It can be formed by applying it to the indium deposited layer by a normal coating method such as solid coating, wire bar coating, flow coating, comma coating, flow coating, brush coating, spray coating, or a transfer coating method.
  • a normal coating method such as solid coating, wire bar coating, flow coating, comma coating, flow coating, brush coating, spray coating, or a transfer coating method.
  • the adhesive layer forming step is an optional step.
  • An adhesion layer is optionally formed on the surface of the primer layer opposite to the surface on which the indium deposition layer is formed (adhesion layer forming step).
  • the method of forming the adhesive layer is not particularly limited.
  • the adhesive layer may be formed by applying a resin solution that constitutes the adhesive layer onto the primer layer.
  • a metal-like product can be produced using the obtained metal-like decorative film.
  • a metal-like product can be produced, for example, by molding a metal-like decorative film (in particular, out-molding) by various molding methods.
  • the molding method can be appropriately selected based on the configuration of the metallic decorative film.
  • a metallic decorative film provided with an adhesive layer is formed by vacuum forming, TOM (Three Dimension Overlay Method) forming, or the like.
  • TOM molding a metallic decorative film is applied to a pre-prepared molded body (for example, resin, metal, glass, wood, etc.) and is softened by heat so that it can be integrated with the molded body. molded.
  • a pre-prepared molded body for example, resin, metal, glass, wood, etc.
  • vacuum forming the metallic decorative film is heated by a heater and softened. The heated metallic decorative film is then pressed against a desired three-dimensional mold while applying vacuum, and is deformed so as to follow the shape of the metallic preparation.
  • the metallic decorative film may be molded by TOM molding, in-line lamination, or the like, or may be molded by insert injection molding, or the like.
  • the metal preparation of the present embodiment is a metal preparation using the metal-like decorative film described above.
  • the metallic decorative film can exhibit excellent metallic luster with suppressed cloudiness. Therefore, the metal-like decorative film can easily impart sufficient shade/highlight properties to various articles to produce metal-like products.
  • the metal preparation is not particularly limited.
  • the metal preparation is a container, a housing or an interior and exterior member for a vehicle.
  • the metal-prepared product using the metal-like decorative film of the present embodiment it is possible to produce various interior and exterior parts for vehicles that are imparted with sufficient shade/highlight characteristics and exhibit excellent design.
  • the container is suitable as, for example, a container for cosmetics, a container for beverages, and the like.
  • the housing is suitable, for example, as a housing for a communication device such as a mobile phone, a household appliance, or the like.
  • a base material, an anchor layer, an indium deposition layer, and a primer layer in this order, the primer layer contains a black dye, and the specular gloss at an incident angle of 60° (GS60°) and the L* value (L*45) at an incident angle and a light receiving angle of 45° (GS60°/L*45) is 75 or more.
  • the black dye-added resin enters between the islands of the sea-island structure of the indium vapor-deposited layer.
  • the metallic decorative film can suppress the scattering effect due to the scattered indium islands, and can exhibit excellent metallic luster with suppressed haze.
  • Such a metallic decorative film can provide sufficient shade/highlight properties when it is out-molded into a three-dimensional structure, for example.
  • the black dye-added resin easily enters between the islands of the sea-island structure of the indium-deposited layer.
  • the metallic decorative film can exhibit excellent metallic luster with less cloudiness.
  • the metal-tone decorative film has excellent formability due to the addition of an appropriate amount of resin to the primer layer.
  • the metallic decorative film can realize color metallic of any color.
  • the metallic decorative film can be used by being attached to various base materials, and can impart metallic luster by a simpler and safer method than painting.
  • the metal-like product can obtain sufficient shade/highlight characteristics when, for example, the above-described metal-like decorative film is out-molded into a three-dimensional structure.
  • metal preparation according to (5) wherein the metal preparation is a container, a housing, or an interior/exterior member for a vehicle.
  • the metal preparation can obtain sufficient shade/highlight characteristics, and is therefore suitable for metal preparation such as containers, housings, or vehicle interior and exterior members.
  • Example 1 A substrate (thickness: 75 ⁇ m) made of PC was prepared. Using a bar coater, a base material is coated with an anchor coating agent solution obtained by mixing an acrylic polyol and an isocyanate-based coating material to a thickness of 1.3 ⁇ m after drying, and then dried at 100° C. for 1 minute. to form an anchor layer. Next, an indium deposition layer was formed on the anchor layer by a vacuum deposition method so as to have a thickness of 40 nm. Then, a primer layer having a thickness of 0.5 ⁇ m was formed using a bar coater. The black dye (N.BLACK X51, manufactured by BASF) contained in the primer layer was 75% by mass.
  • N.BLACK X51 manufactured by BASF
  • a separator PET film with an adhesive layer (25 ⁇ m thick) made of an acrylic adhesive was prepared.
  • the primer layer and the adhesive layer (adhesive layer) were laminated so as to be in contact with each other, and after the adhesive layer was transferred to the primer layer, the separator was peeled off to prepare a metallic decorative film of Example 1.
  • Example 2 A metal-tone decorative film was produced in the same manner as in Example 1, except that the base material (thickness: 75 ⁇ m) made of PMMA was used.
  • Example 5 A metallic decorative film was produced in the same manner as in Example 2, except that the primer layer did not contain a black dye.
  • Example 3 A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 20% by mass.
  • Example 4 A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 30% by mass.
  • Example 5 A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 40% by mass.
  • Example 6 A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 50% by mass.
  • Example 7 A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 60% by mass.
  • Example 8 A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 70% by mass.
  • Example 9 A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 80% by mass.
  • Example 10 A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 90% by mass.
  • FIG. 4 is a schematic diagram for explaining the definition of the angle of the L* value. Since the L* value (L*0) in the incident direction D2 of the specularly reflected light cannot be measured by the apparatus, the degree of specular reflection was measured by separately measuring the gloss value. Regarding the definition of the angle, as described above, the light receiving angle of the light receiver Pd was set (fixed) at 45°. The light-receiving angle of 45° means that the surface of the metallic decorative film F has an inclination angle A of 45° from the normal direction D1.
  • L*0 is the incident direction of the specularly reflected light with respect to the light receiving angle of 45°, that is, from the direction of the light receiving angle of 45° toward the normal direction D1 on the surface of the metal-tone decorative film F, 90° It means the L* value when the light from the light source LS is incident from the direction of the rotated angle.
  • L*0 means the L* value when light is incident from a direction in which the direction of the light-receiving angle of 45° is horizontally reversed with respect to the normal direction D1 on the surface of the metallic decorative film F.
  • L*-15 means the L* value when light is incident from a direction rotated 15° clockwise from the direction of L*0, and L*15 is the direction of L*0.
  • L* means the L* value when light is incident from the direction rotated 15° counterclockwise from the L*0 direction
  • L*25 means the light means the L * value when the light is incident
  • L * 45 means the L * value when the light is incident from the direction rotated 45 ° counterclockwise from the direction of L *
  • L*75 means the L* value when light is incident from a direction rotated counterclockwise by 75° from the direction of L*0
  • L*110 means the value of light incident from the direction counterclockwise from the direction of L*0. It means the L* value when light is incident from a direction rotated clockwise by 110°.
  • the specular glossiness (GS20° and GS60°) was measured using an appearance analyzer (Rhopoint IQ-S, manufactured by Rhopoint).
  • Rhopoint IQ-S appearance analyzer
  • the gloss value was measured in the specular reflection direction of the light from the light source with respect to the incident angle of the light source of 20° (incident at an angle of 20° with respect to the normal direction of the film).
  • the gloss value was measured in the specular reflection direction of the light from the light source with respect to the incident angle of the light source of 60° (incident at an angle inclined by 60° with respect to the normal direction of the film).
  • ⁇ Moldability> The formability was evaluated by stretching each laminated film twice in a 140° C. atmosphere in a uniaxial direction (grip distance: 5 cm) and evaluating the moldability according to the following evaluation criteria. (Evaluation criteria) x: Remarkable cracks occurred, and the metallic luster was remarkably lowered. ⁇ : Some cracks occurred and the metallic luster decreased. Good: No cracks occurred, but the metallic luster was slightly reduced. ⁇ : No cracks occurred, and sufficient metallic luster could be maintained.
  • FIGS. 5 and 6 are photographs of appearances of metal-like products using the metal-like decorative films of Comparative Example 5 and Example 8.
  • FIG. Figure 5 is an exterior photograph taken indoors under LED lighting (assuming how it looks indoors and outdoors during the day)
  • Figure 6 is an exterior photograph taken in a darkroom with LED lighting (illuminated at night). Assuming how it looks when it hits).
  • FIGS. 5 and 6 are photographs of appearances of metal-like products using the metal-like decorative films of Comparative Example 5 and Example 8.
  • FIG. Figure 5 is an exterior photograph taken indoors under LED lighting (assuming how it looks indoors and outdoors during the day)
  • Figure 6 is an exterior photograph taken in a darkroom with LED lighting (illuminated at night). Assuming how it looks when it hits).
  • the metal-like product (left side) using the metal-like decorative film of Comparative Example 5 had a cloudy (whitish) appearance due to diffuse reflection, whereas the appearance of Example 8 was cloudy (whitish) due to diffuse reflection.
  • the metal-tone product (right side) using the metal-tone decorative film of No. 2 had a shaded appearance (excellent shade/highlight characteristics) with suppressed clouding.
  • the metallic decorative film of Comparative Example 1 employed Cr plating. Cr plating is not preferable because it tends to cause environmental problems due to plating waste liquid and requires a plating process.

Abstract

Provided are: a metallic-tone decorative film exhibiting excellent metallic luster with reduced haze and having good shade/highlight properties, for example, when out-molded on three-dimensional structures; and a metallic-tone product. The metallic-tone decorative film has a substrate, an anchor layer, an indium deposition layer, and a primer layer in this order, wherein the primer layer contains a black dye, and the ratio (GS60°/L*45) of specular gloss (GS60°) at an incident angle of 60° to L* value (L*45) at incident and light-receiving angles of 45° is at least 75.

Description

金属調加飾フィルム、金属調製品Metallic decorative films, metallic products
　本発明は、金属調加飾フィルム、金属調製品に関する。より詳細には、本発明は、曇りの抑制された優れた金属光沢を示し、たとえば三次元構造物にアウトモールド成形された際に、充分なシェード・ハイライト特性が得られる金属調加飾フィルム、金属調製品に関する。 The present invention relates to a metal-like decorative film and a metal-like product. More specifically, the present invention provides a metallic decorative film that exhibits excellent metallic luster with suppressed clouding, and provides sufficient shade/highlight properties when, for example, it is out-molded into a three-dimensional structure. , relating to metal preparations.
　従来、三次元成形性を備える加飾シートが開発されている（たとえば特許文献１）。特許文献１に記載の加飾シートは、プライマー層において添加する着色剤として、たとえば、顔料、染料などを使用することができることが開示されている。 Conventionally, decorative sheets with three-dimensional formability have been developed (for example, Patent Document 1). The decorative sheet described in Patent Document 1 discloses that pigments, dyes, and the like, for example, can be used as coloring agents added in the primer layer.
特開２０１４－２０８４３２号公報JP 2014-208432 A
　しかしながら、特許文献１に記載の加飾シートは、金属蒸着層としてインジウムを採用し、着色剤として一般的な顔料を使用する場合において、インジウム蒸着層の海島構造の島同士の間に顔料が入り込みにくい。また、加飾シートは、プライマー層の着色剤として黒色を選択しないと、インジウムの島の周囲で散乱する光を吸収できずに、反射光が散乱性を有してしまう。その結果、加飾シートは、得られる金属光沢が曇りを有する。このような加飾シートは、三次元構造物にアウトモールド成形されると、シェード・ハイライト特性が得られにくい。 However, in the decorative sheet described in Patent Document 1, when indium is used as the metal vapor deposition layer and a general pigment is used as the colorant, the pigment enters between the islands of the sea-island structure of the indium vapor deposition layer. Hateful. Moreover, unless black is selected as the coloring agent for the primer layer, the decorative sheet cannot absorb the light scattered around the indium islands, and the reflected light has a scattering property. As a result, the decorative sheet has a dull metallic luster. When such a decorative sheet is out-molded into a three-dimensional structure, it is difficult to obtain shade/highlight properties.
　本発明は、このような従来の発明に鑑みてなされたものであり、曇りの抑制された優れた金属光沢を示し、たとえば三次元構造物にアウトモールド成形された際に、充分なシェード・ハイライト特性が得られる金属調加飾フィルム、金属調製品を提供することを目的とする。 The present invention has been made in view of such conventional inventions, and exhibits excellent metallic luster with suppressed clouding, for example, when it is out-molded into a three-dimensional structure, it has sufficient shade and high. An object of the present invention is to provide a metal-like decorative film and a metal-like product that can obtain light characteristics.
　本発明者は、鋭意検討した結果、金属蒸着層としてインジウムを採用し、プライマー層として黒色染料を配合することにより、インジウム蒸着層の海島構造の島同士の間に黒色染料が添加された樹脂が入り込み、これにより、インジウムの島が散在していることによる散乱効果を抑制することができ、曇りの抑制された優れた金属光沢を示し得ることを見出し、本発明を完成させた。 As a result of intensive studies, the present inventors have found that by using indium as the metal vapor deposition layer and blending black dye as the primer layer, a resin to which the black dye is added between the islands of the sea-island structure of the indium vapor deposition layer. As a result, the inventors have found that the scattering effect due to the scattered indium islands can be suppressed, and excellent metallic luster with suppressed cloudiness can be exhibited, and the present invention has been completed.
　上記課題を解決する本発明の一実施態様の金属調加飾フィルムは、基材と、アンカー層と、インジウム蒸着層と、プライマー層と、をこの順で有し、前記プライマー層は、黒色染料を含み、入射角が６０°における鏡面光沢度（ＧＳ６０°）と、入射角および受光角が４５°におけるＬ＊値（Ｌ＊４５）との割合（ＧＳ６０°／Ｌ＊４５）は、７５以上である、金属調加飾フィルムである。 A metallic decorative film according to one embodiment of the present invention for solving the above problems has a substrate, an anchor layer, an indium deposition layer, and a primer layer in this order, and the primer layer contains a black dye. Including, the ratio (GS60°/L*45) between the specular glossiness (GS60°) at an incident angle of 60° and the L* value (L*45) at an incident angle and a light receiving angle of 45° is 75 or more It is a metallic decorative film.
　また、上記課題を解決する本発明の一実施態様の金属調製品は、上記金属調加飾フィルムを用いた、金属調製品である。 A metal preparation according to one embodiment of the present invention for solving the above problems is a metal preparation using the metal-like decorative film.
図１は、プライマー層に黒色染料も黒色顔料も添加していないサンプルの模式図である。FIG. 1 is a schematic diagram of a sample in which neither black dye nor black pigment is added to the primer layer. 図２は、プライマー層に黒色染料を添加したサンプルの模式図である。FIG. 2 is a schematic diagram of a sample in which a black dye is added to the primer layer. 図３は、プライマー層に黒色顔料を添加したサンプルの模式図である。FIG. 3 is a schematic diagram of a sample in which a black pigment is added to the primer layer. 図４は、Ｌ＊値の角度の定義を説明するための模式図である。FIG. 4 is a schematic diagram for explaining the definition of the angle of the L* value. 図５は、比較例５および実施例８の金属調加飾フィルムを用いた金属調製品の外観写真である。FIG. 5 is an appearance photograph of a metal-like product using the metal-like decorative films of Comparative Example 5 and Example 8. FIG. 図６は、比較例５および実施例８の金属調加飾フィルムを用いた金属調製品の外観写真である。FIG. 6 is an appearance photograph of a metal tone product using the metal tone decorative films of Comparative Example 5 and Example 8. FIG.
＜金属調加飾フィルム＞
　本発明の一実施形態の金属調加飾フィルムは、基材と、アンカー層と、インジウム蒸着層と、プライマー層と、をこの順で有する。プライマー層は、黒色染料を含む。入射角が６０°における鏡面光沢度（ＧＳ６０°）と、入射角および受光角が４５°におけるＬ＊値（Ｌ＊４５）との割合（ＧＳ６０°／Ｌ＊４５）は、７５以上である。本実施形態の金属調加飾フィルムによれば、曇りの抑制された優れた金属光沢を示し得る。このような金属調加飾フィルムは、たとえば三次元構造物にアウトモールド成形された際に、充分なシェード・ハイライト特性が得られる。なお、シェード・ハイライト特性とは、正反射成分が強く、拡散反射成分が弱い特性をいう。これにより、正反射部分がより明るく、それ以外の影の部分がより暗くなり、優れた陰影加飾効果を実現し得る。以下、それぞれについて説明する。 <Metallic decorative film>
A metallic decorative film of one embodiment of the present invention has a base material, an anchor layer, an indium deposition layer, and a primer layer in this order. The primer layer contains a black dye. The ratio (GS60°/L*45) between the specular glossiness (GS60°) at an incident angle of 60° and the L* value (L*45) at an incident angle and a light receiving angle of 45° is 75 or more. The metallic decorative film of the present embodiment can exhibit excellent metallic luster with suppressed fogging. Such a metallic decorative film can provide sufficient shade/highlight properties when it is out-molded into a three-dimensional structure, for example. Note that the shade/highlight characteristic refers to a characteristic in which a specular reflection component is strong and a diffuse reflection component is weak. As a result, the specular reflection portion becomes brighter and the other shadow portion becomes darker, thereby realizing an excellent shadow decoration effect. Each of these will be described below.
（基材）
　基材は特に限定されない。一例を挙げると、基材は、ポリメタクリル酸メチル（ＰＭＭＡ）等のポリ（メタ）アクリル酸エステル、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート、ポリエチレン－２，６－ナフタレート、ポリフッ化ビニル（ＰＶＦ）、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、エチレン－テトラフルオロエチレン共重合体（ＥＴＦＥ）、エチレン－クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）、テトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体（ＦＥＰ）等からなる。 (Base material)
The base material is not particularly limited. By way of example, the substrate may be poly(meth)acrylic acid ester such as polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate, polyethylene-2,6-naphthalate, polyvinyl fluoride (PVF), polyfluoride. Vinylidene chloride (PVDF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), tetrafluoro It consists of ethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and the like.
　基材の厚みは特に限定されない。一例を挙げると、基材の厚みは、１．０～３００μｍであることが好ましい。基材の厚みが上記範囲内であることにより、金属調加飾フィルムは、耐擦傷性、耐摩耗性が優れる。 The thickness of the base material is not particularly limited. For example, the thickness of the substrate is preferably 1.0 to 300 μm. When the thickness of the substrate is within the above range, the metallic decorative film has excellent scratch resistance and abrasion resistance.
　基材は、所望の表面加工が施されたものが使用されてもよい。表面加工は特に限定されない。一例を挙げると、表面加工は、マット加工、サテン加工、エンボス加工、ヘアライン加工等である。また、基材の表面（アンカー層が形成される面とは反対の面）に、各種コーティング（フッ素加工、ハードコート加工等）、転写等の表面加工が施されてもよい。これにより、基材の表面には、各種意匠性や機能性が付与され得る。 The base material may be one that has undergone desired surface processing. Surface treatment is not particularly limited. Examples of surface finishing include matte finishing, satin finishing, embossing, and hairline finishing. Further, the surface of the base material (the surface opposite to the surface on which the anchor layer is formed) may be subjected to surface processing such as various coatings (fluorine processing, hard coating processing, etc.) and transfer. Thereby, various design properties and functionality can be imparted to the surface of the substrate.
（アンカー層）
　アンカー層は、基材とインジウム蒸着層との密着性を向上させるために設けられる。 (anchor layer)
The anchor layer is provided to improve the adhesion between the substrate and the indium deposition layer.
　アンカー層は特に限定されない。一例を挙げると、アンカー層は、基材との密着性がよく、かつ、インジウム蒸着層を構成するインジウムの受理性がよい原料であればよく、アクリル系樹脂、ニトロセルロース系樹脂、ポリウレタン系樹脂、ポリエステル系樹脂、スチレン－マレイン系酸樹脂、塩素化ＰＰ系樹脂等である。アンカー層は、たとえば、主剤であるポリオール系樹脂に、イソシアネート系化合物を硬化剤として添加したものであってもよい。 The anchor layer is not particularly limited. For example, the anchor layer may be made of any raw material that has good adhesion to the substrate and good receptivity for indium constituting the indium vapor deposition layer. , polyester resins, styrene-maleic acid resins, chlorinated PP resins, and the like. For example, the anchor layer may be formed by adding an isocyanate compound as a curing agent to a polyol resin as a main agent.
　アンカー層の厚みは特に限定されない。一例を挙げると、アンカー層の厚みは、０．１～３μｍが好ましい。アンカー層の厚みが上記範囲内であることにより、金属調加飾フィルムは、基材とインジウム蒸着層との密着性が優れる。 The thickness of the anchor layer is not particularly limited. For example, the thickness of the anchor layer is preferably 0.1 to 3 μm. When the thickness of the anchor layer is within the above range, the metallic decorative film has excellent adhesion between the base material and the indium deposited layer.
　アンカー層は、着色剤や金属顔料が付与されることにより、意匠性が付与されてもよい。たとえば、着色剤としてイエロー顔料が配合されることにより、金属調加飾フィルムは、金色の外観を表現し得る。着色剤の種類や含有量は、所望する金属調の外観に応じて適宜調整され得る。また、アンカー層は、帯電防止剤等が配合されることにより、帯電防止効果などの機能性が付与されてもよい。 The anchor layer may be given designability by adding a coloring agent or a metal pigment. For example, by blending a yellow pigment as a coloring agent, the metallic decorative film can express a golden appearance. The type and content of the coloring agent can be appropriately adjusted according to the desired metallic appearance. Further, the anchor layer may be provided with functionality such as an antistatic effect by blending an antistatic agent or the like.
　アンカー層は、染料または顔料を含んでもよい。また、染料または顔料は、黒色、グレーまたは有彩色の染料または顔料であることが好ましい。アンカー層がこれらの染料または顔料を含むことにより、金属調加飾フィルムは、任意の色彩のカラーメタリックを実現し得る。 The anchor layer may contain dyes or pigments. Also, the dye or pigment is preferably a black, gray or chromatic dye or pigment. By including these dyes or pigments in the anchor layer, the metallic decorative film can achieve a color metallic of any color.
　染料は特に限定されない。一例を挙げると、染料は、アゾ（モノアゾ、ジスアゾ等）染料、アゾ－メチン染料、アントラキノン系染料キノリン染料、ケトンイミン染料、フルオロン染料、ニトロ染料、キサンテン染料、アセナフテン染料、キノフタロン染料、アミノケトン染料、メチン染料、ペリレン染料、クマリン染料、ペリノン染料、トリフェニル染料、トリアリルメタン染料、フタロシアニン染料、インクロフェノール染料、アジン染料、ピラゾロン染料およびこれらの混合物等である。 The dye is not particularly limited. Examples of dyes include azo (monoazo, disazo, etc.) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketoneimine dyes, fluorone dyes, nitro dyes, xanthene dyes, acenaphthene dyes, quinophthalone dyes, aminoketone dyes, methine Dyes, perylene dyes, coumarin dyes, perinone dyes, triphenyl dyes, triallylmethane dyes, phthalocyanine dyes, incrophenol dyes, azine dyes, pyrazolone dyes and mixtures thereof.
　顔料は特に限定されない。一例を挙げると、顔料は、干渉マイカ顔料、ホワイトマイカ顔料、グラファイト顔料などの光輝性顔料；黄鉛、黄色酸化鉄、ベンガラ、カーボンブラック、マンガンフェライト、二酸化チタンなどの無機着色顔料；カオリン、クレー、シリカ、酸化亜鉛、炭酸カルシウム、沈降性硫酸バリウムなどの体質顔料；等である。 The pigment is not particularly limited. Examples of pigments include bright pigments such as interference mica pigments, white mica pigments, and graphite pigments; inorganic coloring pigments such as yellow lead, yellow iron oxide, red iron oxide, carbon black, manganese ferrite, and titanium dioxide; , silica, zinc oxide, calcium carbonate, precipitated barium sulfate, and other extender pigments;
　染料または顔料の含有量は特に限定されない。一例を挙げると、染料または顔料の含有量は、アンカー層中、２．０質量％以上であることが好ましく、４．０質量％以上であることがより好ましい。また、染料または顔料の含有量は、アンカー層中、１５．０質量％以下であることが好ましく、１０．０質量％以下であることがより好ましい。染料または顔料の含有量が上記範囲内であることにより、金属調加飾フィルムは、任意の色彩のカラーメタリックを実現しやすい。 The content of the dye or pigment is not particularly limited. For example, the dye or pigment content in the anchor layer is preferably 2.0% by mass or more, more preferably 4.0% by mass or more. Also, the content of the dye or pigment in the anchor layer is preferably 15.0% by mass or less, more preferably 10.0% by mass or less. When the content of the dye or pigment is within the above range, the metallic decorative film can easily achieve a color metallic color of any desired color.
（インジウム蒸着層）
　インジウム蒸着層において、インジウムは、酸化物、窒化物として含まれてもよい。本実施形態の金属調加飾フィルムは、金属蒸着層がインジウム蒸着層であることにより、成形加工時に白化等の外観不良を生じにくく、成形加工性が優れる。その結果、金属調加飾フィルムは、種々の三次元形状に加工されやすい。 (Indium deposition layer)
The indium vapor deposition layer WHEREIN: Indium may be contained as an oxide and a nitride. In the metal-tone decorative film of the present embodiment, since the metal-deposited layer is an indium-deposited layer, appearance defects such as whitening are less likely to occur during molding, and molding processability is excellent. As a result, the metallic decorative film can be easily processed into various three-dimensional shapes.
　また、インジウム蒸着層は、各種非金属、金属、金属酸化物および金属窒化物を含んでもよい。非金属、金属等は特に限定されない。一例を挙げると、非金属は、アモルファスカーボン（ＤＬＣ）およびその複合体、金属等は、金、銀、白金、スズ、クロム、ケイ素、チタン、亜鉛、アルミニウムおよびマグネシウム等の金属、その酸化物、その窒化物である。 In addition, the indium deposition layer may contain various non-metals, metals, metal oxides and metal nitrides. Non-metals, metals and the like are not particularly limited. To give an example, non-metals are amorphous carbon (DLC) and their composites, metals are metals such as gold, silver, platinum, tin, chromium, silicon, titanium, zinc, aluminum and magnesium, oxides thereof, It is the nitride.
　インジウム蒸着層におけるインジウムの含有量は特に限定されない。一例を挙げると、インジウムの含有量は、インジウム蒸着層中、９５質量％以上であることが好ましく、９８質量％以上であることがより好ましい。インジウムの含有量は、１００質量％であってもよい。インジウム蒸着層は、不可避的に含まれるインジウム以外の不純物を含んでいてもよい。 The content of indium in the indium deposition layer is not particularly limited. For example, the content of indium in the indium deposition layer is preferably 95% by mass or more, more preferably 98% by mass or more. The indium content may be 100% by mass. The indium deposited layer may contain impurities other than indium which is unavoidably contained.
　本実施形態のインジウム蒸着層は、海島構造（いわゆる不連続構造）を有する。これにより、インジウム蒸着層は、たとえば、アルミニウム蒸着層等の他の一般的な金属蒸着層と比較して、成形加工等により、３次元的に延伸されても優れた金属光沢を得ることができる。海島構造において、島の部分はインジウムが存在する領域であり、海の部分はインジウムが存在しない領域である。本実施形態の金属調加飾フィルムは、後述するプライマー層の黒色染料を含む樹脂が、インジウム蒸着層の海島構造の島同士の間に入り込む。その結果、金属調加飾フィルムは、インジウムの島が散在していることによる散乱効果を抑制することができ、曇りの抑制された優れた金属光沢を示し得る。 The indium deposition layer of this embodiment has a sea-island structure (so-called discontinuous structure). As a result, the indium vapor deposition layer, for example, compared to other general metal vapor deposition layers such as an aluminum vapor deposition layer, can obtain an excellent metallic luster even if it is three-dimensionally stretched by a molding process or the like. . In the sea-island structure, the island portion is a region where indium exists, and the sea portion is a region where indium does not exist. In the metal-tone decorative film of the present embodiment, a resin containing a black dye in the primer layer, which will be described later, enters between the islands of the sea-island structure of the indium vapor-deposited layer. As a result, the metallic decorative film can suppress the scattering effect caused by scattered indium islands, and can exhibit excellent metallic luster with suppressed haze.
　インジウム蒸着層の厚みは特に限定されない。一例を挙げると、インジウム蒸着層の厚みは、１０ｎｍ以上であることが好ましく、１５ｎｍ以上であることがより好ましい。また、インジウム蒸着層の厚みは、８０ｎｍ以下であることが好ましく、６０ｎｍ以下であることがより好ましい。インジウム蒸着層の厚みが上記範囲内であることにより、インジウム蒸着層は、金属光沢と成形性とを両立されやすい。なお、本実施形態において、インジウム蒸着層の厚みは、島構造であるインジウム蒸着層の断面積（略扇形断面の面積）と、同横幅で、かつ、同面積となる長方形を想定した場合の高さと考えてもよい。なお、本実施形態のインジウム蒸着層の厚みは、蛍光Ｘ線分析法（ＸＲＦ）を用いて、定量分析により求めた値である。 The thickness of the indium deposition layer is not particularly limited. For example, the thickness of the indium deposition layer is preferably 10 nm or more, more preferably 15 nm or more. Also, the thickness of the indium deposition layer is preferably 80 nm or less, more preferably 60 nm or less. When the thickness of the indium deposition layer is within the above range, the indium deposition layer tends to achieve both metallic luster and formability. In the present embodiment, the thickness of the indium vapor deposition layer is the same as the cross-sectional area of the indium vapor deposition layer having an island structure (the area of the substantially fan-shaped cross section), assuming a rectangle having the same width and area. You can think of it as It should be noted that the thickness of the indium deposited layer in this embodiment is a value determined by quantitative analysis using X-ray fluorescence spectroscopy (XRF).
（プライマー層）
　プライマー層は、本実施形態の金属調加飾フィルムに優れた三次元成形性を付与し、複雑な表面形状を有する金属調製品の形状に充分に追従し得る金属調加飾フィルムとするために設けられる。 (primer layer)
The primer layer imparts excellent three-dimensional formability to the metallic decorative film of the present embodiment, and is intended to provide a metallic decorative film that can sufficiently follow the shape of a metallic preparation having a complicated surface shape. be provided.
　金属調加飾フィルムの三次元成形性をより高める点から、プライマー層は、ガラス転移点が－２０℃～１００℃の樹脂の硬化物を含むことが好ましい。なお、本実施形態において、ガラス転移点（Ｔｇ）は、ＪＩＳ　Ｋ　７１２１－１９８７に基づき、示差走査熱量測定（ＤＳＣ）によって測定し得る。 The primer layer preferably contains a cured resin with a glass transition point of -20°C to 100°C in order to further enhance the three-dimensional formability of the metallic decorative film. In this embodiment, the glass transition point (Tg) can be measured by differential scanning calorimetry (DSC) based on JIS K 7121-1987.
　ガラス転移点（Ｔｇ）が－２０℃～１００℃の樹脂の含有量は、プライマー層を構成する樹脂中、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い。プライマー層を形成する樹脂は、ガラス転移点（Ｔｇ）が－２０℃～１００℃の樹脂のみであってもよい。 The content of the resin having a glass transition point (Tg) of -20°C to 100°C is preferably 50% by mass or more, more preferably 70% by mass or more, in the resin constituting the primer layer. The resin forming the primer layer may be only a resin having a glass transition point (Tg) of -20°C to 100°C.
　ガラス転移点（Ｔｇ）が－２０℃～１００℃の樹脂は特に限定されない。一例を挙げると、ガラス転移点（Ｔｇ）が－２０℃～１００℃の樹脂は、熱硬化性樹脂、熱可塑性樹脂等であり、ポリエステル系樹脂、ポリウレタン系樹脂、ポリアクリル系樹脂、ポリオレフィン系樹脂等であることが好ましく、ポリエステル系樹脂であることがより好ましい。 The resin with a glass transition point (Tg) of -20°C to 100°C is not particularly limited. As an example, resins having a glass transition point (Tg) of -20°C to 100°C include thermosetting resins, thermoplastic resins, polyester resins, polyurethane resins, polyacrylic resins, and polyolefin resins. etc., and more preferably a polyester-based resin.
　ポリエステル系樹脂は、ポリエステルポリオール等である。ポリウレタン系樹脂は、ポリエステルウレタンポリオール、アクリルウレタンポリオール等である。ポリアクリル系樹脂は、アクリルポリオール等である。ポリオレフィン系樹脂は、ポリエチレンポリオール、ポリプロピレンポリオール、ポリブタジエンポリオール、ポリイソプレンポリオール等である。 　Polyester-based resins include polyester polyols. Polyurethane-based resins include polyester urethane polyols, acrylic urethane polyols, and the like. The polyacrylic resin is acrylic polyol or the like. Polyolefin resins include polyethylene polyol, polypropylene polyol, polybutadiene polyol, polyisoprene polyol, and the like.
　プライマー層は、ガラス転移点（Ｔｇ）が－２０℃～１００℃の上記樹脂と硬化剤との硬化物により形成されていることが好ましく、ガラス転移点（Ｔｇ）が－２０℃～１００℃のポリオール樹脂と、イソシアネート化合物等からなる硬化剤とによって得られる、反応硬化型のウレタン樹脂により形成されていることがより好ましい。ガラス転移点（Ｔｇ）が－２０℃～１００℃のポリオール樹脂は、上記で例示したポリエステル系樹脂、ポリウレタン系樹脂、ポリアクリル系樹脂、またはポリオレフィン系樹脂である上記のポリオール等である。 The primer layer is preferably formed of a cured product of the above resin having a glass transition point (Tg) of -20°C to 100°C and a curing agent, and a glass transition point (Tg) of -20°C to 100°C. More preferably, it is made of a reaction-curing urethane resin obtained from a polyol resin and a curing agent such as an isocyanate compound. The polyol resin having a glass transition point (Tg) of −20° C. to 100° C. includes the above-mentioned polyols, which are polyester-based resins, polyurethane-based resins, polyacrylic-based resins, or polyolefin-based resins.
　イソシアネート化合物は特に限定されない。一例を挙げると、イソシアネート化合物は、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、キシレン－１，４－ジイソシアネート、キシレン－１，３－ジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、２，２’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート、ポリメチレンポリフェニレンポリイソシアネート、２－ニトロジフェニル－４，４’－ジイソシアネート、２，２’－ジフェニルプロパン－４，４’－ジイソシアネート、３，３’－ジメチルジフェニルメタン－４，４’－ジイソシアネート、４，４’－ジフェニルプロパンジイソシアネート、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート、ナフチレン－１，４－ジイソシアネート、ナフチレン－１，５－ジイソシアネート、３，３’－ジメトキシジフェニル－４，４’－ジイソシアネートなどの芳香族イソシアネート；１，４－ジイソシアナトブタン、１，５－ジイソシアナトペンタン、１，６－ジイソシアナトヘキサン（１，６－ヘキサメチレンジイソシアネート、ＨＤＩ）、１，６－ジイソシアナト－２，２，４－トリメチルヘキサン、２，６－ジイソシアナトヘキサン酸メチル（リジンジイソシアネート）などの脂肪族イソシアネート；イソホロンジイソシアネート、水素添加キシリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネートなどの脂環式ジイソシアネート等である。 The isocyanate compound is not particularly limited. For example, isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4′-diphenylmethane diisocyanate, 2 ,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, polymethylene polyphenylene polyisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4 ,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene- Aromatic isocyanates such as 1,5-diisocyanate and 3,3′-dimethoxydiphenyl-4,4′-diisocyanate; 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanate Aliphatic isocyanates such as natohexane (1,6-hexamethylene diisocyanate, HDI), 1,6-diisocyanato-2,2,4-trimethylhexane, methyl 2,6-diisocyanatohexanoate (lysine diisocyanate); isophorone Alicyclic diisocyanates such as diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like.
　硬化剤の含有量は特に限定されない。一例を挙げると、硬化剤の含有量は、プライマー層を形成する上記樹脂１００質量部に対して、１～１５質量部であることが好ましく、３～１０質量部であることがより好ましい。 The content of the curing agent is not particularly limited. For example, the content of the curing agent is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, with respect to 100 parts by mass of the resin forming the primer layer.
　本実施形態のプライマー層は、黒色染料を含む。黒色染料は特に限定されない。一例を挙げると、黒色染料は、アゾ（モノアゾ、ジスアゾ等）染料、アゾ－メチン染料、アントラキノン系染料キノリン染料、ケトンイミン染料、フルオロン染料、ニトロ染料、キサンテン染料、アセナフテン染料、キノフタロン染料、アミノケトン染料、メチン染料、ペリレン染料、クマリン染料、ペリノン染料、トリフェニル染料、トリアリルメタン染料、フタロシアニン染料、インクロフェノール染料、アジン染料およびこれらの混合物等である。 The primer layer of this embodiment contains a black dye. Black dyes are not particularly limited. Examples of black dyes include azo (monoazo, disazo, etc.) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketoneimine dyes, fluorone dyes, nitro dyes, xanthene dyes, acenaphthene dyes, quinophthalone dyes, aminoketone dyes, methine dyes, perylene dyes, coumarin dyes, perinone dyes, triphenyl dyes, triallylmethane dyes, phthalocyanine dyes, incrophenol dyes, azine dyes and mixtures thereof.
　黒色染料の含有量は特に限定されない。一例を挙げると、黒色染料の含有量は、プライマー層中、２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることがさらに好ましい。また、黒色染料の含有量は、プライマー層中、７５質量％以下であることが好ましい。黒色染料の含有量が上記範囲内であることにより、金属調加飾フィルムは、インジウム蒸着層の海島構造の島同士の間に黒色染料が充分に入り込み、金属調加飾フィルムは、より曇りの抑制された優れた金属光沢を示し得る。そして、金属調加飾フィルムは、成形性も優れる。 The content of the black dye is not particularly limited. For example, the black dye content in the primer layer is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. Also, the content of the black dye is preferably 75% by mass or less in the primer layer. When the content of the black dye is within the above range, the black dye sufficiently penetrates between the islands of the sea-island structure of the indium vapor-deposited layer in the metal-tone decorative film, and the metal-tone decorative film becomes more cloudy. It can exhibit excellent metallic luster under control. Also, the metallic decorative film has excellent formability.
　図１は、プライマー層に黒色染料も黒色顔料も添加していないサンプルの模式図である。図２は、プライマー層に黒色染料を添加したサンプルの模式図である。図３は、プライマー層に黒色顔料を添加したサンプルの模式図である。なお、図１～図３では、説明の明瞭化のため、アンカー層１、インジウム蒸着層２、プライマー層３のみが図示されている。 Fig. 1 is a schematic diagram of a sample in which neither black dye nor black pigment is added to the primer layer. FIG. 2 is a schematic diagram of a sample in which a black dye is added to the primer layer. FIG. 3 is a schematic diagram of a sample in which a black pigment is added to the primer layer. 1 to 3, only the anchor layer 1, the indium deposited layer 2, and the primer layer 3 are shown for clarity of explanation.
　図１に示されるように、インジウム蒸着層２は、アンカー層１上に、たとえば、真空蒸着法により設けられる。そのため、インジウムの島構造（島の部分２ａ）の突出部分は、プライマー層３側に形成されると考えられる。そうすると、基材側から入射した入射光（入射光Ｌ１）は、インジウムの島の部分２ａの底の部分（アンカー層１とインジウム蒸着層２との界面付近）で正反射（正反射光Ｌ２）、および、拡散反射（拡散反射光Ｌ３）するとともに、プライマー層３に黒色染料も黒色顔料も添加していないサンプルにおいては、インジウムの島の部分２ａの突出部分（断面が略扇形形状の部分）においても拡散反射（拡散反射光Ｌ３）すると考えられる。そして、この拡散反射光の一部は、隣接するインジウムの島の部分２ａの突出部分でも拡散反射を起こし、いわゆる多重拡散反射を引き起こすと考えられる。これが、シェード・ハイライト特性の劣化、すなわち、シェード（影）の部分が充分に暗くならずに、曇りとして視認されていると推察される。なお、最終製品では、製品は、基材側から観察される。 As shown in FIG. 1, the indium deposition layer 2 is provided on the anchor layer 1 by, for example, a vacuum deposition method. Therefore, it is considered that the projecting portion of the indium island structure (island portion 2a) is formed on the primer layer 3 side. Then, the incident light (incident light L1) incident from the substrate side is specularly reflected (specularly reflected light L2) at the bottom portion of the indium island portion 2a (near the interface between the anchor layer 1 and the indium deposition layer 2). , and in a sample in which neither black dye nor black pigment is added to the primer layer 3 while diffusely reflecting (diffuse reflected light L3), the protruding portion of the indium island portion 2a (portion with a substantially fan-shaped cross section) is also considered to be diffusely reflected (diffuse reflected light L3). Part of this diffusely reflected light is also thought to be diffusely reflected by the protruding portions of the adjacent indium island portions 2a, causing so-called multiple diffuse reflection. This is presumed to be the deterioration of the shade/highlight characteristics, that is, the shade (shadow) portion is not sufficiently darkened and is visually recognized as cloudy. In the final product, the product is observed from the substrate side.
　一方、図２に示されるように、プライマー層３に黒色染料を添加したサンプルにおいては、黒色染料を添加した樹脂Ｒがインジウムの島の部分２ａの突出部分の周囲にも充分に回り込む。その結果、インジウムの島の部分２ａの突出部分において、拡散反射が起こりにくく（拡散反射光が黒色染料を添加した樹脂で吸収されるため）、シェード（影）の部分が充分に暗くなり、シェード・ハイライト特性が優れると推察される。 On the other hand, as shown in FIG. 2, in the sample in which the black dye is added to the primer layer 3, the black dye-added resin R sufficiently wraps around the projecting portion of the indium island portion 2a. As a result, diffuse reflection is less likely to occur at the projecting portion of the indium island portion 2a (because the diffusely reflected light is absorbed by the resin to which the black dye is added), and the shade (shadow) portion becomes sufficiently dark.・Highlight characteristics are presumed to be excellent.
　なお、図３に示されるように、プライマー層３に黒色顔料Ｐ１を添加したサンプルについて、一般的な顔料の粒径は小さくても４０ｎｍ～５０ｎｍである。そのため、インジウムの島構造（島の部分２ａ）同士の間に黒色顔料Ｐ１が充分に入り込めない。その結果、拡散反射が起こり、シェード・ハイライト特性の劣化、すなわち、シェード（影）の部分が充分に暗くならずに、曇りとして視認されると推察される。 In addition, as shown in FIG. 3, for the sample in which the black pigment P1 is added to the primer layer 3, the particle size of the general pigment is 40 nm to 50 nm at the smallest. Therefore, the black pigment P1 cannot sufficiently enter between the indium island structures (island portions 2a). As a result, diffuse reflection occurs, and the shade/highlight characteristics are degraded, that is, the shade (shadow) portion is not sufficiently darkened and is visually recognized as cloudiness.
　以上より、優れたシェード・ハイライト特性を得るためには、黒色染料を含むプライマー層は、インジウムの島構造（島の部分）が突出している側に設けることが好ましいと考えられる。 From the above, in order to obtain excellent shade/highlight characteristics, it is considered preferable to provide a primer layer containing a black dye on the side where the indium island structure (island portion) protrudes.
　なお、プライマー層は、上記黒色染料のほか、金属調加飾フィルムの色彩を整えたり、意匠性を向上する等を目的として、着色剤をさらに含んでもよい。このような着色剤は、たとえば、各種顔料、染料等であり、チタン白（酸化チタン）、アンチモン白、黄鉛、チタン黄、弁柄、カドミウム赤、群青、コバルトブルーなどの無機顔料、キナクリドンレッド、イソインドリノンイエロー、フタロシアニンブルーなどの有機顔料または染料、アルミニウム、真鍮などの鱗片状箔片からなる金属顔料、二酸化チタン被覆雲母、塩基性炭酸鉛などの鱗片状箔片からなる真珠光沢（パール）顔料等である。 In addition to the black dye, the primer layer may further contain a coloring agent for the purpose of adjusting the color of the metallic decorative film and improving the design. Such coloring agents include, for example, various pigments, dyes, etc., and inorganic pigments such as titanium white (titanium oxide), antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, cobalt blue, quinacridone red. , isoindolinone yellow, phthalocyanine blue, and other organic pigments or dyes; metal pigments consisting of scale-like foils such as aluminum and brass; titanium dioxide-coated mica; ) pigments and the like.
　プライマー層の厚みは特に限定されない。一例を挙げると、プライマー層の厚みは、０．１μｍ以上であることが好ましく、０．５μｍ以上であることがより好ましい。また、プライマー層の厚みは、３μｍ以下であることが好ましく、２μｍ以下であることがより好ましい。 The thickness of the primer layer is not particularly limited. For example, the thickness of the primer layer is preferably 0.1 μm or more, more preferably 0.5 μm or more. Also, the thickness of the primer layer is preferably 3 μm or less, more preferably 2 μm or less.
（接着層）
　接着層は、被着体に、金属調加飾フィルムを貼り合わせるために設けられる。また、接着層は、プライマー層の表面のうち、インジウム蒸着層が形成された面と反対側の面に設けられ得る層である。 (adhesive layer)
The adhesive layer is provided for bonding the metallic decorative film to the adherend. Also, the adhesion layer is a layer that can be provided on the surface of the primer layer opposite to the surface on which the indium deposition layer is formed.
　本実施形態において、接着層は、任意である。すなわち、接着層は、上記したプライマー層に設けられてもよく、プライマー層が接着層の機能を兼ねる場合には省略されてもよい。本実施形態の金属調加飾フィルムは、接着層が設けられることにより、種々の基材に貼り付けて用いることができ、塗装よりも簡易かつ安全な方法で、金属光沢感を付与することができる。一方、プライマー層が接着層の機能を兼ねることにより接着層が省略される場合、金属調加飾フィルムは、コストが削減され得る。 In this embodiment, the adhesive layer is optional. That is, the adhesive layer may be provided on the primer layer described above, or may be omitted when the primer layer also functions as the adhesive layer. Since the metallic decorative film of the present embodiment is provided with an adhesive layer, it can be used by being attached to various substrates, and a metallic luster can be imparted by a simpler and safer method than painting. can. On the other hand, when the adhesive layer is omitted because the primer layer also functions as the adhesive layer, the cost of the metallic decorative film can be reduced.
　接着層は特に限定されない。一例を挙げると、接着層は、各種接着剤、粘着剤、感圧粘着剤（ＰＳＡ：Pressure Sensitive Adhesive）等からなる。接着剤は特に限定されない。一例を挙げると、接着剤は、アクリル樹脂系、ウレタン樹脂系、ウレタン変性ポリエステル樹脂系、ポリエステル樹脂系、エポキシ樹脂系、エチレン－酢酸ビニル共重合樹脂（ＥＶＡ）系、ビニル樹脂系（塩ビ、酢ビ、塩ビ－酢ビ共重合樹脂）、スチレン－エチレン－ブチレン共重合体樹脂系、ポリビニルアルコール樹脂系、ポリアクリルアミド樹脂系、ポリアクリルアミド樹脂系、イソブチレンゴム、イソプレンゴム、天然ゴム、ＳＢＲ、ＮＢＲ、シリコーンゴム等の樹脂からなる。これらの樹脂は、適宜、溶剤に溶解されて使用されてもよく、無溶剤で使用されてもよい。 The adhesive layer is not particularly limited. For example, the adhesive layer consists of various adhesives, adhesives, pressure sensitive adhesives (PSA: Pressure Sensitive Adhesive), and the like. The adhesive is not particularly limited. Examples of adhesives include acrylic resins, urethane resins, urethane-modified polyester resins, polyester resins, epoxy resins, ethylene-vinyl acetate copolymer (EVA), vinyl resins (vinyl chloride, vinegar vinyl chloride-vinyl acetate copolymer resin), styrene-ethylene-butylene copolymer resin system, polyvinyl alcohol resin system, polyacrylamide resin system, polyacrylamide resin system, isobutylene rubber, isoprene rubber, natural rubber, SBR, NBR, It is made of resin such as silicone rubber. These resins may be appropriately dissolved in a solvent and used, or may be used without a solvent.
　接着層の厚みは特に限定されない。一例を挙げると、接着層の厚みは、１０μｍ以上であることが好ましく、１５μｍ以上であることがより好ましい。また、接着層の厚みは、６０μｍ以下であることが好ましく、５５μｍ以下であることがより好ましい。接着層の厚みが上記範囲内であることにより、得られる金属調加飾フィルムは、接着時の外観および接着性がさらに優れる。 The thickness of the adhesive layer is not particularly limited. For example, the thickness of the adhesive layer is preferably 10 μm or more, more preferably 15 μm or more. Also, the thickness of the adhesive layer is preferably 60 μm or less, more preferably 55 μm or less. By setting the thickness of the adhesive layer within the above range, the resulting metallic decorative film is more excellent in appearance and adhesiveness when adhered.
　接着層は、上記着色剤のほか、金属顔料が付与されることにより、意匠性が付与されてもよい。また、接着層は、帯電防止剤等が配合されることにより、帯電防止効果などの機能性が付与されてもよい。これにより、接着層は、貼り合わせ適性が向上し得る。 The adhesive layer may be imparted with a design property by being imparted with a metallic pigment in addition to the above-mentioned coloring agent. Further, the adhesive layer may be provided with functionality such as an antistatic effect by blending an antistatic agent or the like. Thereby, the adhesive layer can be improved in bonding aptitude.
　金属調加飾フィルム全体の説明に戻り、本実施形態の金属調加飾フィルムは、入射角が６０°における鏡面光沢度（ＧＳ６０°）と、入射角および受光角が４５°におけるＬ＊値（Ｌ＊４５）との割合（ＧＳ６０°／Ｌ＊４５）が、７５以上であればよく、８２以上であることが好ましく、８５以上であることがより好ましい。このような割合（ＧＳ６０°／Ｌ＊４５）を示す金属調加飾フィルムは、より曇りの抑制された優れた金属光沢を示し得る。本実施形態において、入射角が６０°における鏡面光沢度（ＧＳ６０°）は、アピアランスアナライザー（Ｒｈｏｐｏｉｎｔ　ＩＱ－Ｓ、Ｒｈｏｐｏｉｎｔ社製）を使用して、金属調加飾フィルム表面に対して、入射角６０°から光を照射して、正反射光を受光することにより測定し得る。また、入射角および受光角が４５°におけるＬ＊値（Ｌ＊４５）は、多角度分光光度計（ＭＡ－Ｔ６、エックスライト社製）を使用して、金属調加飾フィルムの表面に対して光源からの光を４５°の入射角で入射させ、受光器の受光角を４５°に設置して金属調加飾フィルムの表面からの反射光を受光器で受光させてＬ＊値を算出することにより測定し得る。ここで、受光角４５°とは、金属調加飾フィルムの表面における法線方向からの傾斜角が４５°であることを意味する。入射角４５°とは、受光角４５°の方向に対し、金属調加飾フィルムの表面における法線方向に向かって４５°傾斜した方向、すなわち、金属調加飾フィルムの表面における法線方向を意味する。 Returning to the description of the entire metallic decorative film, the metallic decorative film of the present embodiment has a specular glossiness (GS60°) at an incident angle of 60° and an L* value ( L*45) (GS60°/L*45) should be 75 or more, preferably 82 or more, and more preferably 85 or more. A metallic decorative film exhibiting such a ratio (GS60°/L*45) can exhibit excellent metallic luster with more suppressed fogging. In this embodiment, the specular glossiness (GS60°) at an incident angle of 60° was measured using an appearance analyzer (Rhopoint IQ-S, manufactured by Rhopoint) with respect to the metallic decorative film surface at an incident angle of 60°. It can be measured by irradiating light from 10° and receiving specularly reflected light. In addition, the L* value (L*45) at an incident angle and a light receiving angle of 45° was measured using a multi-angle spectrophotometer (MA-T6, manufactured by X-Rite) with respect to the surface of the metallic decorative film. The light from the light source is incident at an incident angle of 45°, the light receiving angle of the light receiver is set at 45°, and the reflected light from the surface of the metal-like decorative film is received by the light receiver to calculate the L* value. It can be measured by Here, the light-receiving angle of 45° means that the surface of the metallic decorative film has an inclination angle of 45° from the normal direction. The incident angle of 45° means a direction inclined by 45° toward the normal to the surface of the metal-like decorative film with respect to the direction of the light-receiving angle of 45°, that is, the direction of the normal to the surface of the metal-like decorative film. means.
　本実施形態において、鏡面光沢度（ＧＳ６０°）を調整する方法は特に限定されない。一例を挙げると、鏡面光沢度（ＧＳ６０°）は、インジウム蒸着層におけるインジウム蒸着層の厚みを変えることにより調整し得る。インジウム蒸着層の厚みが薄いと、アンカー層とインジウム蒸着層との界面付近において、インジウムの島構造の底の部分の割合が少なくなり、正反射成分が相対的に少なくなり、鏡面光沢度（ＧＳ６０°）は下がる方向にシフトする傾向がある。一方、インジウム蒸着層の厚みが厚いと、アンカー層とインジウム蒸着層との界面付近において、インジウムの島構造の底の部分の割合が多くなり、正反射成分が相対的に多くなり、鏡面光沢度（ＧＳ６０°）は上がる方向にシフトする傾向がある。 In this embodiment, the method for adjusting the specular glossiness (GS60°) is not particularly limited. For example, the specular glossiness (GS60°) can be adjusted by changing the thickness of the indium deposition layer in the indium deposition layer. When the thickness of the indium deposition layer is thin, the ratio of the bottom portion of the island structure of indium in the vicinity of the interface between the anchor layer and the indium deposition layer decreases, the specular reflection component decreases, and the specular glossiness (GS60 °) tends to shift downward. On the other hand, when the thickness of the indium vapor deposition layer is thick, the ratio of the bottom portion of the indium island structure increases near the interface between the anchor layer and the indium vapor deposition layer, and the specular reflection component becomes relatively large. (GS60°) tends to shift upwards.
　本実施形態においてＬ＊値（Ｌ＊４５）を上記範囲に調整する方法は特に限定されない。一例を挙げると、Ｌ＊値（Ｌ＊４５）は、プライマー層中に添加する黒色染料の濃度を変えることにより調整し得る。黒色染料の濃度が低いと、プライマー層側に突出しているインジウムの島構造の突出部分における拡散反射光を吸収する割合が低下するため、シェード・ハイライト特性の劣化、つまり、シェード（影）の部分が充分に暗くならずに、曇りとして視認されてしまう方向にシフトする傾向がある。この場合、Ｌ＊値（Ｌ＊４５）は大きくなる。一方、黒色染料の濃度が高いと、プライマー層側に突出しているインジウムの島構造の突出部分における拡散反射光を吸収する割合が増加するため、シェード・ハイライト特性の良化、つまり、シェード（影）の部分が充分に暗くなり、曇りとして視認されない方向にシフトする傾向がある。この場合、Ｌ＊値（Ｌ＊４５）は小さくなる。 In this embodiment, the method of adjusting the L* value (L*45) within the above range is not particularly limited. For example, the L* value (L*45) can be adjusted by changing the concentration of black dye added in the primer layer. If the concentration of the black dye is low, the proportion of diffusely reflected light absorbed by the protruding portion of the indium island structure protruding toward the primer layer decreases, resulting in deterioration of the shade/highlight characteristics, that is, the shade (shadow). There is a tendency to shift in the direction where the part is not dark enough and is perceived as cloudy. In this case, the L* value (L*45) will be large. On the other hand, when the concentration of the black dye is high, the proportion of diffusely reflected light absorbed by the protruding portions of the indium island structure protruding toward the primer layer side increases, so the shade/highlight characteristics are improved. The shaded area tends to become sufficiently dark and shift in the direction where it is not visually recognized as cloudiness. In this case, the L* value (L*45) becomes smaller.
　鏡面光沢度（ＧＳ６０°）は、正反射成分の強度と相関があり、Ｌ＊値（Ｌ＊４５）は、拡散反射成分の強度と相関がある。この両者の割合であるＧＳ６０°／Ｌ＊４５の値は、正反射成分の強度が強く（ＧＳ６０°の値が大きく）、および／または、拡散反射成分の強度が弱い（Ｌ＊４５の値が小さい）と大きくなる。一方、ＧＳ６０°／Ｌ＊４５の値は、正反射成分の強度が弱く（ＧＳ６０°の値が小さく）、および／または、拡散反射成分の強度が強い（Ｌ＊４５の値が大きい）と小さくなる。すなわち、ＧＳ６０°／Ｌ＊４５の値は、シェード・ハイライト特性の指標となり得る。この値と、目視観察した際のシェード・ハイライト感の視認性とも相関が取れている。シェード・ハイライト感が優れるとは、外光が当たった際に、曇りが感じられにくいことを意味する。すなわち、シェード・ハイライト感が優れるとは、シェード（影）がより暗く、ハイライト（正反射）がより明るく、メリハリの利いた外観を示すことを意味する。 The specular glossiness (GS60°) correlates with the intensity of the regular reflection component, and the L* value (L*45) correlates with the intensity of the diffuse reflection component. The value of GS60°/L*45, which is the ratio of the two, indicates that the intensity of the specular reflection component is strong (the value of GS60° is large) and/or the intensity of the diffuse reflection component is weak (the value of L*45 is smaller) and larger. On the other hand, the value of GS60°/L*45 is small when the intensity of the specular reflection component is low (the value of GS60° is small) and/or when the intensity of the diffuse reflection component is high (the value of L*45 is large). Become. That is, the value of GS60°/L*45 can be an index of shade/highlight characteristics. There is a correlation between this value and the visibility of shades and highlights when visually observed. The excellent shade/highlight feeling means that cloudiness is hardly felt when exposed to external light. In other words, an excellent shade/highlight feeling means that the shade (shadow) is darker and the highlight (specular reflection) is brighter, showing a sharp appearance.
　以上、本実施形態の金属調加飾フィルムは、インジウム蒸着層の海島構造の島同士の間に黒色染料が添加された樹脂が入り込む。これにより、金属調加飾フィルムは、インジウムの島が散在していることによる散乱効果を抑制することができ、曇りの抑制された優れた金属光沢を示し得る。このような金属調加飾フィルムは、たとえば三次元構造物にアウトモールド成形された際に、充分なシェード・ハイライト特性が得られる。 As described above, in the metal-tone decorative film of the present embodiment, the resin to which the black dye is added enters between the islands of the sea-island structure of the vapor-deposited indium layer. As a result, the metallic decorative film can suppress the scattering effect due to the scattered indium islands, and can exhibit excellent metallic luster with suppressed haze. Such a metallic decorative film can provide sufficient shade/highlight properties when it is out-molded into a three-dimensional structure, for example.
　金属調加飾フィルムおよび金属調製品の製造方法は特に限定されない。一例を挙げると、金属調加飾フィルムは、上記した基材にアンカー層を形成する工程（アンカー層形成工程）、アンカー層にインジウム蒸着層を形成する工程（蒸着工程）、インジウム蒸着層にプライマー層を形成する工程（プライマー層形成工程）、および、プライマー層に接着層を形成する工程（接着層形成工程）を主に含む。なお、プライマー層が接着層を兼ねる場合には、接着層形成工程は省略されてもよい。 The manufacturing method of the metallic decorative film and metallic products is not particularly limited. To give an example, the metal-tone decorative film includes a step of forming an anchor layer on the substrate (anchor layer forming step), a step of forming an indium vapor deposition layer on the anchor layer (vapor deposition step), and a primer on the indium vapor deposition layer. It mainly includes a step of forming a layer (primer layer forming step) and a step of forming an adhesive layer on the primer layer (adhesive layer forming step). When the primer layer also serves as the adhesive layer, the adhesive layer forming step may be omitted.
・アンカー層形成工程
　まず、準備された基材に対して、アンカー層が形成される。アンカー層の形成方法は特に限定されない。一例を挙げると、アンカー層は、グラビアコート、グラビアリバースコート、グラビアオフセットコート、スピンナーコート、ロールコート、リバースロールコート、キスコート、ホイラーコート、ディップコート、シルクスクリーンによるベタコート、ワイヤーバーコート、フローコート、コンマコート、かけ流しコート、刷毛塗り、スプレーコート等の通常の塗布方法や転写コーティング法等により基材層上に付与することにより形成し得る。 Anchor Layer Forming Step First, an anchor layer is formed on a prepared base material. A method for forming the anchor layer is not particularly limited. For example, the anchor layer may be gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, foiler coat, dip coat, solid coat by silk screen, wire bar coat, flow coat, It can be formed by applying it to the substrate layer by a normal coating method such as comma coating, pouring coating, brush coating, spray coating, or a transfer coating method.
・蒸着工程
　次いで、アンカー層上にインジウム蒸着層が形成される。インジウム蒸着層の形成方法は特に限定されない。一例を挙げると、蒸着方法は、従来公知の真空蒸着法、スパッタリング法、イオンプレーティング法等の物理蒸着法、または、化学蒸着法等を適宜採用し得る。これらの中でも、生産性が高いという理由により、真空蒸着法によりインジウム蒸着層を設けることが好ましい。蒸着条件は、所望するインジウム蒸着層の厚みに基づいて、従来公知の条件が適宜採用され得る。なお、金属材料は、不純物が少なく、純度が９９質量％以上であることが好ましく、９９．５質量％以上であることがより好ましい。また、金属材料は、粒状、ロッド状、タブレット状、ワイヤー状あるいは使用するルツボ形状に加工したものであることが好ましい。金属材料を蒸発させるための加熱方法は、ルツボ中に金属材料を入れて抵抗加熱あるいは高周波加熱を行う方式や、電子ビーム加熱を行う方法、窒化硼素などのセラミック製のボードに金属材料を入れ直接抵抗加熱を行う方法など、周知の方法を用いることができる。真空蒸着に用いるルツボは、カーボン製であることが望ましく、アルミナやマグネシア、チタニア、ベリリア製のルツボであってもよい。 - Vapor deposition step Next, an indium deposition layer is formed on the anchor layer. A method for forming the indium deposition layer is not particularly limited. As an example of the vapor deposition method, a conventionally known physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a chemical vapor deposition method can be appropriately adopted. Among these, it is preferable to form the indium vapor deposition layer by the vacuum vapor deposition method because of its high productivity. As the vapor deposition conditions, conventionally known conditions can be suitably adopted based on the desired thickness of the indium vapor deposition layer. The metal material preferably contains few impurities and has a purity of 99% by mass or more, more preferably 99.5% by mass or more. Moreover, the metal material is preferably processed into a granular, rod-shaped, tablet-shaped, wire-shaped, or crucible-shaped shape to be used. Heating methods for evaporating metal materials include a method in which the metal material is placed in a crucible and subjected to resistance heating or high-frequency heating, a method in which electron beam heating is performed, and a method in which the metal material is placed directly in a ceramic board such as boron nitride. A well-known method such as a method of performing resistance heating can be used. A crucible used for vacuum deposition is desirably made of carbon, and may be a crucible made of alumina, magnesia, titania, or beryllia.
・プライマー層形成工程
　プライマー層を形成する方法は特に限定されない。一例を挙げると、プライマー層は、上記樹脂を含むプライマー組成物を、グラビアコート、グラビアリバースコート、グラビアオフセットコート、スピンナーコート、ロールコート、リバースロールコート、キスコート、ホイラーコート、ディップコート、シルクスクリーンによるベタコート、ワイヤーバーコート、フローコート、コンマコート、かけ流しコート、刷毛塗り、スプレーコート等の通常の塗布方法や転写コーティング法によりインジウム蒸着層上に付与することにより形成し得る。 - Primer layer forming step The method of forming the primer layer is not particularly limited. For example, the primer layer is coated with a primer composition containing the above resin by gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, foiler coating, dip coating, and silk screen. It can be formed by applying it to the indium deposited layer by a normal coating method such as solid coating, wire bar coating, flow coating, comma coating, flow coating, brush coating, spray coating, or a transfer coating method.
・接着層形成工程
　接着層形成工程は、上記のとおり、任意の工程である。プライマー層の表面のうち、インジウム蒸着層が形成された面と反対側の面に、所望により、接着層が形成される（接着層形成工程）。接着層を形成する方法は特に限定されない。上記のとおり、接着層は、接着層を構成する樹脂溶液を、プライマー層上に塗布することにより形成してもよい。 - Adhesive Layer Forming Step As described above, the adhesive layer forming step is an optional step. An adhesion layer is optionally formed on the surface of the primer layer opposite to the surface on which the indium deposition layer is formed (adhesion layer forming step). The method of forming the adhesive layer is not particularly limited. As described above, the adhesive layer may be formed by applying a resin solution that constitutes the adhesive layer onto the primer layer.
　得られた金属調加飾フィルムを用いて、金属調製品が作製され得る。金属調製品は、たとえば、各種成形方法によって金属調加飾フィルムが成形（特にアウトモールド成形）されることにより製造され得る。成形方法は、金属調加飾フィルムの構成に基づき、適宜選択され得る。一例を挙げると、接着層を付与した金属調加飾フィルムは、真空成形、ＴＯＭ（Three dimension Overlay Method）成形等によって成形される。ＴＯＭ成形では、金属調加飾フィルムは、あらかじめ準備された被成形体（たとえば、樹脂、金属、ガラス、木材等）に付与され、熱により軟化されることにより、被成形体に追随するよう一体成形される。一方、真空成形では、金属調加飾フィルムは、ヒーターによって加熱され、軟化される。次いで、加熱された金属調加飾フィルムは、所望の３次元形状の金型に対して、真空吸引しながら押し付けられ、金属調製品の形状に追随するよう変形される。 A metal-like product can be produced using the obtained metal-like decorative film. A metal-like product can be produced, for example, by molding a metal-like decorative film (in particular, out-molding) by various molding methods. The molding method can be appropriately selected based on the configuration of the metallic decorative film. For example, a metallic decorative film provided with an adhesive layer is formed by vacuum forming, TOM (Three Dimension Overlay Method) forming, or the like. In TOM molding, a metallic decorative film is applied to a pre-prepared molded body (for example, resin, metal, glass, wood, etc.) and is softened by heat so that it can be integrated with the molded body. molded. On the other hand, in vacuum forming, the metallic decorative film is heated by a heater and softened. The heated metallic decorative film is then pressed against a desired three-dimensional mold while applying vacuum, and is deformed so as to follow the shape of the metallic preparation.
　ほかにも、金属調加飾フィルムは、ＴＯＭ成形、インラインラミネート等によって成形されてもよく、インサートインジェクション成形等によって成形されてもよい。 In addition, the metallic decorative film may be molded by TOM molding, in-line lamination, or the like, or may be molded by insert injection molding, or the like.
　このように、本実施形態の金属調製品は、上記した金属調加飾フィルムを用いた金属調製品である。上記のとおり、金属調加飾フィルムは、曇りの抑制された優れた金属光沢を示し得る。そのため、金属調加飾フィルムは、種々の物品に対して、簡便に充分なシェード・ハイライト特性を付与し、金属調製品を作製することができる。 Thus, the metal preparation of the present embodiment is a metal preparation using the metal-like decorative film described above. As described above, the metallic decorative film can exhibit excellent metallic luster with suppressed cloudiness. Therefore, the metal-like decorative film can easily impart sufficient shade/highlight properties to various articles to produce metal-like products.
　金属調製品は特に限定されない。一例を挙げると、金属調製品は、容器、筐体または車両用内外装部材である。 The metal preparation is not particularly limited. To give an example, the metal preparation is a container, a housing or an interior and exterior member for a vehicle.
　すなわち、本実施形態の金属調加飾フィルムを用いた金属調製品によれば、充分なシェード・ハイライト特性を付与した、優れた意匠性を示す種々の車両用内外装部材が作製され得る。 That is, according to the metal-prepared product using the metal-like decorative film of the present embodiment, it is possible to produce various interior and exterior parts for vehicles that are imparted with sufficient shade/highlight characteristics and exhibit excellent design.
　また、本実施形態の金属調加飾フィルムを用いた金属調製品によれば、充分なシェード・ハイライト特性を付与した、優れた意匠性を示す種々の容器が作製され得る。容器は、たとえば、化粧品の容器、飲料の容器等として好適である。 In addition, according to the metal-like products using the metal-like decorative film of the present embodiment, it is possible to produce various containers that are imparted with sufficient shade/highlight properties and exhibit excellent design properties. The container is suitable as, for example, a container for cosmetics, a container for beverages, and the like.
　さらに、本実施形態の金属調加飾フィルムを用いた金属調製品によれば、充分なシェード・ハイライト特性を付与した、優れた意匠性を示す種々の筺体が作製され得る。筺体は、たとえば、携帯電話等の通信機器、家電製品の筐体等として好適である。 Furthermore, according to the metal-like products using the metal-like decorative film of the present embodiment, it is possible to produce various housings that are imparted with sufficient shade/highlight properties and exhibit excellent design properties. The housing is suitable, for example, as a housing for a communication device such as a mobile phone, a household appliance, or the like.
　以上、本発明の一実施形態について説明した。本発明は、上記実施形態に格別限定されない。なお、上記した実施形態は、以下の構成を有する発明を主に説明するものである。 An embodiment of the present invention has been described above. The present invention is not particularly limited to the above embodiments. It should be noted that the above-described embodiment mainly describes an invention having the following configuration.
　（１）基材と、アンカー層と、インジウム蒸着層と、プライマー層と、をこの順で有し、前記プライマー層は、黒色染料を含み、入射角が６０°における鏡面光沢度（ＧＳ６０°）と、入射角および受光角が４５°におけるＬ＊値（Ｌ＊４５）との割合（ＧＳ６０°／Ｌ＊４５）は、７５以上である、金属調加飾フィルム。 (1) A base material, an anchor layer, an indium deposition layer, and a primer layer, in this order, the primer layer contains a black dye, and the specular gloss at an incident angle of 60° (GS60°) and the L* value (L*45) at an incident angle and a light receiving angle of 45° (GS60°/L*45) is 75 or more.
　このような構成によれば、金属調加飾フィルムは、インジウム蒸着層の海島構造の島同士の間に黒色染料が添加された樹脂が入り込む。これにより、金属調加飾フィルムは、インジウムの島が散在していることによる散乱効果を抑制することができ、曇りの抑制された優れた金属光沢を示し得る。このような金属調加飾フィルムは、たとえば三次元構造物にアウトモールド成形された際に、充分なシェード・ハイライト特性が得られる。 According to such a configuration, in the metal-tone decorative film, the black dye-added resin enters between the islands of the sea-island structure of the indium vapor-deposited layer. As a result, the metallic decorative film can suppress the scattering effect due to the scattered indium islands, and can exhibit excellent metallic luster with suppressed haze. Such a metallic decorative film can provide sufficient shade/highlight properties when it is out-molded into a three-dimensional structure, for example.
　（２）前記プライマー層における黒色染料の添加量は、２０～７５質量％である、（１）記載の金属調加飾フィルム。 (2) The metallic decorative film according to (1), wherein the black dye is added in an amount of 20 to 75% by mass in the primer layer.
　このような構成によれば、金属調加飾フィルムは、インジウム蒸着層の海島構造の島同士の間に黒色染料が添加された樹脂が入り込みやすい。これにより、金属調加飾フィルムは、より曇りの抑制された優れた金属光沢を示し得る。さらに、金属調加飾フィルムは、プライマー層に適量の樹脂が添加されていることにより、成形性においても、より優れる。 According to such a configuration, in the metal-tone decorative film, the black dye-added resin easily enters between the islands of the sea-island structure of the indium-deposited layer. As a result, the metallic decorative film can exhibit excellent metallic luster with less cloudiness. Furthermore, the metal-tone decorative film has excellent formability due to the addition of an appropriate amount of resin to the primer layer.
　（３）前記アンカー層は、染料または顔料を含み、前記染料または顔料は、黒色、グレーまたは有彩色の染料または顔料である、（１）または（２）記載の金属調加飾フィルム。 (3) The metallic decorative film according to (1) or (2), wherein the anchor layer contains a dye or pigment, and the dye or pigment is a black, gray or chromatic dye or pigment.
　このような構成によれば、金属調加飾フィルムは、任意の色彩のカラーメタリックを実現し得る。 According to such a configuration, the metallic decorative film can realize color metallic of any color.
　（４）前記プライマー層は、前記インジウム蒸着層が形成された面と反対側の面に、さらに、接着層が設けられている、（１）～（３）のいずれかに記載の金属調加飾フィルム。 (4) The metal preparation according to any one of (1) to (3), wherein the primer layer is further provided with an adhesive layer on the surface opposite to the surface on which the indium deposition layer is formed. decorative film.
　このような構成によれば、金属調加飾フィルムは、種々の基材に貼り付けて用いることができ、塗装よりも簡易かつ安全な方法で、金属光沢感を付与することができる。 According to such a configuration, the metallic decorative film can be used by being attached to various base materials, and can impart metallic luster by a simpler and safer method than painting.
　（５）（１）～（４）のいずれかに記載の金属調加飾フィルムを用いた、金属調製品。 (5) A metal-prepared product using the metal-like decorative film according to any one of (1) to (4).
　このような構成によれば、金属調製品は、たとえば上記した金属調加飾フィルムを三次元構造物にアウトモールド成形する場合に、充分なシェード・ハイライト特性が得られる。 According to such a configuration, the metal-like product can obtain sufficient shade/highlight characteristics when, for example, the above-described metal-like decorative film is out-molded into a three-dimensional structure.
　（６）前記金属調製品は、容器、筐体または車両用内外装部材である、（５）記載の金属調製品。 (6) The metal preparation according to (5), wherein the metal preparation is a container, a housing, or an interior/exterior member for a vehicle.
　このような構成によれば、金属調製品は、充分なシェード・ハイライト特性が得られるため、容器、筐体または車両用内外装部材といった金属調製品において好適である。 According to such a configuration, the metal preparation can obtain sufficient shade/highlight characteristics, and is therefore suitable for metal preparation such as containers, housings, or vehicle interior and exterior members.
　以下、実施例により本発明をより具体的に説明する。本発明は、これら実施例に何ら限定されない。なお、特に制限のない限り、「％」は「質量％」を意味し、「部」は「質量部」を意味する。 The present invention will be described in more detail below with reference to examples. The present invention is by no means limited to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass".
＜実施例１＞
　ＰＣからなる基材（厚み７５μｍ）を準備した。基材に対して、バーコーターを用いて、乾燥後１．３μｍとなるようにアクリルポリオールとイソシアネート系塗材とを混合したアンカーコート剤溶液を塗工し、ついでそれを１００℃で１分間乾燥させ、アンカー層を形成した。次いで、アンカー層に対して、真空蒸着法により、厚みが４０ｎｍとなるようにインジウム蒸着層を形成した。次いで、バーコーターを用いて、厚みが０．５μｍであるプライマー層を形成した。プライマー層に含まれる黒色染料（Ｎ．ＢＬＡＣＫ　Ｘ５１、ＢＡＳＦ社製）は７５質量％であった。これとは別に、アクリル系粘着剤からなる粘着層（厚み２５μｍ）付きセパレータ（ＰＥＴフィルム）を準備した。プライマー層と粘着層（接着層）とが接するように貼り合わせ、接着層をプライマー層に転写させた後、セパレータを剥離し、実施例１の金属調加飾フィルムを作製した。 <Example 1>
A substrate (thickness: 75 μm) made of PC was prepared. Using a bar coater, a base material is coated with an anchor coating agent solution obtained by mixing an acrylic polyol and an isocyanate-based coating material to a thickness of 1.3 μm after drying, and then dried at 100° C. for 1 minute. to form an anchor layer. Next, an indium deposition layer was formed on the anchor layer by a vacuum deposition method so as to have a thickness of 40 nm. Then, a primer layer having a thickness of 0.5 μm was formed using a bar coater. The black dye (N.BLACK X51, manufactured by BASF) contained in the primer layer was 75% by mass. Separately, a separator (PET film) with an adhesive layer (25 μm thick) made of an acrylic adhesive was prepared. The primer layer and the adhesive layer (adhesive layer) were laminated so as to be in contact with each other, and after the adhesive layer was transferred to the primer layer, the separator was peeled off to prepare a metallic decorative film of Example 1.
＜実施例２＞
　ＰＭＭＡからなる基材（厚み７５μｍ）に変更した以外は、実施例１と同様の方法により、金属調加飾フィルムを作製した。 <Example 2>
A metal-tone decorative film was produced in the same manner as in Example 1, except that the base material (thickness: 75 μm) made of PMMA was used.
＜比較例１＞
　湿式めっき法によりＣｒめっきを施した一般的なＣｒめっき品を用意した。 <Comparative Example 1>
A general Cr-plated product was prepared by applying Cr-plating by a wet plating method.
＜比較例２＞
　プライマー層を設けなかった以外は、実施例１と同様の方法により、金属調加飾フィルムを作製した。 <Comparative Example 2>
A metallic decorative film was produced in the same manner as in Example 1, except that no primer layer was provided.
＜比較例３＞
　プライマー層を設けなかった以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Comparative Example 3>
A metallic decorative film was produced in the same manner as in Example 2, except that no primer layer was provided.
＜比較例４＞
　プライマー層に黒色染料に代えて、黒色顔料として、スピネル構造のマンガンフェライト（平均粒子径：２００ｎｍ、カラーインデックス：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　２６）を５０質量％となるよう用いた以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Comparative Example 4>
Instead of the black dye in the primer layer, as a black pigment, manganese ferrite with a spinel structure (average particle size: 200 nm, color index: C.I. Pigment Black 26) was used in an amount of 50% by mass. A metallic decorative film was produced in the same manner as in 2.
＜比較例５＞
　プライマー層に黒色染料を配合しなかった以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Comparative Example 5>
A metallic decorative film was produced in the same manner as in Example 2, except that the primer layer did not contain a black dye.
＜比較例６＞
　プライマー層に含まれる黒色染料の濃度を１０質量％に変更した以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Comparative Example 6>
A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 10% by mass.
＜実施例３＞
　プライマー層に含まれる黒色染料の濃度を２０質量％に変更した以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Example 3>
A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 20% by mass.
＜実施例４＞
　プライマー層に含まれる黒色染料の濃度を３０質量％に変更した以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Example 4>
A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 30% by mass.
＜実施例５＞
　プライマー層に含まれる黒色染料の濃度を４０質量％に変更した以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Example 5>
A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 40% by mass.
＜実施例６＞
　プライマー層に含まれる黒色染料の濃度を５０質量％に変更した以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Example 6>
A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 50% by mass.
＜実施例７＞
　プライマー層に含まれる黒色染料の濃度を６０質量％に変更した以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Example 7>
A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 60% by mass.
＜実施例８＞
　プライマー層に含まれる黒色染料の濃度を７０質量％に変更した以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Example 8>
A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 70% by mass.
＜実施例９＞
　プライマー層に含まれる黒色染料の濃度を８０質量％に変更した以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Example 9>
A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 80% by mass.
＜実施例１０＞
　プライマー層に含まれる黒色染料の濃度を９０質量％に変更した以外は、実施例２と同様の方法により、金属調加飾フィルムを作製した。 <Example 10>
A metallic decorative film was produced in the same manner as in Example 2, except that the concentration of the black dye contained in the primer layer was changed to 90% by mass.
　実施例１～１０および比較例１～６において得られた金属調加飾フィルムについて、以下の方法に従って、Ｌ＊値および鏡面光沢度（ＧＳ）を測定した。また、成形性およびシェード・ハイライト特性を評価した。結果を表１に示す。 For the metallic decorative films obtained in Examples 1-10 and Comparative Examples 1-6, the L* value and specular glossiness (GS) were measured according to the following methods. The moldability and shade/highlight properties were also evaluated. Table 1 shows the results.
＜Ｌ＊値＞
　Ｌ＊値は、多角度分光光度計（ＭＡ－Ｔ６、エックスライト社製）を用いて、光源の入射角度を振って測定した。図４は、Ｌ＊値の角度の定義を説明するための模式図である。なお、正反射光の入射方向Ｄ２のＬ＊値（Ｌ＊０）は、当該装置では測定できないため、別途、グロス値を測定して正反射度合を測定した。角度の定義について、上記のとおり、受光器Ｐｄの受光角は４５°に設置（固定）した。受光角４５°とは、金属調加飾フィルムＦの表面における法線方向Ｄ１からの傾斜角Ａが４５°である。ここで、Ｌ＊０とは、受光角４５°に対する正反射光の入射方向、すなわち、受光角４５°の方向から、金属調加飾フィルムＦの表面における法線方向Ｄ１に向かって、９０°回転させた角度の方向より光源ＬＳからの光を入射させた時のＬ＊値を意味する。言い換えると、Ｌ＊０とは、受光角４５°の方向を金属調加飾フィルムＦの表面における法線方向Ｄ１に対して左右反転させた方向より光を入射させた時のＬ＊値を意味する。そして、Ｌ＊－１５とは、Ｌ＊０の方向から時計回りに１５°回転させた方向より光を入射させた時のＬ＊値を意味し、Ｌ＊１５とは、Ｌ＊０の方向から反時計回りに１５°回転させた方向より光を入射させた時のＬ＊値を意味し、Ｌ＊２５とは、Ｌ＊０の方向から反時計回りに２５°回転させた方向より光を入射させた時のＬ＊値を意味し、Ｌ＊４５とは、Ｌ＊０の方向から反時計回りに４５°回転させた方向より光を入射させた時のＬ＊値を意味し、Ｌ＊７５とは、Ｌ＊０の方向から反時計回りに７５°回転させた方向より光を入射させた時のＬ＊値を意味し、Ｌ＊１１０とは、Ｌ＊０の方向から反時計回りに１１０°回転させた方向より光を入射させた時のＬ＊値を意味する。 <L* value>
The L* value was measured by changing the incident angle of the light source using a multi-angle spectrophotometer (MA-T6, manufactured by X-Rite). FIG. 4 is a schematic diagram for explaining the definition of the angle of the L* value. Since the L* value (L*0) in the incident direction D2 of the specularly reflected light cannot be measured by the apparatus, the degree of specular reflection was measured by separately measuring the gloss value. Regarding the definition of the angle, as described above, the light receiving angle of the light receiver Pd was set (fixed) at 45°. The light-receiving angle of 45° means that the surface of the metallic decorative film F has an inclination angle A of 45° from the normal direction D1. Here, L*0 is the incident direction of the specularly reflected light with respect to the light receiving angle of 45°, that is, from the direction of the light receiving angle of 45° toward the normal direction D1 on the surface of the metal-tone decorative film F, 90° It means the L* value when the light from the light source LS is incident from the direction of the rotated angle. In other words, L*0 means the L* value when light is incident from a direction in which the direction of the light-receiving angle of 45° is horizontally reversed with respect to the normal direction D1 on the surface of the metallic decorative film F. do. L*-15 means the L* value when light is incident from a direction rotated 15° clockwise from the direction of L*0, and L*15 is the direction of L*0. L* means the L* value when light is incident from the direction rotated 15° counterclockwise from the L*0 direction, and L*25 means the light means the L * value when the light is incident, and L * 45 means the L * value when the light is incident from the direction rotated 45 ° counterclockwise from the direction of L * 0, L*75 means the L* value when light is incident from a direction rotated counterclockwise by 75° from the direction of L*0, and L*110 means the value of light incident from the direction counterclockwise from the direction of L*0. It means the L* value when light is incident from a direction rotated clockwise by 110°.
＜鏡面光沢度＞
　鏡面光沢度（ＧＳ２０°およびＧＳ６０°）は、アピアランスアナライザー（Ｒｈｏｐｏｉｎｔ　ＩＱ－Ｓ、Ｒｈｏｐｏｉｎｔ社製）を用いて測定した。ＧＳ２０°については、光源の入射角２０°（フィルムの法線方向に対して２０°傾斜した角度から入射）に対する光源からの光のフィルムでの正反射方向におけるグロス値を測定した。ＧＳ６０°については、光源の入射角６０°（フィルムの法線方向に対して６０°傾斜した角度から入射）に対する光源からの光のフィルムでの正反射方向におけるグロス値を測定した。 <Specular Glossiness>
The specular glossiness (GS20° and GS60°) was measured using an appearance analyzer (Rhopoint IQ-S, manufactured by Rhopoint). For GS20°, the gloss value was measured in the specular reflection direction of the light from the light source with respect to the incident angle of the light source of 20° (incident at an angle of 20° with respect to the normal direction of the film). For GS60°, the gloss value was measured in the specular reflection direction of the light from the light source with respect to the incident angle of the light source of 60° (incident at an angle inclined by 60° with respect to the normal direction of the film).
＜成形性＞
　成形性は、それぞれの積層フィルムを１４０℃雰囲気下で一軸方向に２倍延伸し（つかみ間隔：５ｃｍ）、以下の評価基準に従って評価した。
（評価基準）
　×：クラックが顕著に発生し、金属光沢が著しく低下した。
　△：クラックが若干発生し、金属光沢が低下した。
　○：クラックの発生は無いが、金属光沢が若干低下した。
　◎：クラックの発生は無く、金属光沢を充分に維持することができた。 <Moldability>
The formability was evaluated by stretching each laminated film twice in a 140° C. atmosphere in a uniaxial direction (grip distance: 5 cm) and evaluating the moldability according to the following evaluation criteria.
(Evaluation criteria)
x: Remarkable cracks occurred, and the metallic luster was remarkably lowered.
Δ: Some cracks occurred and the metallic luster decreased.
Good: No cracks occurred, but the metallic luster was slightly reduced.
⊚: No cracks occurred, and sufficient metallic luster could be maintained.
＜シェード・ハイライト特性＞
　室内のLED照明下で目視観察し、以下の評価基準に従って評価した。
（評価基準）
　×：陰影感が感じられなかった。
　△：陰影感が感じられた（程度は中）。
　○：陰影感が感じられた（程度は大）。
　◎：陰影感が顕著に感じられた（程度は非常に大）。 <Shade/Highlight Characteristics>
It was visually observed under indoor LED lighting and evaluated according to the following evaluation criteria.
(Evaluation criteria)
x: A feeling of shade was not felt.
Δ: A feeling of shade was felt (medium degree).
◯: A feeling of shade was felt (to a large degree).
(double-circle): A feeling of shadow was felt notably (the degree is very large).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示されるように、実施例１～１０の金属調加飾フィルムは、いずれも優れたシェード・ハイライト特性が得られた。特に、黒色染料の含有量が２０～７５質量％であった実施例１～８の金属調加飾フィルムは、成形性が優れていた。具体的には、図５、図６は、比較例５および実施例８の金属調加飾フィルムを用いた金属調製品の外観写真である。図５は、室内のＬＥＤ照明下で撮影された外観写真（日中の屋内外での見え方を想定）であり、図６は、暗室でＬＥＤを照射して撮影した外観写真（夜間に照明が当たった際の見え方を想定）である。図５、図６に示されるように、比較例５の金属調加飾フィルムを用いた金属調製品（左側）は、拡散反射によって曇った（白っぽい）外観であったのに対し、実施例８の金属調加飾フィルムを用いた金属調製品（右側）は、曇りが抑制された陰影のある（シェード・ハイライト特性が優れた）外観であった。 As shown in Table 1, all of the metallic decorative films of Examples 1 to 10 had excellent shade/highlight properties. In particular, the metallic decorative films of Examples 1 to 8, in which the content of the black dye was 20 to 75% by mass, were excellent in formability. Specifically, FIGS. 5 and 6 are photographs of appearances of metal-like products using the metal-like decorative films of Comparative Example 5 and Example 8. FIG. Figure 5 is an exterior photograph taken indoors under LED lighting (assuming how it looks indoors and outdoors during the day), and Figure 6 is an exterior photograph taken in a darkroom with LED lighting (illuminated at night). Assuming how it looks when it hits). As shown in FIGS. 5 and 6, the metal-like product (left side) using the metal-like decorative film of Comparative Example 5 had a cloudy (whitish) appearance due to diffuse reflection, whereas the appearance of Example 8 was cloudy (whitish) due to diffuse reflection. The metal-tone product (right side) using the metal-tone decorative film of No. 2 had a shaded appearance (excellent shade/highlight characteristics) with suppressed clouding.
　なお、比較例１の金属調加飾フィルムは、Ｃｒめっきを採用していた。Ｃｒめっきは、メッキ廃液による環境負荷の問題が生じやすく、かつ、めっき工程が必要となるため、好ましくなかった。 It should be noted that the metallic decorative film of Comparative Example 1 employed Cr plating. Cr plating is not preferable because it tends to cause environmental problems due to plating waste liquid and requires a plating process.
　１　アンカー層
　２　インジウム蒸着層
　２ａ　島の部分
　３　プライマー層
　Ａ　傾斜角
　Ｄ１　法線方向
　Ｄ２　正反射光の入射方向
　Ｆ　金属調加飾フィルム
　Ｌ１　入射光
　Ｌ２　正反射光
　Ｌ３　拡散反射光
　ＬＳ　光源
　Ｐ１　黒色顔料
　Ｐｄ　受光器
　Ｒ　樹脂 REFERENCE SIGNS LIST 1 anchor layer 2 indium deposition layer 2a island portion 3 primer layer A tilt angle D1 normal direction D2 incidence direction of specularly reflected light F metallic decorative film L1 incident light L2 specularly reflected light L3 diffusely reflected light LS light source P1 black pigment Pd Receiver R Resin

Claims (6)

  1. 　基材と、アンカー層と、インジウム蒸着層と、プライマー層と、をこの順で有し、
    　前記プライマー層は、黒色染料を含み、
    　入射角が６０°における鏡面光沢度（ＧＳ６０°）と、入射角および受光角が４５°におけるＬ＊値（Ｌ＊４５）との割合（ＧＳ６０°／Ｌ＊４５）は、７５以上である、金属調加飾フィルム。     Having a base material, an anchor layer, an indium deposition layer, and a primer layer in this order,
    The primer layer contains a black dye,
    The ratio (GS60°/L*45) between the specular glossiness (GS60°) at an incident angle of 60° and the L* value (L*45) at an incident angle and a light receiving angle of 45° is 75 or more. Metallic decorative film.
  2. 　前記プライマー層における黒色染料の添加量は、２０～７５質量％である、請求項１記載の金属調加飾フィルム。 The metallic decorative film according to claim 1, wherein the amount of the black dye added to the primer layer is 20 to 75% by mass.
  3. 　前記アンカー層は、染料または顔料を含み、
    　前記染料または顔料は、黒色、グレーまたは有彩色の染料または顔料である、請求項１または２記載の金属調加飾フィルム。     The anchor layer contains a dye or pigment,
    3. The metallic decorative film according to claim 1, wherein said dye or pigment is a black, gray or chromatic dye or pigment.
  4. 　前記プライマー層は、前記インジウム蒸着層が形成された面と反対側の面に、さらに、接着層が設けられている、請求項１～３のいずれか１項に記載の金属調加飾フィルム。 The metallic decorative film according to any one of claims 1 to 3, wherein the primer layer is further provided with an adhesive layer on the surface opposite to the surface on which the indium deposition layer is formed.
  5. 　請求項１～４のいずれか１項に記載の金属調加飾フィルムを用いた、金属調製品。 A metal-like product using the metal-like decorative film according to any one of claims 1 to 4.
  6. 　前記金属調製品は、容器、筐体または車両用内外装部材である、請求項５記載の金属調製品。 The metal preparation according to claim 5, wherein the metal preparation is a container, a housing, or an interior/exterior member for a vehicle.
PCT/JP2022/029154 2021-09-13 2022-07-28 Metallic-tone decorative film and metallic-tone product WO2023037789A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53134877A (en) * 1977-04-30 1978-11-24 Nissha Printing Production of decorating sheet
JP2019051633A (en) * 2017-09-14 2019-04-04 日産自動車株式会社 Dark chromium-tone decorative film
WO2020059255A1 (en) * 2018-09-21 2020-03-26 尾池工業株式会社 Decorative film molded body, producing method of decorative film molded body, satin plated product, container, case, and interior and exterior members for vehicle
JP2020116782A (en) * 2019-01-21 2020-08-06 尾池工業株式会社 Vapor-deposited film, black-color metal-tone product, vehicle interior/exterior member, container, and enclosure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53134877A (en) * 1977-04-30 1978-11-24 Nissha Printing Production of decorating sheet
JP2019051633A (en) * 2017-09-14 2019-04-04 日産自動車株式会社 Dark chromium-tone decorative film
WO2020059255A1 (en) * 2018-09-21 2020-03-26 尾池工業株式会社 Decorative film molded body, producing method of decorative film molded body, satin plated product, container, case, and interior and exterior members for vehicle
JP2020116782A (en) * 2019-01-21 2020-08-06 尾池工業株式会社 Vapor-deposited film, black-color metal-tone product, vehicle interior/exterior member, container, and enclosure

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