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WO2023037789A1 - Film décoratif à tons métalliques et produit à tons métalliques - Google Patents

Film décoratif à tons métalliques et produit à tons métalliques 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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English (en)
Japanese (ja)
Inventor
義広 赤座
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Oike and Co Ltd
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Oike and Co Ltd
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Publication of WO2023037789A1 publication Critical patent/WO2023037789A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin

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.

Landscapes

  • Laminated Bodies (AREA)

Abstract

L'invention concerne : un film décoratif à tons métalliques présentant un excellent éclat métallique avec un voile réduit, et de bonnes propriétés de nuance et de rehaut, par exemple, lorsqu'il est moulé sur des structures tridimensionnelles ; ainsi qu'un produit à tons métalliques. Le film décoratif selon l'invention comprend, dans cet ordre, un substrat, une couche d'ancrage, une couche de dépôt d'indium et une couche d'apprêt, cette dernière contenant un colorant noir, et le rapport (GS60 °/L*45) brillant spéculaire à un angle d'incidence de 60 ° (GS60 °) / valeur L* à un angle d'incidence et de réception de lumière de 45 ° (L*45) étant d'au moins 75.
PCT/JP2022/029154 2021-09-13 2022-07-28 Film décoratif à tons métalliques et produit à tons métalliques Ceased WO2023037789A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116355574A (zh) * 2023-03-29 2023-06-30 江西省盛纬材料有限公司 一种蓝黑色聚氨酯胶黏剂及其制备方法和应用

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 (ja) * 2017-09-14 2019-04-04 日産自動車株式会社 ダーククロム調加飾フィルム
WO2020059255A1 (fr) * 2018-09-21 2020-03-26 尾池工業株式会社 Corps moulé en film décoratif, procédé de production d'un corps moulé en film décoratif, produit plaqué satiné, récipient, boîtier et éléments intérieurs et extérieurs pour véhicule
JP2020116782A (ja) * 2019-01-21 2020-08-06 尾池工業株式会社 蒸着フィルム、黒色金属調製品、車両内外装部材、容器、筐体

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 (ja) * 2017-09-14 2019-04-04 日産自動車株式会社 ダーククロム調加飾フィルム
WO2020059255A1 (fr) * 2018-09-21 2020-03-26 尾池工業株式会社 Corps moulé en film décoratif, procédé de production d'un corps moulé en film décoratif, produit plaqué satiné, récipient, boîtier et éléments intérieurs et extérieurs pour véhicule
JP2020116782A (ja) * 2019-01-21 2020-08-06 尾池工業株式会社 蒸着フィルム、黒色金属調製品、車両内外装部材、容器、筐体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116355574A (zh) * 2023-03-29 2023-06-30 江西省盛纬材料有限公司 一种蓝黑色聚氨酯胶黏剂及其制备方法和应用

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