Decorative sheet

Abstract

To provide a decorative sheet having an excellent design property and an adhesion property between a base film and a metal vapor deposition layer.SOLUTION: A decorative sheet 1 at least comprises: a backer layer 3 at least having a non-crystalline resin layer 8, a metal vapor deposition layer 9 provided on the surface of the non-crystalline resin layer 8 and a primer layer 10 provided on the surface of the metal vapor deposition layer 9; and a transparent resin layer 5 provided on a primer layer 10 side of the backer layer 3.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a decorative sheet. [Background technology]

[0002] Conventionally, stainless steel sheets, which have excellent design properties, have been widely used in home appliances and other products, but because these sheets are hard and require special jigs and dies for forming, there has been a problem in that conventional forming jigs, dies, and processing methods cannot be used as is. In addition, the surface of stainless steel sheets is easily stained with fingerprints, which significantly impairs the appearance in areas that are frequently touched by people's hands.

[0003] Therefore, in order to improve the appearance and protect the surface, a metallic decorative sheet with excellent brightness and design has been proposed. For example, a metallic decorative film with hairlines has been proposed, which includes a base film (polyester film) with a hairline finish on one side and a metal deposition layer on the hairline-finished surface, and a thermoplastic resin film is provided on the metal deposition surface via an adhesive layer. It is described that by using such a metallic decorative film, it is possible to provide a metallic decorative film with excellent fingerprint resistance and scratch resistance without impairing moldability, as well as improving the hairline design (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2005-169740 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, the decorative film described in Patent Document 1 has a problem in that the adhesion between the polyester film and the metal vapor deposition layer is low, and peeling occurs at the interface between the polyester film and the metal vapor deposition layer. In particular, the decorative film described in Patent Document 1 requires separate printing in order to impart a design other than the hairline, and when printing is performed on the surface on which the hairline is to be processed (i.e., the surface on the metal vapor deposition layer side) instead of the hairline processing (providing a printing layer between the polyester film and the metal vapor deposition layer), the adhesion between the polyester film and the metal vapor deposition layer decreases, and peeling occurs at the interface between the polyester film and the metal vapor deposition layer.

[0006] Therefore, the present invention has been made in consideration of the above problems, and has an object to provide a decorative sheet which is excellent in design and also has excellent adhesion between the base film and the metal vapor deposition layer. [Means for solving the problem]

[0007] In order to achieve the above-mentioned object, the decorative sheet of the present invention is characterized by comprising at least a laminate comprising at least an amorphous resin layer, a metal vapor deposition layer provided on the surface of the amorphous resin layer, and a primer layer provided on the surface of the metal vapor deposition layer, and at least a transparent resin layer provided on the primer layer side of the laminate.

[0008] Another decorative sheet of the present invention comprises at least a laminate having at least an amorphous resin layer, a metal vapor deposition layer provided on the surface of the amorphous resin layer, and an adhesive layer provided on the surface of the metal vapor deposition layer, and a transparent resin layer provided on the adhesive layer side of the laminate, and is characterized in that the viscosity of the adhesive forming the adhesive layer is 1 mPa·s or more and 2000 mPa·s or less, and the surface tension of the adhesive is 20 mN / m or more and 32 mN / m or less. Effect of the Invention

[0009] According to the decorative sheet of the present invention, since a metal vapor deposition layer is provided on the surface of the amorphous resin layer, which is the base film, the adhesion between the base film and the metal vapor deposition layer can be improved. In addition, a primer layer is provided between the transparent resin layer and the metal vapor deposition layer, which have low adhesion, and an adhesive layer is provided between the transparent resin layer and the primer layer, so that the transparent resin layer and the metal vapor deposition layer can be laminated at a distance via the primer layer, which has a higher adhesiveness to the adhesive layer than the metal vapor deposition layer, and peeling at the interface between the transparent resin layer and the metal vapor deposition layer can be reliably prevented.

[0010] According to another decorative sheet of the present invention, a metal deposition layer is provided on the surface of the amorphous resin layer, which is the base film, so that the adhesion between the base film and the metal deposition layer can be improved. Also, since an adhesive layer that also serves as a primer layer is provided between the transparent resin layer and the metal deposition layer, which have low adhesion, the transparent resin layer and the metal deposition layer can be laminated at a distance via the adhesive layer without providing a separate primer layer, and peeling at the interface between the transparent resin layer and the metal deposition layer can be reliably prevented. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a cross-sectional view showing a decorative sheet according to a first embodiment of the present invention. [Diagram 2] FIG. 1 is a cross-sectional view showing micropores formed in a metal vapor deposition layer in a decorative sheet according to a first embodiment of the present invention. [Diagram 3] FIG. 4 is a cross-sectional view showing a decorative sheet according to a second embodiment of the present invention. [Figure 4] FIG. 4 is a cross-sectional view showing micropores formed in a metal vapor deposition layer in a decorative sheet according to a second embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The decorative sheet of the present invention will be specifically described below. Note that the present invention is not limited to the following embodiments, and can be appropriately modified and applied within the scope of the present invention.

[0013] (First embodiment) As shown in FIG. 1, the decorative sheet 1 of this embodiment comprises a surface layer 2, a backer layer 3 provided on the back side of the surface layer 2, and an adhesive layer 4 provided between the surface layer 2 and the backer layer 3.

[0014] <Surface layer> The surface layer 2 is a layer for preventing scratches and the like from occurring on the surface of the decorative sheet 1, and as shown in Figure 1, is a laminate comprising a transparent resin layer 5 which is a surface substrate layer, a printed layer 6 provided on the back side of the transparent resin layer 5, and a hard coat layer 7 provided on the front side of the transparent resin layer 5.

[0015] (Transparent resin layer) As shown in Fig. 1, the transparent resin layer 5 is provided on the primer layer 10 side of the backer layer 3, and a film made of a transparent resin mainly composed of a polyethylene terephthalate resin or a polyvinyl chloride resin is used as the transparent resin layer 5. This film is preferably one having excellent surface hardness and chemical resistance, such as a stretched polyethylene terephthalate film. In addition, since a hard coat layer 7 is formed on the surface of the transparent resin layer 5, a biaxially stretched polyethylene terephthalate film is preferable from the viewpoint of ensuring durability such as solvent resistance and heat resistance, versatility, smoothness, etc.

[0016] The thickness of the transparent resin layer 5 is preferably 20 to 300 μm, and more preferably 50 to 200 μm. If the thickness of the transparent resin layer 5 is 20 μm or more, the thickness from the surface to the printed layer 6 is large, so that a design with depth (a luxurious feel) can be ensured, the appearance and surface performance as a decorative sheet are improved, and the occurrence of scratches in the printed layer 6 can be prevented. If the thickness of the transparent resin layer 5 is 300 μm or less, it is advantageous in terms of cost and the workability during folding can be improved (springback can be prevented).

[0017] From the viewpoint of imparting stain resistance, weather resistance, and the like to the transparent resin layer 5, a coating layer, a transfer layer, and the like may be provided on the transparent resin layer 5.

[0018] (Printing layer) The printed layer 6 enhances the design of the decorative sheet 1, and is formed by printing on the surface of the transparent resin layer 5 facing the backer layer 3 (i.e., the surface facing the primer layer 10), and examples of the designs and patterns formed by printing on the printed layer 6 include wood grain, stone grain, cloth grain, sand grain, tiled patterns, brickwork patterns, leather-grained patterns, geometric patterns, letters, symbols, metallic patterns, etc. These designs and patterns may be formed alone, or two or more types may be combined to form the designs.

[0019] Examples of printing methods include gravure printing, screen printing, flexographic printing, letterpress printing, and inkjet printing.

[0020] The ink used for the printing layer 6 contains a binder resin and a colorant. Examples of the binder resin include acrylic resin, vinyl chloride-vinyl acetate copolymer, chlorinated polypropylene, polyester resin, cellulose-based resin, and urethane-based resin. Examples of the colorant include inorganic pigments such as titanium white, zinc oxide, carbon black, iron black, red oxide, chrome vermilion, cadmium red, ultramarine blue, cobalt blue, yellow lead, and titanium yellow; organic pigments such as phthalocyanine blue, indanthrene blue, isoindolinone yellow, benzylidine yellow, quinacridone red, polyazo red, perylene red, and aniline black; and pearlescent (pearl) pigments such as scaly foil powder of aluminum, brass, and the like. The above colorants can be used alone or in combination of two or more.

[0021] The ink used for the printed layer 6 may contain additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a storage stabilizer, a plasticizer, a lubricant, a filler, etc. The thickness of the printed layer 6 is preferably 0.1 to 10 μm.

[0022] (Hard coat layer) The hard coat layer 7 is intended to further enhance prevention of scratches on the surface of the decorative sheet 1, and is a layer having a pencil hardness harder than HB. This hard coat layer 7 is a layer formed from an active energy ray curable resin that polymerizes when irradiated with active energy rays (ultraviolet rays or electron beams).

[0023] Examples of this active energy ray-curable resin include polyfunctional (meth)acrylates having two or more (meth)acryloyl groups in the molecule, and monofunctional (meth)acrylates having one (meth)acryloyl group in the molecule.

[0024] Examples of polyfunctional (meth)acrylates having two or more (meth)acryloyl groups in the molecule include polyol poly(meth)acrylates such as neopentyl glycol di(meth)acrylate, 1,6-hexanediol diacrylate, (meth)trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; bisphenol A diglyceride; Examples of the epoxy (meth)acrylate include diglycidyl ether di(meth)acrylate, di(meth)acrylate of neopentyl glycol diglycidyl ether, and di(meth)acrylate of 1,6-hexanediol diglycidyl ether; polyester (meth)acrylate obtained by esterifying a polyhydric alcohol, a polycarboxylic acid and / or anhydride thereof, and (meth)acrylic acid; urethane (meth)acrylate obtained by reacting a polyhydric alcohol, a polyisocyanate, and a hydroxyl group-containing (meth)acrylate; and polysiloxane poly(meth)acrylate.

[0025] Examples of the monofunctional (meth)acrylate include hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and glycidyl (meth)acrylate.

[0026] These may be used alone or in combination of two or more.

[0027] The thickness of the hard coat layer 7 is preferably 1 to 30 μm, and more preferably 2 to 20 μm. If the thickness of the hard coat layer 7 is 1 μm or more, the occurrence of scratches in the decorative sheet 1 can be effectively prevented, and if it is 30 μm or less, the occurrence of cracks in the hard coat layer 7 can be prevented.

[0028] <Adhesive layer> The adhesive layer 4 is provided between the surface layer 2 and the backer layer 3 to bond them together.

[0029] Any adhesive that is typically used for adhesive layers in decorative sheets can be used as the adhesive forming the adhesive layer 4. The adhesive forming the adhesive layer 4 may be of a two-component curing type, a one-component curing type, or an ultraviolet curing type.

[0030] Specific examples of adhesives include heat-sealable resins such as polyester resins, polyurethane resins, polyester-polyurethane resins, acrylic resins, and ethylene-vinyl acetate copolymers. Of these, polyester resins and polyester-polyurethane resins are preferred. These may be used alone or in combination of two or more. The adhesive may contain a curing agent such as isocyanate, and from the viewpoint of improving the appearance and adhesive strength of the decorative sheet 1, polyester resins containing isocyanate as a curing agent are preferred. The adhesive layer 4 is also preferably free of colorants, i.e., uncolored.

[0031] The thickness of the adhesive layer 4 is preferably 2 to 30 μm, and more preferably 5 to 15 μm. In particular, when the thickness of the adhesive layer 4 is 5 μm or more, the surface layer 2 and the backer layer 3 can be bonded with sufficient adhesive strength. Furthermore, when the thickness of the adhesive layer 4 is 15 μm or less, the effect on the transparency and production costs of the decorative sheet 1 is small, and flammability can also be suppressed.

[0032] <Backer layer> The backer layer 3 is a layer that improves the design of the decorative sheet 1, and as shown in Figure 1, is a laminate comprising an amorphous resin layer 8 which is a base layer, a metal vapor deposition layer 9 provided on the surface of the amorphous resin layer 8, and a primer layer 10 provided on the surface of the metal vapor deposition layer 9.

[0033] (Amorphous resin layer) The amorphous resin layer 8 is a resin layer formed from an amorphous resin. Here, the term "amorphous resin" includes an amorphous resin and an amorphous crystalline resin.

[0034] The term "non-crystalline resin" refers to a resin that has only a glass transition point and whose molecular chains are arranged randomly. Examples of such resins include polystyrene (PS) resin, polyvinyl chloride (PVC) resin, acrylonitrile styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, polymethyl methacrylate (PMMA) resin, polycarbonate (PC) resin, modified polyphenylene ether (PPE) resin, and glycol-modified polyethylene terephthalate (PETG) resin.

[0035] Additionally, "crystalline resin in an amorphous state" refers to a resin that has been made amorphous by processing (e.g., by rapidly cooling from a molten state), and examples of such resins include "crystalline polyethylene terephthalate (APET) resin in an amorphous state and recycled polyethylene terephthalate (hereinafter sometimes referred to as "RPET")-based resins" described in paragraph

[0011] of Patent No. 4760356.

[0036] The recycled PET resin is a recycled resin derived from PET bottles, and is preferably made from crushed PET bottles, because it is inexpensive and easy to obtain. The recycled PET resin may contain crushed labels (including printing, adhesives, etc.) and caps that were attached to the PET bottles, as long as the effect of the present invention is not impaired. The amorphous resin layer 8 may contain recycled PET resin in the range of 50% by mass to 100% by mass.

[0037] The transparent resin layer 5 may be made of a resin material containing recycled PET resin. In this case, the transparent resin layer 5 may contain 50% by mass or more and 95% by mass or less of recycled PET resin.

[0038] The content of recycled PET resin in the entire decorative sheet 1 can be 50% by mass or more and 95% by mass or less. In the decorative sheet 1 of this embodiment, the resin component of the decorative sheet 1 contains 50% by mass or more of recycled PET resin derived from PET bottles, so a more environmentally friendly decorative sheet 1 can be provided compared to decorative sheets that have a low proportion of recycled resin in the total resin component.

[0039] The thickness of the amorphous resin layer 8 is preferably 50 to 500 μm, and more preferably 80 to 350 μm. If the thickness of the amorphous resin layer 8 is 50 μm or more, it is possible to prevent damage to the decorative sheet 1 caused by small stress (for example, stress of 15 N or less), and to reduce the influence of uneven surfaces formed on the substrate when the decorative sheet 1 is adhered to a substrate such as wood to which it is attached. If the thickness of the amorphous resin layer 8 is 500 μm or less, it is possible to improve the workability during bending (prevent springback).

[0040] The amorphous resin layer 8 may be a colored layer containing a color pigment. By using a colored layer as the amorphous resin layer 8, it becomes possible to reliably conceal the color of the base, such as wood, to which the decorative sheet 1 is attached. The color pigment is not particularly limited, and for example, the colorant used in the printing layer 6 can be used.

[0041] (Metal deposited layer) The metal vapor deposition layer 9 is a layer that improves the brightness and design (metallic appearance) of the decorative sheet 1, and in the decorative sheet 1 of this embodiment, as shown in Fig. 1, the metal vapor deposition layer 9 is provided on the surface of an amorphous resin layer 8, which is a base film. The metal vapor deposition layer 9 is a thin film that has a sea-island structure or micropores, and when an organic solvent component of a primer or adhesive is applied, it directly penetrates the amorphous resin layer that is not metal vapor deposited, thereby improving the adhesion between the amorphous resin layer 8 and the metal vapor deposition layer 9.

[0042] The metal material for forming the metal deposition layer 9 is not particularly limited, and examples of the metal material that can be used include aluminum, indium, tin, chromium, zinc, gold, and silver. The metal material can be deposited by known methods such as vacuum deposition, physical deposition such as sputtering, and chemical deposition such as CVD (Chemical Vapor Deposition).

[0043] The thickness of the metal vapor deposition layer 9 is preferably 0.001 to 0.2 μm, and more preferably 0.001 to 0.1 μm. If the thickness of the metal vapor deposition layer 9 is 0.001 μm or more, a metal design can be imparted. If the thickness of the metal vapor deposition layer 9 is 0.2 μm or less, an increase in costs can be suppressed.

[0044] The metal vapor deposition layer 9 is in a state where the metal particles are physically laminated on the base material, and there are minute areas where the metal particles are not laminated. Also, since the amorphous resin layer 8 is difficult to subject to high-temperature heat treatment (annealing treatment, etc.), and the grain growth of the metal particles is difficult and gaps occur, the metal vapor deposition layer 9 has multiple micropores 11 as shown in Figure 2.

[0045] (Primer layer) The primer layer 10 is a layer for protecting the metal vapor deposition layer 9, and is provided on the surface of the metal vapor deposition layer 9 as shown in FIG.

[0046] The primer for forming the primer layer 10 is not particularly limited, and for example, a two-component curing type primer whose main component is a polyester resin, or a primer whose main components are an acrylic resin and a vinyl chloride-vinyl acetate copolymer can be used.

[0047] The thickness of the primer layer 10 is preferably 1 to 10 μm, and more preferably 1 to 5 μm. If the thickness of the primer layer 10 is 1 μm or more, the metal vapor deposition layer 9 can be reliably protected, and if the thickness is 10 μm or less, the cost can be suppressed.

[0048] 1, in the decorative sheet 1 of this embodiment, since the primer layer 10 is provided between the transparent resin layer 5 and the metal vapor deposition layer 9, which have low adhesion, an adhesive layer 4 can be provided separately between the transparent resin layer 5 and the primer layer 10, and the transparent resin layer 5 and the metal vapor deposition layer 9 can be laminated at a distance via the primer layer 10, which has higher adhesion to the adhesive layer 4 than the metal vapor deposition layer 9. As a result, peeling at the interface between the transparent resin layer 5 and the metal vapor deposition layer 9 can be reliably prevented.

[0049] As described above, the metal vapor deposition layer 9 has a plurality of micropores 11, and therefore, as shown in Fig. 2, a portion of the primer layer 10 comes into direct contact with the amorphous resin layer 8 through the micropores 11. Therefore, due to the anchor effect of the micropores 11, it is possible to improve the adhesion between the amorphous resin layer 8 and the metal vapor deposition layer 9 without providing an undercoat layer.

[0050] <Manufacturing method> Next, an example of a method for producing the decorative sheet 1 of this embodiment will be described.

[0051] An active energy ray curable resin is applied to one side of the transparent resin layer 5, and active energy rays (ultraviolet rays or electron beams) are irradiated to form the hard coat layer 7. Next, a printing ink is applied by gravure printing or the like to the surface of the transparent resin layer 5 opposite to the side on which the hard coat layer 7 is provided, to form the printing layer 6, and thus the surface layer 2 is formed.

[0052] Alternatively, a coloring pigment is mixed with an amorphous resin such as recycled PET resin, and the resin mixture is used to form a sheet, forming an amorphous resin layer 8. Next, a metal material such as aluminum is deposited on one side of the amorphous resin layer 8 by vacuum deposition or the like to form a metal deposition layer 9. A primer is then applied to the surface of the metal deposition layer 9 to form a primer layer 10, and a backer layer 3 is formed.

[0053] Next, an adhesive that will become the adhesive layer 4 is applied to the surface of the printed layer 6 in the surface layer 2, and the surface layer 2 and the backer layer 3 are laminated so that the printed layer 6 to which the adhesive has been applied faces the primer layer 10 in the backer layer 3 via the adhesive, and the printed layer 6 and the primer layer 10 are bonded together by a dry lamination method using a roll, thereby bonding the surface layer 2 and the backer layer 3, and providing the adhesive layer 4 between the transparent resin layer 5 and the primer layer 10, thereby producing the decorative sheet 1 shown in FIG. 1. At this time, since the primer layer 10 is provided on the surface of the metal vapor deposition layer 9, damage to the metal vapor deposition layer 9 caused by the roll can be prevented when bonding the surface layer 2 and the backer layer 3.

[0054] Examples of methods for applying the active energy ray-curable resin, primer, and adhesive include gravure coating (including microgravure coating), comma coating, roll knife coating, die coating, roll coating, reverse roll coating, and cast coating.

[0055] Furthermore, if the overall thickness of the decorative sheet 1 is 530 μm or less, it is advantageous in terms of cost and can improve workability during folding (prevention of springback).

[0056] Second Embodiment Next, a second embodiment of the present invention will be described. Note that the same components as those in the first embodiment are given the same reference numerals and the description thereof will be omitted.

[0057] FIG. 3 is a cross-sectional view showing a decorative sheet according to this embodiment, and FIG. 4 is a cross-sectional view showing micropores formed in a vapor-deposited metal layer in the decorative sheet according to this embodiment.

[0058] As shown in Figure 3, in the decorative sheet 20 of this embodiment, an adhesive layer 4 is provided on the surface of a metal vapor deposition layer 9, and the adhesive layer 4 is also configured to serve as a primer layer in the backer layer 3 (the primer layer 10 in the first embodiment described above).

[0059] 3, in the decorative sheet 20 of this embodiment, an adhesive layer 4 that also serves as the above-mentioned primer layer 10 is provided between the transparent resin layer 5 and the metal vapor deposition layer 9, which have low adhesion, so that the transparent resin layer 5 and the metal vapor deposition layer 9 can be laminated at a distance from each other via the adhesive layer 4, as in the decorative sheet 1 of the first embodiment, without providing a separate primer layer 10. As a result, peeling at the interface between the transparent resin layer 5 and the metal vapor deposition layer 9 can be reliably prevented.

[0060] As described above, the metal vapor deposition layer 9 has a plurality of micropores 11, and therefore, as shown in Fig. 4, a part of the adhesive layer 4, which also serves as a primer layer, comes into direct contact with the amorphous resin layer 8 through the micropores 11. Therefore, the anchor effect of the micropores 11 can improve the adhesion between the amorphous resin layer 8 and the metal vapor deposition layer 9 without providing an undercoat layer.

[0061] Furthermore, in the decorative sheet 20 of this embodiment, the viscosity of the adhesive forming the adhesive layer 4 is from 1 mPa·s to 2000 mPa·s, and preferably from 10 mPa·s to 500 mPa·s. By setting the viscosity of the adhesive to from 1 mPa·s to 2000 mPa·s, the metal vapor deposition layer 9 can be protected and the design of the decorative sheet 20 can be improved, similar to the primer layer 10 described above.

[0062] The term "viscosity" used here refers to the viscosity of the coating liquid at the time of coating the adhesive, measured at 25°C using a tuning fork vibro viscometer (SV viscometer).

[0063] Furthermore, in the decorative sheet 2 of this embodiment, the surface tension of the adhesive forming the adhesive layer 4 is 20 mN / m or more and 32 mN / m or less. By setting the surface tension of the adhesive to 20 mN / m or more and 32 mN / m or less, the adhesive layer 4 can be provided on the surface of the metal vapor deposition layer 9 without reducing the coatability of the metal vapor deposition layer 9, and similarly to the primer layer 10 described above, the metal vapor deposition layer 9 can be protected, improving the design of the decorative sheet 20.

[0064] The "surface tension" referred to here means the surface tension of the coating liquid at the time of coating the adhesive, measured at 25°C by the pendant drop method.

[0065] <Manufacturing method> Next, an example of a method for producing the decorative sheet 1 of this embodiment will be described.

[0066] An active energy ray curable resin is applied to one side of the transparent resin layer 5, and active energy rays (ultraviolet rays or electron beams) are irradiated to form the hard coat layer 7. Next, a printing ink is applied by gravure printing or the like to the surface of the transparent resin layer 5 opposite to the side on which the hard coat layer 7 is provided, to form the printing layer 6, and thus the surface layer 2 is formed.

[0067] Alternatively, a coloring pigment is mixed with an amorphous resin such as recycled PET resin, and the resin mixture is used to form a sheet, forming an amorphous resin layer 8. Next, a metal material such as aluminum is deposited on one side of the amorphous resin layer 8 by vacuum deposition or the like to form a metal deposition layer 9. An adhesive that will become the adhesive layer 4 is then applied to the surface of the metal deposition layer 9 to form the adhesive layer 4, and the backer layer 3 is formed.

[0068] Next, the surface layer 2 and the backer layer 3 are laminated so that the printed layer 6 and the metal vapor deposition layer 9 of the backer layer 3 face each other via the adhesive layer 4, and the printed layer 6 and the adhesive layer 4 are bonded together by a dry lamination method using a roll, thereby bonding the surface layer 2 and the backer layer 3, and providing the adhesive layer 4, which also serves as a primer layer, between the transparent resin layer 5 and the metal vapor deposition layer 9, to produce the decorative sheet 20 shown in Fig. 3. In this case, since the adhesive layer 4, which also serves as a primer layer, is provided on the surface of the metal vapor deposition layer 9, damage to the metal vapor deposition layer 9 caused by the roll can be prevented when bonding the surface layer 2 and the backer layer 3.

[0069] The active energy ray curable resin, primer, and adhesive can be applied in the same manner as in the first embodiment.

[0070] Furthermore, similar to the decorative sheet 1 in the first embodiment described above, if the overall thickness of the decorative sheet 20 is 530 μm or less, it is advantageous in terms of cost and can improve workability when bending (preventing springback). EXAMPLES

[0071] The present invention will be described below based on examples. Note that the present invention is not limited to these examples, and these examples can be modified or changed based on the spirit of the present invention, and they are not excluded from the scope of the present invention.

[0072] The materials used in producing the decorative sheet are shown below. (1) UV-curable resin (manufactured by DIC Graphics, product name: DR2 WB-1) (2) Transparent resin film A (biaxially oriented PET film, manufactured by Toyobo Co., Ltd., product name: Cosmoshine A4300, thickness: 100 μm, crystalline) (3) Transparent resin film B (biaxially oriented RPET film, manufactured by Toyobo Co., Ltd., product name: Reshine TA065, thickness: 50 μm, crystalline) (4) Transparent resin film C (film mainly composed of polyvinyl chloride resin (manufactured by Taiyo Vinyl Corporation, product name: E-650), thickness: 60 μm, non-crystalline) (5) Transparent resin film D (biaxially oriented PET film, manufactured by DuPont, product name: Mylar 816, thickness: 12 μm, crystalline) (6) Two-component curing adhesive (manufactured by Dainichiseika Chemicals Co., Ltd., product name: polyester polyol / polyisocyanate-based two-component curing type for dry lamination, base agent: Seikabond E-295NT (100 parts by mass), curing agent: Seikabond C-75N-1.5 (10 parts by mass), solvent: ethyl acetate, diluted for 19 seconds with Zahn cup #3 (solid content: approximately 30%)) (7) Gravure printing ink (manufactured by DIC Graphics, product name: XS Ink) (8) Colored resin film A (a film in which a color pigment is added to the main component PETG resin (manufactured by Eastman Chemical Company, product name: GN071), thickness: 100 μm, non-crystalline) (9) Colored resin film B (a film in which color pigments are added to RPET resin (manufactured by ALIPLAST, product name: Alimpet), which is the main component; thickness: 150 μm, non-crystalline) (10) Colored resin film C (a film in which a color pigment is added to polyvinyl chloride resin (manufactured by Taiyo Vinyl Corporation, product name: TE-650) as the main component, thickness: 150 μm, non-crystalline) (11) Aluminum deposition layer (thickness: 60 nm) (12) Primer A (manufactured by Nippon Kako Toryo Co., Ltd., product name: SUV-381, a two-component curing primer whose main component is polyester resin) (13) Primer B (manufactured by Nippon Kako Toryo Co., Ltd., product name: BRIGHT TK, a primer whose main components are acrylic resin and vinyl chloride-vinyl acetate copolymer) (14) One-component curing adhesive (Japan Coating Resin Co., Ltd., product name: Rikabond BA-53)

[0073] Example 1 <Creating the surface layer> First, the above-mentioned ultraviolet-curable resin was applied to one side of the above-mentioned transparent resin film A, and ultraviolet rays were irradiated to form a hard coat layer. Next, the above-mentioned gravure printing ink was applied to the surface of the transparent resin film A opposite to the side on which the hard coat layer was provided, by gravure printing, to form a printed layer, thereby producing a surface layer that is a laminate in which the transparent resin layer, the printed layer provided on the back side of the transparent resin layer, and the hard coat layer provided on the front side of the transparent resin layer are laminated.

[0074] <Preparation of backer layer> First, a master batch (containing a color pigment and PETG resin) was added to the main component PETG resin (manufactured by Eastman Chemical Company, product name: GN071) to prepare a resin mixture. Next, the resin mixture was molded using an extruder (OSE-35φmm extruder) manufactured by Nagata Manufacturing Co., Ltd. under conditions of a temperature of 240° C. and a screw rotation speed of 44 rpm to obtain the above-mentioned colored resin film A. Next, aluminum was vapor-deposited on one side of the colored resin film A by a vacuum vapor deposition method to form an aluminum vapor-deposited layer. Then, the above-mentioned primer B was applied to the surface of the aluminum vapor-deposited layer to form a primer layer, and a backer layer was prepared as a laminate in which a resin layer in a non-crystalline state, a metal vapor-deposited layer provided on the surface of the resin layer in a non-crystalline state, and a primer layer provided on the surface of the metal vapor-deposited layer were laminated.

[0075] <Preparation of decorative sheet> Next, the above-mentioned two-component curing adhesive was applied to the surface of the printed layer of the surface layer at a rate of 10 g / m using a Comma Coater (registered trademark). 2 The solvent was evaporated in a drying oven, and the surface layer and backer layer were laminated so that the printed layer to which the adhesive was applied and the primer layer in the backer layer faced each other via the adhesive. The printed layer and primer layer were bonded together using a dry lamination method using a nip roll heated to 50°C, thereby adhering the surface layer and backer layer. After that, an aging treatment was performed at 35°C for 72 hours to produce the decorative sheet of this example (total decorative sheet thickness: 210 μm).

[0076] <Design evaluation> The prepared decorative sheets were inspected under illumination of 500 lux, with direct and oblique vision at a distance of 30 cm, and the design was evaluated according to the following evaluation criteria. The results are shown in Table 1. ◯: No scratches were observed on the metal deposition layer or scraping of the colored layer (amorphous resin layer). ×: Scratches on the metal vapor deposition layer or scraping of the colored layer (amorphous resin layer) were observed.

[0077] <Abrasion resistance evaluation> The edge of the cutter was pressed against the surface of the prepared decorative sheet with a force of 100 g and run horizontally for 5 cm. This process was repeated five times, and the scratch resistance was evaluated according to the following evaluation criteria. The results are shown in Table 1. ◯: The colored layer (amorphous resin layer) was not scraped off, and the aluminum vapor deposition layer was not exposed. ×: The colored layer (amorphous resin layer) was scraped off, and the aluminum vapor deposition layer was exposed.

[0078] <Peel strength evaluation> A rectangular sample with a width of 15 mm and a length of 100 mm was cut out from the prepared decorative sheet and used as a specimen. Next, a cut (15 mm) was made in the width direction of one layer (backer layer side) of this sample with a cutter and folded. Next, about 10 mm of the film of one layer was peeled off from the cut part to set as the starting point of interlayer peeling. If peeling at the cut part was difficult, the cut part was immersed in ethyl acetate for 30 seconds.

[0079] Then, using a peel tester (Shimadzu Corporation, product name: Autograph AGS-500NJ+250), one layer of film was peeled in a 90° direction at a speed of 200 mm / min, and the peel strength in the 90° peel was evaluated according to the following evaluation criteria. The results are shown in Table 1. ○: Peel strength is 10N or more. ×: Peel strength is less than 10N.

[0080] In addition, using the same samples, one layer of film was peeled off in a 180° direction at a speed of 200 mm / min using the above-mentioned peel tester, and the peel strength in the 180° peel was evaluated according to the following evaluation criteria. The results are shown in Table 1. ○: Peel strength is 15N or more. ×: Peel strength is less than 15N.

[0081] <Evaluation of peeling durability> The decorative sheets were left for one month at 70°C and one month at 45°C and 95% RH to prepare samples. Next, in the same manner as in the peel strength evaluation described above, the peel strength at 90° peeling was measured, and the decrease rate [%] of the peel strength at 90° peeling after leaving was calculated based on the following formula (1).

[0082] [Number 1] Decrease rate of peel strength at 90° peeling after standing [%] = [(peel strength at 90° peeling of sample before standing - peel strength at 90° peeling of sample after standing) / peel strength at 90° peeling of sample before standing] × 100 (1) The peel durability at 90° peeling was evaluated according to the following evaluation criteria. The results are shown in Table 1. ○: Decrease rate of peel strength at 90° peeling after standing [%]≦10. ×: Decrease rate of peel strength at 90° peeling after standing [%]>10.

[0083] Similarly, the peel strength in 180° peeling after standing was measured, and the reduction rate [%] of the peel strength in 180° peeling after standing was calculated based on the following formula (2).

[0084] [Number 2] Decrease rate of peel strength at 180° peeling after standing [%] = [(peel strength at 180° peeling of sample before standing - peel strength at 180° peeling of sample after standing) / peel strength at 180° peeling of sample before standing] x 100 (2) The peel durability in 180° peeling was evaluated according to the following evaluation criteria. The results are shown in Table 1. ○: Decrease rate of peel strength at 180° peeling after standing [%]≦10. ×: Decrease rate of peel strength at 180° peeling after standing [%]>10.

[0085] <Evaluation of peeling interface> For each sample peeled in the above peel strength evaluation and peel durability evaluation, the peel interface was evaluated according to the following evaluation criteria. The results are shown in Table 1. ◯: No peeling occurred at either the upper or lower interface of the metal vapor deposition layer. ×: Peeling occurred at either the upper or lower interface of the metal vapor deposition layer, or the material was easily broken at a peel strength of 5 N or less.

[0086] Example 2 A decorative sheet was produced in the same manner as in Example 1, except that the above-mentioned colored resin film C was used instead of the colored resin film A, and design evaluation, scratch resistance evaluation, peel strength evaluation, peel durability evaluation, and peel interface evaluation were performed. The results are shown in Table 1.

[0087] The colored resin film C was obtained by preparing a resin mixture by adding color pigments and various additives (heat stabilizers, reinforcing agents, processing aids, internal lubricants, external lubricants, and plate-out prevention agents) to the main component polyvinyl chloride resin (manufactured by Taiyo PVC, product name: TE-650), and then molding the resin mixture using an extruder manufactured by Nagata Manufacturing Co., Ltd. (OSE-35φmm extruder) at a temperature of 185°C and a screw rotation speed of 44 rpm.

[0088] Example 3 A decorative sheet was produced in the same manner as in Example 1, except that the transparent resin film C was used instead of the transparent resin film A, and evaluations of design, scratch resistance, peel strength, peel durability, and peel interface were performed. The results are shown in Table 1.

[0089] The transparent resin film C was obtained by preparing a resin mixture by adding various additives (heat stabilizers, reinforcing agents, processing aids, internal lubricants, external lubricants, and plate-out prevention agents) to the main component polyvinyl chloride resin (manufactured by Taiyo PVC, product name: E-650), and molding the resin mixture using an extruder manufactured by Nagata Manufacturing Co., Ltd. (OSE-35φmm extruder) at a temperature of 185°C and a screw rotation speed of 44 rpm.

[0090] Example 4 A decorative sheet was produced in the same manner as in Example 1, except that the transparent resin film B was used instead of the transparent resin film A, the colored resin film B was used instead of the colored resin film A, and no hard coat layer was formed. The decorative sheet was evaluated for design, scratch resistance, peel strength, peel durability, and peel interface. The results are shown in Table 1.

[0091] The colored resin film B was prepared by adding a master batch (containing a color pigment and virgin A-PET resin (manufactured by Huarun, product name: CR8816)) to the main component RPET resin (manufactured by ALIPLAST, product name: Alimpet) to prepare a resin mixture, and then molding the resin mixture using an extruder (OSE-35φmm extruder) manufactured by Nagata Manufacturing Co., Ltd. under conditions of a temperature of 265°C and a screw rotation speed of 44 rpm.

[0092] Example 5 A decorative sheet was produced in the same manner as in Example 1, except that the transparent resin film C was used instead of the transparent resin film A, and the colored resin film C was used instead of the colored resin film A, and design evaluation, scratch resistance evaluation, peel strength evaluation, peel durability evaluation, and peel interface evaluation were performed. The results are shown in Table 1.

[0093] Example 6 A decorative sheet was produced and evaluated for design, scratch resistance, peel strength, peel durability, and peel interface in the same manner as in Example 1, except that the primer A was used instead of primer B. The results are shown in Table 1.

[0094] Comparative Example 1 Except for not forming a primer layer, a decorative sheet was produced and evaluated for design and scratch resistance in the same manner as in Example 1. The results are shown in Table 2.

[0095] In this comparative example, since no primer layer was formed on the surface of the metal deposition layer, scratches were generated on the metal deposition layer, and the design was significantly deteriorated. Also, since the design was significantly deteriorated, the peel strength evaluation, peel durability evaluation, and peel interface evaluation were not performed.

[0096] Comparative Example 2 <Creating the surface layer> A surface layer was produced in the same manner as in Example 1 above, except that the transparent resin film C was used instead of the transparent resin film A.

[0097] <Preparation of backer layer> Instead of preparing the resin-bonded resin film A, the above-mentioned transparent resin film C was prepared. Next, the above-mentioned primer A was applied to one side of the transparent resin film A to form a primer layer A, and aluminum was vapor-deposited on the surface of this primer layer A by a vacuum vapor deposition method to form an aluminum vapor-deposited layer. Then, the above-mentioned primer B was applied to the surface of the aluminum vapor-deposited layer to form a primer layer B, and a backer layer was prepared as a laminate in which an amorphous resin layer, a primer layer A provided on the surface of the amorphous resin layer, a metal vapor-deposited layer provided on the surface of the primer layer A, and a primer layer B provided on the surface of the metal vapor-deposited layer were laminated.

[0098] <Preparation of decorative sheet> Next, the surface layer and the backer layer were laminated so that the printed layer in the surface layer and the primer layer B in the backer layer faced each other, and the printed layer and the primer layer B were bonded together by a thermal lamination method using a thermal laminator (speed: 1.8 m / min, thermal laminating rubber roll temperature: 170°C, pressure: 5 kg / cm), thereby adhering the surface layer and the backer layer together, thereby producing the decorative sheet of this comparative example.

[0099] Then, the design evaluation, the scratch resistance evaluation, the peel strength evaluation, the peel durability evaluation, and the peel interface evaluation were performed in the same manner as in the above-mentioned Example 1. The results are shown in Table 2.

[0100] Comparative Example 3 A decorative sheet was produced in the same manner as in Comparative Example 2, except that the transparent resin film D was used instead of the transparent resin film A, and the design, scratch resistance, peel strength, peel durability, and peel interface were evaluated. The results are shown in Table 2.

[0101] Comparative Example 4 <Creating the surface layer> First, the above-mentioned gravure printing ink was applied to the surface of the above-mentioned transparent resin film A by gravure printing to form a printed layer, and the above-mentioned ultraviolet curable resin was applied to the surface of this printed layer and irradiated with ultraviolet light to form a hard coat layer. Next, the above-mentioned primer A was applied to the surface of the transparent resin film A opposite to the side on which the hard coat layer was provided to form a primer layer A, and aluminum was vapor-deposited on the surface of this primer layer A by vacuum vapor deposition to form an aluminum vapor-deposited layer. Then, the above-mentioned primer B was applied to the surface of the aluminum vapor-deposited layer to form a primer layer B, and a surface layer was produced.

[0102] <Preparation of decorative sheet> As the backer layer, only the above-mentioned colored resin film A was prepared, and the above-mentioned two-component curing adhesive was applied to the surface of the primer layer B in the surface layer at a rate of 10 g / m using a Comma Coater (registered trademark). 2The solvent was evaporated in a drying oven, and then the surface layer and backer layer were laminated so that the primer layer B to which the adhesive was applied and the colored resin film A, which serves as the backer layer, faced each other via the adhesive. The primer layer B and the colored resin film A were then bonded together by a dry lamination method using a nip roll heated to 50°C, thereby adhering the surface layer and the backer layer. After that, an aging treatment was performed at 35°C for 72 hours, thereby producing the decorative sheet of this comparative example.

[0103] Then, the design evaluation, the scratch resistance evaluation, the peel strength evaluation, the peel durability evaluation, and the peel interface evaluation were performed in the same manner as in the above-mentioned Example 1. The results are shown in Table 2.

[0104] Comparative Example 5 <Creating the surface layer> First, the above-mentioned ultraviolet-curable resin was applied to one side of the above-mentioned transparent resin film A, and ultraviolet rays were irradiated to form a hard coat layer. Next, the above-mentioned gravure printing ink mixed with the above-mentioned primer A was applied to the surface of the transparent resin film A opposite to the side on which the hard coat layer was provided, by gravure printing, to form a printed layer containing primer A, and aluminum was vapor-deposited on the surface of this printed layer by vacuum deposition to form an aluminum vapor-deposited layer. Then, the above-mentioned primer B was applied to the surface of the aluminum vapor-deposited layer to form primer layer B, and a surface layer was produced.

[0105] <Preparation of decorative sheet> Next, the surface layer and the backer layer were bonded together in the same manner as in Comparative Example 4 above, to produce the decorative sheet of this comparative example.

[0106] Then, the design evaluation, the scratch resistance evaluation, the peel strength evaluation, the peel durability evaluation, and the peel interface evaluation were performed in the same manner as in the above-mentioned Example 1. The results are shown in Table 2.

[0107] Comparative Example 6 <Creating the surface layer> First, the above-mentioned ultraviolet-curable resin was applied to one side of the above-mentioned transparent resin film A, and ultraviolet rays were irradiated to form a hard coat layer. Next, the above-mentioned gravure printing ink was applied to the surface of the transparent resin film A opposite to the side on which the hard coat layer was provided, by gravure printing, to form a printed layer. Then, the above-mentioned primer A was applied to the surface of this printed layer to form a primer layer A, and aluminum was vapor-deposited on the surface of this primer layer A by vacuum vapor deposition to form an aluminum vapor-deposited layer. Then, the above-mentioned primer B was applied to the surface of the aluminum vapor-deposited layer to form a primer layer B, and a surface layer was produced.

[0108] <Preparation of decorative sheet> Next, the surface layer and the backer layer were bonded together in the same manner as in Comparative Example 4 above, to produce the decorative sheet of this comparative example.

[0109] Then, the design evaluation, the scratch resistance evaluation, the peel strength evaluation, the peel durability evaluation, and the peel interface evaluation were performed in the same manner as in the above-mentioned Example 1. The results are shown in Table 2.

[0110] Example 7 <Creating the surface layer> First, the above-mentioned ultraviolet-curable resin was applied to one side of the above-mentioned transparent resin film A, and ultraviolet rays were irradiated to form a hard coat layer. Next, the above-mentioned gravure printing ink was applied to the surface of the transparent resin film A opposite to the side on which the hard coat layer was provided, by gravure printing, to form a printed layer, thereby producing a surface layer that is a laminate in which the transparent resin layer, the printed layer provided on the back side of the transparent resin layer, and the hard coat layer provided on the front side of the transparent resin layer are laminated.

[0111] <Preparation of backer layer> First, a master batch (containing color pigment and PETG resin) was added to the main component PETG resin (trade name: GN071, manufactured by Eastman Chemical Co.) to prepare a resin mixture. Next, the resin mixture was molded using an extruder (OSE-35φmm extruder) manufactured by Nagata Manufacturing Co., Ltd. under conditions of a temperature of 240°C and a screw rotation speed of 44 rpm to obtain the above-mentioned colored resin film A. Next, the above-mentioned primer A was applied to one side of the colored resin film A to form a primer layer, and aluminum was vapor-deposited on the surface of this primer layer by a vacuum vapor deposition method to form an aluminum vapor-deposited layer. Then, 10 g / m of the above-mentioned two-component curing adhesive (viscosity: 80 mPa·s, surface tension: 21 mN / m) was applied to the surface of the aluminum vapor-deposited layer using a Comma Coater (registered trademark). 2 and the solvent was evaporated in a drying oven to form an adhesive layer that also served as a primer layer, thereby producing a backer layer which was a laminate comprising an amorphous resin layer, a primer layer provided on the surface of the amorphous resin layer, a metal vapor deposition layer provided on the surface of the primer layer, and an adhesive layer provided on the surface of the metal vapor deposition layer.

[0112] <Preparation of decorative sheet> Next, the surface layer and the backer layer were laminated so that the printed layer of the surface layer and the metal vapor deposition layer of the backer layer faced each other via the adhesive layer provided on the backer layer, and the printed layer and the adhesive layer were bonded together by a dry lamination method using a nip roll heated to 50°C, thereby adhering the surface layer and the backer layer.After that, an aging treatment was performed at 35°C for 72 hours to produce the decorative sheet of this example (total thickness of the decorative sheet: 210 μm).

[0113] Then, evaluation of design, scratch resistance, peel strength, peel durability, and peel interface was performed in the same manner as in Example 1. The results are shown in Table 3.

[0114] In addition to the evaluation criteria in Example 1 described above, for design evaluation, the prepared decorative sheet was inspected under illumination of 500 lux, with a direct and oblique view from a distance of 30 cm, and the presence or absence of air bubbles in the adhesive layer was evaluated according to the following evaluation criteria. ◯: No air bubbles were found in the adhesive layer. ×: Air bubbles were found in the adhesive layer.

[0115] Example 8 A decorative sheet (total thickness of decorative sheet: 260 μm) was produced in the same manner as in Example 7 above, except that the above-mentioned colored resin film C was used instead of the colored resin film A, and design evaluation, scratch resistance evaluation, peel strength evaluation, peel durability evaluation, and peel interface evaluation were performed. The results are shown in Table 3.

[0116] Example 9 A decorative sheet (total thickness of decorative sheet: 210 μm) was produced in the same manner as in Example 7 described above, except that a primer layer was not provided on the surface of the amorphous resin layer, and design evaluation, scratch resistance evaluation, peel strength evaluation, peel durability evaluation, and peel interface evaluation were performed. The results are shown in Table 3.

[0117] Example 10 A decorative sheet (total thickness of decorative sheet: 260 μm) was produced in the same manner as in Example 7 above, except that the above-mentioned colored resin film C was used instead of the colored resin film A and a primer layer was not provided on the surface of the amorphous resin layer, and design evaluation, scratch resistance evaluation, peel strength evaluation, peel durability evaluation, and peel interface evaluation were performed. The results are shown in Table 3.

[0118] Comparative Example 7 A decorative sheet (total thickness of decorative sheet: 210 μm) was produced in the same manner as in Example 7 above, except that a two-component curing adhesive (viscosity: 1050 mPa s, surface tension: 30 mN / m) was used instead of the two-component curing adhesive (viscosity: 80 mPa s, surface tension: 21 mN / m), and evaluations of design, scratch resistance, peel strength, peel durability, and peel interface were performed. The results are shown in Table 3.

[0119] Comparative Example 8 A decorative sheet (total thickness of decorative sheet: 280 μm) was produced in the same manner as in Example 7 above, except that a one-component curing adhesive (viscosity: 10 mPa s, surface tension: 37 mN / m) was used instead of the two-component curing adhesive (viscosity: 80 mPa s, surface tension: 21 mN / m), the above-mentioned colored resin film C was used instead of the colored resin film A, and no primer layer was provided on the surface of the amorphous resin layer. The decorative sheet was then evaluated for design, scratch resistance, peel strength, peel durability, and peel interface. The results are shown in Table 3.

[0120] Comparative Example 9 A decorative sheet (total thickness of decorative sheet: 170 μm) was produced in the same manner as in Example 7 described above, except that crystalline transparent resin film A was used instead of colored resin film A, and design evaluation, scratch resistance evaluation, peel strength evaluation, peel durability evaluation, and peel interface evaluation were performed. The results are shown in Table 3.

[0121] Comparative Example 10 A decorative sheet (total thickness of decorative sheet: 75 μm) was produced in the same manner as in Example 7 described above, except that a crystalline transparent resin film D was used instead of the colored resin film A, and design evaluation, scratch resistance evaluation, peel strength evaluation, peel durability evaluation, and peel interface evaluation were performed. The results are shown in Table 3.

[0122] [Table 1]

[0123] [Table 2]

[0124] [Table 3]

[0125] As shown in Table 1, the decorative sheets of Examples 1 to 6 have excellent design and scratch resistance, as well as high peel strength and peel durability, and furthermore, improved adhesion at the interface of the metal vapor deposition layer.

[0126] On the other hand, in comparison example 2, in which crystalline transparent resin film A was used as the base layer of the backer layer, peeling occurred between the transparent resin film A and the metal vapor deposition layer, resulting in low peel strength and peel durability, and further reduced adhesion at the interface of the metal vapor deposition layer.

[0127] In Comparative Example 3, in which crystalline transparent resin film D was used as the substrate layer of the backer layer, peeling occurred between the transparent resin film D and the metal deposition layer, resulting in low peel strength and peel durability, and further reduced adhesion at the interface of the metal deposition layer. In addition, because the transparent resin film D was crystalline and thin (12 μm), the transparent resin film D broke.

[0128] In Comparative Example 4, since the printed layer is not on the side of the transparent resin film A opposite to the side where the hard coat layer is provided (i.e., the backer layer side), the colored resin film A is scraped off, and it is found that the scratch resistance is poor. Also, since peeling occurs between the metal vapor deposition layer and the primer layer A, it is found that the peel strength in 90° peeling is low and the adhesion at the interface of the metal vapor deposition layer is reduced. Furthermore, it is found that the peel durability in 90° peeling and 180° peeling is low.

[0129] In addition, in Comparative Example 5, a mixture of gravure printing ink and primer A was applied to form a printed layer containing primer A, which inhibited the primer function, resulting in reduced peel strength and peel durability as well as reduced adhesion at the interface of the metal vapor deposition layer.

[0130] Furthermore, in Comparative Example 6, a printed layer without primer function is provided between the primer layer A and the transparent resin layer, which results in reduced peel strength and peel durability as well as reduced adhesion at the interface with the metal vapor deposition layer.

[0131] Furthermore, as shown in Table 3, the decorative sheets of Examples 7 to 10 have excellent design and scratch resistance, as well as high peel strength and peel durability, and furthermore, improved adhesion at the interface of the metal vapor deposition layer.

[0132] On the other hand, in Comparative Example 7, in which the adhesive forming the adhesive layer had a high viscosity (1050 mPa·s), scratches were found on the metal vapor deposition layer and air bubbles were generated in the adhesive layer, showing a significant decrease in design.

[0133] In addition, in Comparative Example 8, in which the adhesive forming the adhesive layer had a high surface tension (37 mN / m), the coating properties on the aluminum vapor deposition layer were poor, and scratches on the metal vapor deposition layer were confirmed and air bubbles were generated in the adhesive layer, resulting in a significant decrease in design.

[0134] In Comparative Example 9, in which crystalline transparent resin film A was used as the substrate layer of the backer layer, peeling occurred between the transparent resin film A and the metal deposition layer, resulting in low peel strength and peel durability, and furthermore, poor adhesion at the interface of the metal deposition layer. Similarly, in Comparative Example 10, in which crystalline transparent resin film D was used as the substrate layer of the backer layer, peeling occurred between the transparent resin film D and the metal deposition layer, resulting in low peel strength and peel durability, and furthermore, poor adhesion at the interface of the metal deposition layer. [Industrial Applicability]

[0135] As described above, the present invention is suitable for decorative sheets. [Explanation of symbols]

[0136] 1 Decorative sheet 2 Surface layer 3. Backer Tier 4 Adhesive layer 5 Transparent resin layer 6 printing layer 7 Hard Coat Layer 8. Amorphous resin layer 9 Metal deposited layer 10 Primer layer 11 Micropore 20 Decorative Sheet

Claims

1. A laminate including at least an amorphous resin layer, a metal vapor deposition layer provided on a surface of the amorphous resin layer, and a primer layer provided on the surface of the metal vapor deposition layer; a transparent resin layer provided on the primer layer side of the laminate; At least The decorative sheet is characterized in that the metal vapor deposition layer has a plurality of micropores.

2. 2. The decorative sheet according to claim 1, wherein an adhesive layer is provided between the transparent resin layer and the primer layer.

3. 3. The decorative sheet according to claim 1, wherein the amorphous resin layer has a thickness of 50 to 500 μm.

4. The decorative sheet according to any one of claims 1 to 3, wherein the amorphous resin layer is a colored layer.

5. The decorative sheet according to any one of claims 1 to 4, characterized in that at least one of the amorphous resin layer and the transparent resin layer is formed from a recycled polyethylene terephthalate-based resin.

6. The decorative sheet according to any one of claims 1 to 5, wherein a printed layer is provided on a surface of the transparent resin layer on the side of the primer layer.

7. A laminate including at least a resin layer in an amorphous state, a metal vapor deposition layer provided on a surface of the resin layer in an amorphous state, and an adhesive layer provided on the surface of the metal vapor deposition layer; a transparent resin layer provided on the adhesive layer side of the laminate; At least The metal deposition layer has a plurality of micropores, A decorative sheet characterized in that the viscosity of the adhesive forming the adhesive layer is 10 mPa·s or more and 500 mPa·s or less, and the surface tension of the adhesive is 20 mN / m or more and 32 mN / m or less.

8. 8. The decorative sheet according to claim 7, wherein the thickness of the amorphous resin layer is 50 to 500 μm.

9. 9. The decorative sheet according to claim 7, wherein the amorphous resin layer is a colored layer.

10. The decorative sheet according to any one of claims 7 to 9, characterized in that at least one of the amorphous resin layer and the transparent resin layer is formed from a recycled polyethylene terephthalate-based resin.

11. The decorative sheet according to any one of claims 7 to 10, wherein a printed layer is provided on a surface of the transparent resin layer on the side of the adhesive layer.

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