Decorative vapor deposition sheet

Abstract

To provide vapor deposition sheet for decoration which can reduce or prevent inconveniences such as breaks of a metal vapor deposition layer or whole sheet even if applied to a molding method requiring high temperature.SOLUTION: Vapor deposition sheet for decoration includes a cover resin layer and a metal vapor deposition layer. The cover resin layer has thickness equal to or more than approximately 50 micrometers. The metal vapor deposition layer presents granular structure. The break rate of increase at 20°C of the vapor deposition sheet for decoration is equal to or more than approximately 120%, and at 160°C, the rate is equal to or more than approximately 350%.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a decorative vapor deposition sheet. [Background technology]

[0002] In recent years, various metal vapor-deposited sheets have been developed and are used in a wide range of fields, such as interior and exterior applications.

[0003] Patent Document 1 (WO 2015 / 050011) describes a decorative vapor-deposited film having a tin vapor-deposited film on a polymer film, in which the tin vapor-deposited film has a black layer on either or both of its surface and the interface with the polymer film, and the black layer is formed by applying a vacuum of 0.8 × 10 -2 Pa ~ 5.0 × 10 -2 This document describes a decorative vapor-deposited film in which oxygen gas is introduced into the vicinity of the surface of a polymer film so that the oxygen gas reaches a range of Pa, and the tin vapor-deposited film is colored black.

[0004] Patent document 2 (JP 62-174189 A) describes an insulating transfer material in which a release layer, a protective layer, a metal vapor deposition layer, and an adhesive layer are sequentially laminated on one side of a substrate, and the metal vapor deposition layer has an island structure to provide insulation.

[0005] Patent Document 3 (Utility Model Registration No. 3198079) describes a three-dimensionally molded signboard obtained by attaching a resin-moldable transparent metal-deposited film to a transparent colored acrylic plate and then three-dimensionally molding it. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2015 / 050011 [Patent Document 2] Japanese Unexamined Patent Publication No. 62-174189 [Patent Document 3] Utility Model Registration No. 3198079 Summary of the Invention [Problem to be solved by the invention]

[0007] There is a known technique for forming a resin plate using a vacuum forming method or the like to obtain a three-dimensional molded product such as a signboard. The vacuum forming method typically requires a thick resin plate to be at least partially highly bent, and therefore high-temperature conditions exceeding 100°C may be applied.

[0008] Metal-vapor-deposited sheets capable of exhibiting metallic decorative properties have generally been used by laminating them to prefabricated molded articles with low bending properties, such as curved surfaces. In such cases, defects such as breakage of the metal-vapor-deposited layer or the entire sheet rarely occur. However, when a resin plate to which a metal-vapor-deposited sheet has been laminated is used in a molding process, such as a vacuum molding process, which involves harsh conditions exceeding 100°C, defects such as those described above are more likely to occur than when the metal-vapor-deposited sheet is laminated to a molded article.

[0009] The present disclosure provides a decorative vapor deposition sheet that can reduce or prevent defects such as breakage of the metal vapor deposition layer or the entire sheet, even when applied to a forming method that requires high temperatures, etc. [Means for solving the problem]

[0010] According to one embodiment of the present disclosure, there is provided a decorative vapor-deposited sheet comprising a cover resin layer and a metal vapor-deposited layer, wherein the cover resin layer has a thickness of at least about 50 micrometers, the metal vapor-deposited layer exhibits a granular structure, and the decorative vapor-deposited sheet has a breaking elongation of at least about 120% at 20°C and a breaking elongation of at least about 350% at 160°C.

[0011] According to another embodiment of the present disclosure, there is provided an article in which the above decorative vapor deposition sheet is adhered to a substrate.

[0012] According to another embodiment of the present disclosure, there is provided a method for producing an article having a three-dimensional shape, which includes applying the decorative vapor deposition sheet described above to a substrate and then vacuum forming the applied sheet. [Effects of the Invention]

[0013] According to the present disclosure, it is possible to provide a decorative vapor deposition sheet that can reduce or prevent defects such as breakage of the metal vapor deposition layer or the entire sheet, even when applied to a forming method that requires high temperatures, etc.

[0014] The above description should not be considered as a disclosure of all embodiments of the present invention and all advantages associated with the present invention. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1( a) is a schematic cross-sectional view of an article in which a decorative vapor deposition sheet according to one embodiment of the present disclosure is applied to a substrate, and FIG. 1( b) is a schematic cross-sectional view of an article in which a decorative vapor deposition sheet according to another embodiment of the present disclosure is applied to a substrate. [Figure 2] 1 is a scanning electron micrograph of a metal vapor deposition layer having a grain structure according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0016]

[0023] The present invention will now be described in more detail with reference to the drawings for the purpose of illustrating exemplary embodiments thereof, but the present invention is not limited to these embodiments. With regard to the reference numerals of the drawings, like numbered elements in different drawings indicate similar or corresponding elements.

[0017] In the present disclosure, the term "sheet" also encompasses articles called "films."

[0018] In the present disclosure, for example, the term "on" in "a metal vapor deposition layer is disposed on an adhesive layer" means that the metal vapor deposition layer is disposed directly on top of the adhesive layer, or that the metal vapor deposition layer is disposed indirectly on top of the adhesive layer via another layer.

[0019] In the present disclosure, for example, the term "under" in "the metal vapor deposition layer is disposed under the cover resin layer" means that the metal vapor deposition layer is disposed directly under the cover resin layer, or that the metal vapor deposition layer is disposed indirectly under the cover resin layer via another layer.

[0020] In the present disclosure, the term "granular structure" refers to a structure in which, when the surface of the metal vapor deposition layer is observed directly or indirectly through a cover resin layer or the like using a scanning electron microscope or an optical microscope, at least one surface portion of the metal vapor deposition layer exhibits a discontinuous state as shown in FIG. 2, appearing granular. Here, the "discontinuous state" refers to any structure in which at least the surface portion of the metal vapor deposition layer is discontinuous in a regular or random manner. The cross-sectional surface of the metal vapor deposition layer in the thickness direction is not necessarily entirely discontinuous; the surface portion opposite the discontinuous surface portion of the metal vapor deposition layer may be entirely or partially continuous. In other words, in the present disclosure, a "metal vapor deposition layer exhibiting a granular structure" is not limited to a structure in which the entire metal vapor deposition layer is discontinuous, as shown in FIG. 1(a), but can also include a structure in which one surface portion of the metal vapor deposition layer is partially continuous, as shown in FIG. 1(b).

[0021] In the present disclosure, the term "three-dimensional shape" refers to a three-dimensional shape in which the Z axis is added to a two-dimensional shape (a planar shape having only the X axis and Y axis).

[0022] In this disclosure, the term "approximately" means that variations caused by manufacturing errors and the like are included, and it is intended that a variation of about ±20% is allowed.

[0023] In the present disclosure, "transparent" refers to an average transmittance of about 80% or more, and preferably about 85% or more, or about 90% or more, in the visible light region (wavelength 400 nm to 700 nm) measured in accordance with JIS K 7375. There is no particular upper limit to the average transmittance, but it can be specified, for example, as less than about 100%, about 99% or less, or about 98% or less.

[0024] In the present disclosure, the term "semi-transparent" refers to an average transmittance in the visible light region (wavelength 400 nm to 700 nm) measured in accordance with JIS K 7375 of less than approximately 80%, preferably approximately 75% or less, and is intended to not completely conceal the underlying layer.

[0025] In the present disclosure, "(meth)acrylic" means acrylic or methacrylic.

[0026] The decorative vapor deposition sheet of the present disclosure will be described below with reference to the drawings.

[0027] 1 includes a cover resin layer 101, a metal vapor deposition layer 103, and an adhesive layer 105. The adhesive layer 105 is an optional constituent layer, and the decorative vapor deposition sheet of the present disclosure does not necessarily include such a layer.

[0028] Hereinafter, for the purpose of illustrating representative embodiments of the present disclosure, details of each component will be described with some reference numerals omitted.

[0029] The cover resin layer of the present disclosure has a thickness of about 50 micrometers or more. The cover resin layer is a layer that can be applied to cover at least the metal vapor deposition layer when the decorative vapor deposition sheet is applied to a substrate such as a polycarbonate plate. A cover resin layer having this specific thickness can contribute to reducing or suppressing defects such as breakage of the metal vapor deposition layer or the entire sheet during molding.

[0030] For example, when a substrate to which a decorative vapor deposition sheet is applied is bent severely using a vacuum forming method, stress such as pressure may be locally applied to the bent portion under high-temperature conditions exceeding 100° C. The cover resin layer of the present disclosure is thicker than the surface protective coating layer or the like applied to conventional decorative vapor deposition sheets. Therefore, even if stress is locally applied under such high-temperature conditions, the decorative vapor deposition sheet of the present disclosure including such a cover resin layer can stretch without breaking at that location, thereby reducing or suppressing defects such as breakage of the metal vapor deposition layer or the entire sheet.

[0031] In some embodiments, the decorative vapor deposition sheet of the present disclosure is applied to a substrate (e.g., a polycarbonate plate) via an adhesive layer and then subjected to molding. When local stress is applied under high-temperature conditions, the adhesive layer as well as the cover resin layer are stretched. Resin layers thinner than the cover resin layer of the present disclosure are susceptible to the elongation of the adhesive layer, which may trap air during molding, resulting in air pockets (foaming). The cover resin layer of the present disclosure, which has a specific thickness, is less susceptible to the elongation of the adhesive layer and can therefore contribute to reducing or preventing the occurrence of such air pockets.

[0032] The thickness of the cover resin layer is not particularly limited as long as it is about 50 micrometers or more, but from the viewpoints of preventing breakage, preventing air trapping, etc., it can be, for example, about 60 micrometers or more, about 70 micrometers or more, or about 80 micrometers or more. The upper limit of the thickness of the cover resin layer is not particularly limited, but from the viewpoints of moldability, manufacturing costs, etc., it can be, for example, about 200 micrometers or less, about 150 micrometers or less, about 100 micrometers or less, or about 90 micrometers or less. Here, the thickness of each layer in a decorative vapor deposition sheet having a laminated structure can be defined as the average thickness of at least five arbitrary locations in the target layer of the laminated structure, for example, the cover resin layer, measured using a scanning electron microscope or an optical microscope.

[0033] The resin material for the cover resin layer is not particularly limited, and may be at least one selected from urethane, polyvinylidene fluoride, and (meth)acrylic. Among these, urethane and polyvinylidene fluoride are preferred from the viewpoints of rust prevention, curl resistance, and outgassing resistance of the metal vapor deposition layer, and urethane is even more preferred from the viewpoint of transparency after bending. While the mechanism by which a cover resin layer containing urethane and / or polyvinylidene fluoride has excellent outgassing resistance is unclear, it is believed that cover resin layers containing these resins have superior gas permeability compared to cover resin layers composed of other resins, allowing gas generated from substrates such as polycarbonate to pass through, thereby reducing or suppressing defects such as air trapping (foaming) caused by the generated gas. Cover resin layers obtained using such materials may have a single-layer or multilayer structure. Examples of the laminated cover resin layer include a layer made of polyvinylidene fluoride (PVDF) and a layer made of polymethyl methacrylate (PMMA), or two or more layers containing PVDF and PMMA in different ratios.

[0034] The cover resin layer is typically preferably transparent, but may be entirely or partially transparent, semi-transparent, or opaque in the visible range to provide a desired appearance.

[0035] The surface of the cover resin layer may be subjected to a surface treatment such as a corona treatment or a plasma treatment in order to improve adhesion to the metal vapor deposition layer or the like.

[0036] The metal vapor deposition layer of the present disclosure has a granular structure and can exhibit decorative properties generally referred to as a metallic or metallic look. When the surface of the metal vapor deposition layer of the present disclosure is observed directly or indirectly through a cover resin layer or the like with a scanning electron microscope or an optical microscope, at least one surface of the metal vapor deposition layer exhibits a discontinuous state as shown in Figure 2. As a result, for example, an internally illuminated sign or sign obtained using a decorative vapor deposition sheet having such a metal vapor deposition layer can transmit light from an internal light source such as an LED, and can exhibit metallic or metallic decorative properties even at night.

[0037] The light transmission performance of such a metal vapor deposition layer can be evaluated, for example, by optical density (OD value) using the test method described below. The optical density of the metal vapor deposition layer can be, for example, about 1.0 or more, about 1.1 or more, or about 1.2 or more, and about 1.9 or less, about 1.8 or less, or about 1.7 or less. A decorative vapor deposition sheet having a metal vapor deposition layer with an optical density within this range can transmit light from an internal light source even when used in, for example, an internally illuminated sign or sign, and can therefore exhibit good metallic or metallic decorative performance even at night.

[0038] Because the metal vapor deposition layer of the present disclosure has such a granular structure, when the metal vapor deposition layer is stretched, for example, by vacuum forming, the force is more likely to be transmitted between the granular portions as shown in Figure 2, rather than acting to break or destroy the granular portions themselves that exhibit metallic or metallic decorative properties. As a result, a decorative vapor deposition sheet including the metal vapor deposition layer of the present disclosure can exhibit good metallic or metallic decorative performance even when stretched to a high degree.

[0039] When a cross section of the metal vapor deposition layer of the present disclosure is observed in the thickness direction, the entire layer may be discontinuous, as shown in Figure 1(a), or the surface opposite the discontinuous surface of the metal vapor deposition layer may be entirely or partially continuous, as shown in Figure 1(b). Even if the surface on one side of the metal vapor deposition layer is continuous, the continuous metal vapor deposition portion located between the granular portions is typically thinner than the thickness of the granular portions, and therefore can exhibit the light transmission performance described above.

[0040] In some embodiments, from the viewpoint of outgassing resistance, i.e., reducing or suppressing defects such as air pockets caused by gases generated from the substrate to which the decorative vapor deposition sheet is applied, it is preferable that the metal vapor deposition layer has a structure in which part or the entire layer is discontinuous when observed at a cross section in the thickness direction.

[0041] Whether the metal vapor deposition layer is partially or entirely discontinuous can be evaluated by observing a cross section of the metal vapor deposition layer in the thickness direction using a scanning electron microscope or an optical microscope. However, since such a discontinuous metal vapor deposition layer has poorer conductivity than a continuous metal vapor deposition layer, it can also be evaluated indirectly by measuring the surface resistance of the metal vapor deposition layer. The surface resistance of a partially or entirely discontinuous metal vapor deposition layer is, for example, about 8.0 × 10 10 Ω / □ or more, approximately 9.0×10 10 Ω / □ or more, or approximately 10 x 10 10 The surface resistance may be expressed in units of Ω / □ or more. Here, the unit of surface resistance may be expressed as "Ω per square," "ohm per square," "Ω / sq.", or "ohm / sq." instead of "Ω / □."

[0042] As shown in Figure 2, there are no particular restrictions on the size and shape of the granular portions of the granular structure on the surface of the metal vapor deposition layer, the spacing between the granular portions, or the thickness of the metal vapor deposition layer. For example, these can be appropriately selected by adjusting the deposition rate, deposition time, deposition material, etc., taking into consideration the required performance depending on the intended use (e.g., decorativeness such as metallic tone, light transmittance, outgassing resistance).

[0043] The material for the metal vapor deposition layer is not particularly limited, and examples thereof include aluminum, nickel, gold, silver, copper, platinum, chromium, iron, tin, indium, titanium, lead, zinc, and germanium. These may be used alone or in combination of two or more. Among these, indium and / or tin are preferred from the viewpoint of ease of forming a granular structure, and indium is more preferred from the viewpoint of water resistance.

[0044] The decorative vapor-deposited sheet of the present disclosure includes a cover resin layer having a thickness of approximately 50 micrometers or more and a vapor-deposited metal layer having a granular structure, and therefore can reduce or prevent defects such as breakage of the vapor-deposited metal layer or the entire sheet, even when applied to a molding method requiring high temperatures exceeding 100° C. Such performance can be evaluated, for example, by the elongation at break or stretch test described below.

[0045] In some embodiments, the decorative vapor deposition sheet of the present disclosure can achieve a breaking elongation at 20°C of, for example, about 120% or more, about 125% or more, or about 130% or more. The decorative vapor deposition sheet of the present disclosure has good elongation properties not only at high temperatures but also at room temperature of about 20°C, which can reduce or prevent air entrapment during lamination to a substrate such as a polycarbonate plate. There is no particular upper limit to the breaking elongation, but it can be, for example, about 200% or less, about 190% or less, or about 180% or less.

[0046] In some embodiments, the decorative vapor deposition sheet of the present disclosure can achieve, for example, a breaking elongation of about 350% or more, about 355% or more, or about 360% or more at 160° C. There is no particular upper limit to the breaking elongation, but it can be, for example, about 500% or less, about 480% or less, or about 450% or less.

[0047] In some embodiments, the decorative vapor-deposited sheet of the present disclosure can achieve a "good" result in the stretch test described below, i.e., visual observation reveals no obvious breaks or cracks in the metal vapor-deposited layer. Here, "obvious breaks or cracks in the metal vapor-deposited layer" refers to breaks or cracks in the granular portions that contribute to the metallic luster. For example, as shown in Figure 1(b), the thickness of the connecting portions between granular portions is usually significantly thinner than the thickness of the granular portions, making it less likely to affect the metallic luster and not visible to the naked eye. Therefore, breaks or cracks in such connecting portions are not included in the "obvious breaks or cracks in the metal vapor-deposited layer."

[0048] In some embodiments, the decorative vapor deposition sheet of the present disclosure can maintain excellent metallic luster even after being highly stretched. For example, when forming articles such as signs using a vacuum forming method, the sheet may be highly bent. In conventional vapor deposition sheets, the metal vapor deposition layer is highly stretched at such bends, which can easily cause defects such as cracks, resulting in a decrease in metallic luster. The decorative vapor deposition sheet of the present disclosure simultaneously includes a specific cover resin layer and a specific metal vapor deposition layer. Even when subjected to high stretching, the cover resin layer suppresses the elongation of the metal vapor deposition layer at the stretched area, and the stretching force propagates between the granular portions rather than through the granular portions that contribute to the metallic luster, thereby enabling the sheet to exhibit excellent metallic luster. This performance can be evaluated by measuring the reflectance after stretching using the test method described below. The decorative vapor deposition sheet of the present disclosure can achieve a reflectance of at least about 20%, at least about 23%, or at least about 25% when the sheet is stretched 1.5 times in both the longitudinal and transverse directions to an area magnification of 300%. There is no particular upper limit to the reflectance, but it can be, for example, about 50% or less, about 45% or less, about 40% or less, or about 35%.

[0049] In some embodiments, the decorative vapor deposition sheet of the present disclosure may further include additional layers as optional components, such as a decorative layer other than the above-described metal vapor deposition layer, a bonding layer (sometimes referred to as a "primer layer") that bonds the constituent layers together, an adhesive layer, a release liner for protecting the adhesive layer, etc. These additional layers may be used alone or in combination of two or more.

[0050] In some embodiments, the decorative vapor deposition sheet of the present disclosure may have a decorative layer disposed above or below the cover resin layer. The decorative layer may be entirely or partially transparent, semi-transparent, or opaque in the visible range, and may be applied to, for example, the entire surface or a portion of the cover resin layer.

[0051] Decorative layers include, but are not limited to, color layers that exhibit paint colors, such as light colors such as white and yellow, and dark colors such as red, brown, green, blue, gray, and black; pattern layers that impart patterns such as wood grain, stone grain, geometric patterns, and leather patterns, logos, and designs to articles; relief (embossed pattern) layers that have an uneven surface; and combinations of these.

[0052] Materials for the color layer are not limited to the following, but include, for example, inorganic pigments such as carbon black, yellow lead, yellow iron oxide, red iron oxide, and red iron oxide; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; organic pigments such as azo lake pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, and quinacridone pigments such as quinacridone red; and other pigments dispersed in a binder resin such as a (meth)acrylic resin or polyurethane resin.

[0053] The color layer can be formed using such materials by a coating method such as gravure coating, roll coating, die coating, bar coating, or knife coating, or by a printing method such as inkjet printing.

[0054] The pattern layer is not limited to the following, but may be, for example, a layer in which a pattern such as a design, logo, or picture is directly applied to the cover resin layer or the like using a printing method such as gravure direct printing, gravure offset printing, inkjet printing, laser printing, or screen printing, or a film, sheet, or the like having a pattern, logo, or picture formed by coating such as gravure coating, roll coating, die coating, bar coating, or knife coating, punching, etching, or the like. The material for the pattern layer may be, for example, the same material as that used for the color layer.

[0055] The relief layer can be a thermoplastic resin film having a textured surface formed by a conventional method such as embossing, scratching, laser processing, dry etching, or hot pressing. The relief layer can also be formed by applying a thermosetting or radiation-curable resin such as a curable (meth)acrylic resin onto a release liner having a textured surface, curing it by heating or irradiating it with radiation, and then removing the release liner.

[0056] The thermoplastic resin, thermosetting resin, and radiation-curable resin used in the relief layer are not particularly limited, and examples thereof include fluororesin, polyester resin such as PET or PEN, (meth)acrylic resin, polyolefin resin such as polyethylene or polypropylene, thermoplastic elastomer, polycarbonate resin, polyamide resin, ABS resin, acrylonitrile-styrene resin, polystyrene resin, vinyl chloride resin, polyurethane resin, etc. The relief layer may contain at least one of the pigments used in the color layer.

[0057] The thickness of the decorative layer may be adjusted appropriately depending on the required decorativeness, etc., and is not particularly limited, but can be, for example, about 1 micrometer or more, about 3 micrometers or more, or about 5 micrometers or more, and can be about 30 micrometers or less, about 20 micrometers or less, or about 15 micrometers or less.

[0058] In some embodiments, the decorative vapor deposition sheet of the present disclosure can include a bonding layer for bonding the constituent layers. The bonding layer can be, for example, a commonly used adhesive, such as a (meth)acrylic, polyolefin, polyurethane, polyester, or rubber adhesive, which can be solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting, or UV-curable. The bonding layer can be applied by a known coating method.

[0059] The thickness of the bonding layer can be, for example, about 0.05 micrometers or more, about 0.5 micrometers or more, or about 5 micrometers or more, and can be about 30 micrometers or less, about 20 micrometers or less, or about 10 micrometers or less.

[0060] In some embodiments, the decorative vapor-deposited sheet may further include an adhesive layer for attaching the decorative vapor-deposited sheet to a substrate (described later) as an adherend. The adhesive layer is preferably disposed below the metal vapor-deposited layer 103 disposed below the cover resin layer 101, as shown in FIG.

[0061] The adhesive layer may be made of the same material as the joining layer, but a (meth)acrylic pressure-sensitive adhesive (pressure-sensitive adhesive) is preferred from the viewpoints of formability, penetration into the granular structure of the metal vapor deposition layer, outgassing resistance, etc. The adhesive layer may be applied to the adherend instead of the decorative vapor deposition sheet.

[0062] The thickness of the adhesive layer is not limited to, but may be, for example, about 5 micrometers or more, about 10 micrometers or more, or about 20 micrometers or more, and may be about 100 micrometers or less, about 80 micrometers or less, or about 50 micrometers or less. Although a portion of the adhesive layer may penetrate into the grain structure of the metal vapor deposition layer 103 as shown in FIG. 1, the thickness of the adhesive layer in this disclosure refers to the distance from the bottom of the metal vapor deposition layer 103 to the substrate 107 according to FIG. 1.

[0063] Materials that can be used to form the cover resin layer, decorative layer, bonding layer, adhesive layer, or any other layer described above can include optional components such as fillers, reinforcing materials, antioxidants, UV absorbers, light stabilizers, heat stabilizers, tackifiers, crosslinking agents, curing agents, thickeners, dispersants, plasticizers, flow improvers, surfactants, leveling agents, rust inhibitors, silane coupling agents, catalysts, pigments, and dyes, provided that the effects of the present disclosure are not impaired. These can be used alone or in combination. For example, the use of a thickener can contribute to thick coating of the cover resin layer.

[0064] In some embodiments, any suitable release liner can be used to protect the adhesive layer. Typical release liners include those made from paper (e.g., kraft paper), polymer materials (e.g., polyolefins such as polyethylene or polypropylene, polyesters such as ethylene vinyl acetate, polyurethane, and polyethylene terephthalate), etc. If necessary, the release liner may be coated with a layer of a release agent such as a silicone-containing material or a fluorocarbon-containing material.

[0065] The thickness of the release liner can be, for example, about 5 micrometers or more, about 15 micrometers or more, or about 25 micrometers or more, and can be about 300 micrometers or less, about 200 micrometers or less, or about 150 micrometers or less. The thickness of the release liner can be defined as the average value calculated by measuring the thickness of any portion of the release liner at least five times using a high-precision Digimatic Micrometer (MDH-25MB, manufactured by Mitutoyo Corporation) after removing the release liner from the adhesive layer.

[0066] Each layer other than the metal vapor deposition layer of the decorative vapor deposition sheet of the present disclosure can be prepared as appropriate by a known method, for example, a printing method such as gravure direct printing, gravure offset printing, inkjet printing, or screen printing; a coating method such as gravure coating, roll coating, die coating, bar coating, knife coating, or extrusion coating; a lamination method; a transfer method; or the like, either alone or in combination.

[0067] The metal vapor deposition layer of the present disclosure is not particularly limited in its manufacturing method as long as it can exhibit a granular structure, and known vapor deposition methods such as vacuum vapor deposition, ion plating, and chemical vapor deposition can be used. However, from the viewpoint of the formability of the granular structure, vacuum vapor deposition is preferred.

[0068] The following manufacturing method is described as an example, but the manufacturing method of the decorative vapor deposition sheet is not limited thereto. For example, in the case of the decorative vapor deposition sheet having the above-mentioned configuration including a cover resin layer, a metal vapor deposition layer, an adhesive layer, and a release liner, a cover resin composition is coated on a release liner, and a drying process and a curing process are performed as necessary to form a cover resin layer, and then a metal vapor deposition layer is vapor-deposited on the cover resin layer. An adhesive is coated on the resulting metal vapor deposition layer, and a drying process and a curing process are performed as necessary to form an adhesive layer, thereby preparing the decorative vapor deposition sheet. Here, the cover resin layer may be previously formed into a film or sheet.

[0069] According to one embodiment of the present disclosure, an article can be provided in which the decorative vapor deposition sheet described above is adhered to a substrate. Examples of such articles include a substantially flat, unmolded article obtained by bonding the decorative vapor deposition sheet to a substrate such as a polycarbonate plate, a three-dimensionally shaped article obtained by further molding such a substantially flat article, or an article obtained by bonding the decorative vapor deposition sheet to a curved or other shaped substrate. The decorative vapor deposition sheet of the present disclosure reduces or prevents defects such as breakage of the metal vapor deposition layer or the entire sheet even when applied to a molding method requiring high temperatures, such as vacuum molding (vacuum pressure forming). Therefore, it is advantageous to use the decorative vapor deposition sheet for a three-dimensionally shaped article obtained by further molding a substantially flat article. Here, "high temperature" in the present disclosure can refer to, for example, temperatures of about 100°C or higher, more than about 100°C, about 120°C or higher, or about 150°C or higher, and about 250°C or lower, about 230°C or lower, or about 200°C or lower. The pressure applied in the vacuum / pressure forming method can be, for example, greater than about 3 atm, about 4 atm or more, or about 5 atm or more, where atmospheric pressure is 1 atm. There is no particular upper limit to the pressure, but it can be, for example, about 20 atm or less, about 15 atm or less, or about 10 atm or less.

[0070] In the present disclosure, the term "three-dimensional shape" typically refers to a three-dimensional shape in which the Z axis is added to a two-dimensional shape (a planar shape with only the X and Y axes), but it can also refer to a three-dimensional shape having a highly curved portion among such three-dimensional shapes. Here, in the present disclosure, the term "highly curved portion" can refer to an article, for example, an article in an internally illuminated sign, in which either the angle of the curved portion when viewed from the lighting arrangement side of the cover portion of the cover portion or the angle of the curved portion when viewed from the outside of the cover portion is about 140 degrees or less, about 130 degrees or less, about 120 degrees or less, about 110 degrees or less, or about 100 degrees or less, or can refer to an angle of about 50 degrees or more, about 60 degrees or more, about 70 degrees or more, about 80 degrees or more, about 90 degrees or more, or more than about 90 degrees.

[0071] The substrate material is not particularly limited, and examples thereof include glycol-modified polyethylene terephthalate (PET-G), (meth)acrylic, polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS), and mixtures thereof. (Meth)acrylic and polycarbonate substrates are more likely to generate gas during molding or over time than PET-G substrates, potentially resulting in problems such as air trapping (foaming) between the substrate and the decorative vapor deposition sheet. The use of a decorative vapor deposition sheet according to one embodiment of the present disclosure, such as a cover resin layer containing urethane and / or polyvinylidene fluoride with excellent outgassing resistance and a metal vapor deposition layer that is partially or entirely discontinuous in the thickness direction cross section, can contribute to improving problems such as air trapping and can be advantageously used with substrates prone to gas trapping.

[0072] The substrate is typically transparent or translucent (e.g., milky white), but may be wholly or partially transparent, translucent, or opaque in the visible range to provide the desired appearance.

[0073] The thickness of the substrate is not particularly limited, and can be, for example, about 0.2 mm or more, about 0.5 mm or more, about 1.0 mm or more, or about 1.5 mm or more, and can be about 3.0 mm or less, about 2.5 mm or less, or about 2.0 mm or less.

[0074] In some embodiments, the decorative vapor deposition sheet of the present disclosure can be used for, for example, signs (e.g., internally illuminated signs, externally illuminated signs), signs (e.g., internally illuminated signs, externally illuminated signs), various interior or exterior parts, for example, interior or exterior parts of vehicles such as automobiles, trains, airplanes, and ships (e.g., roof members, pillar members, door trim members, instrument panel members, front members such as hoods, bumper members, fender members, side sill members, interior panel members), building members (e.g., roof members such as window glass, doors, sashes, and roofing tiles, exterior wall members, wallpaper), etc. In addition, the heat-shrinkable adhesive film of the present disclosure can be used for electrical appliances such as personal computers, smartphones, mobile phones, refrigerators, and air conditioners, stationery, furniture, desks, various containers such as cans, etc. In particular, the decorative vapor deposition sheet of the present disclosure is preferably used for signs or signs, and more preferably for internally illuminated signs or signs.

[0075] The method for forming a substantially flat article formed by laminating the decorative vapor deposition sheet of the present disclosure to a substrate into a three-dimensional shape is not particularly limited, and known methods can be used as appropriate. For example, thermoforming can be used, specifically, three-dimensional overlay molding (TOM), vacuum forming methods such as vacuum pressure forming, pressure forming, and press molding. Even when applied to forming methods requiring high temperatures, the decorative vapor deposition sheet of the present disclosure can reduce or suppress defects such as breakage of the metal vapor deposition layer or the entire sheet. Therefore, it can be applied to methods that are prone to such defects, such as vacuum pressure forming, which is a known method of obtaining high-precision molded products by exposing the sheet to high temperatures and then applying compressed air higher than atmospheric pressure and vacuuming. [Example]

[0076] The following examples illustrate specific embodiments of the present disclosure, but the invention is not limited thereto. All parts and percentages are by weight unless otherwise specified.

[0077] The materials used in this example are listed in Table 1 below.

[0078] [Table 1]

[0079] <Preparation of decorative vapor deposition sheet> Example 1 A mixture containing approximately 6.2 parts by weight of Tinuvin 292, approximately 10.4 parts by weight of Tinuvin 1130, approximately 26.9 parts by weight of V-02, and approximately 56.5 parts by weight of IPA was prepared, and this mixture was blended into a solution containing approximately 83.3 parts by weight of E UW-5002 to prepare a cover resin composition containing a urethane resin. The cover resin composition was then coated onto a polyester release liner using a knife coater and dried in an oven at approximately 60°C for approximately 1 minute, approximately 90°C for approximately 1 minute, and approximately 120°C for approximately 1 minute to prepare a cover resin layer with a thickness of approximately 60 micrometers.

[0080] A granular metal vapor deposition layer composed of indium was prepared by vacuum deposition on a film having a cover resin layer so that the optical density was approximately 1.1. A decorative vapor deposition sheet was then prepared by attaching a release sheet with a pressure-sensitive adhesive to this metal vapor deposition layer via an adhesive layer.

[0081] Example 2 A decorative vapor-deposited sheet of Example 2 was prepared in the same manner as in Example 1, except that the thickness of the cover resin layer was changed to about 90 micrometers.

[0082] Example 3 A decorative vapor-deposited sheet of Example 3 was prepared in the same manner as in Example 1, except that the film having a cover resin layer was replaced with Denka DX film 14S0250 having a thickness of about 50 micrometers.

[0083] (Comparative Example 1) A decorative vapor-deposited sheet of Comparative Example 1 was prepared in the same manner as in Example 1, except that the thickness of the cover resin layer was changed to about 40 micrometers.

[0084] (Comparative Example 2) A decorative vapor-deposited sheet of Comparative Example 2 was prepared in the same manner as in Example 3, except that the film was changed to Denka DX Film 14S0250 having a thickness of about 30 micrometers.

[0085] (Comparative Example 3) A decorative vapor-deposited sheet of Comparative Example 3 was prepared in the same manner as in Example 3, except that the metal vapor-deposited layer was changed to a vapor-deposited layer made of aluminum without a granular structure.

[0086] Example 4 A cover resin composition containing a urethane resin was prepared by blending a mixture of about 6.2 parts by weight of Tinuvin 292, about 10.4 parts by weight of Tinuvin 1130, about 26.9 parts by weight of V-02, and about 56.5 parts by weight of IPA into a solution containing about 83.3 parts by weight of E UW-5002, about 2.0 parts by weight of ACRYSOL RM-8W, and about 0.5 parts by weight of Dynol 604. The cover resin composition was then coated onto a polyester release liner using a knife coater and dried in an oven at about 60°C for about 1 minute, about 90°C for about 1 minute, and about 120°C for about 1 minute to prepare a cover resin layer having a thickness of about 60 micrometers.

[0087] A granular metal vapor deposition layer composed of indium was prepared by vacuum deposition on a film having a cover resin layer so that the optical density was approximately 1.7. A release sheet with a pressure-sensitive adhesive was then attached to this metal vapor deposition layer via an adhesive layer to prepare a decorative vapor deposition sheet.

[0088] <Physical property evaluation test> The properties of the decorative vapor deposition sheet were evaluated using the following methods.

[0089] (Evaluation test of the granular structure of the metal deposition layer) The surface of the metal vapor deposition layer before bonding the adhesive layer was observed at a magnification of 50,000 times using a scanning electron microscope (S-3400N, manufactured by Hitachi High-Technologies Corporation). If the surface of the metal vapor deposition layer exhibited a granular structure, it was evaluated as "present," and if it did not exhibit a granular structure, it was evaluated as "absent." The results are shown in Table 2.

[0090] (Breaking elongation test) A test sample was prepared by cutting the decorative vapor deposition sheet to a size of 25 mm wide and 150 mm long. This test sample was attached to a Tensilon tensile tester (manufactured by Orientec Co., Ltd.) so that the length of the check area was approximately 100 mm. The test sample was then pulled at a temperature of 20°C or 160°C at a pulling rate of 300 mm / min, and the value at which the test sample broke was measured. Five measurements were taken, and the average values ​​are shown in Table 2.

[0091] (Tensile test) A decorative vapor-deposited sheet cut to a width of 100 mm and a length of 100 mm was laminated to a PET-G film (Peteres™, manufactured by Mitsubishi Chemical Corporation) approximately 100 micrometers thick to prepare a test sample. This test sample was attached to a biaxial stretching machine (KARO, manufactured by Itochu Machine-Technos Corporation) and stretched 1.75 times in the length direction and 1.75 times in the width direction at 160°C. The appearance of the metal vapor-deposited layer after stretching was visually observed, and samples with no cracks and / or breaks in the metal vapor-deposited layer were rated "good" and samples with cracks and / or breaks in the metal vapor-deposited layer were rated "poor." The results are shown in Table 2.

[0092] (Optical Density Test) The optical density (OD value) of the metal vapor deposition layer of the decorative vapor deposition sheet before bonding the adhesive layer was measured using a Gretag Macbeth D200-II densitometer (manufactured by Sakata Inx Engineering Corporation). Measurements were performed at five random locations on the metal vapor deposition layer, and the average values ​​are shown in Table 2. Here, the metal vapor deposition layer of the decorative vapor deposition sheet of Comparative Example 3 did not have light transmission properties, so the optical density was not measured.

[0093] (Surface resistance test) The surface resistance of the metal vapor deposition layer of the decorative vapor deposition sheet before bonding the adhesive layer was measured using an MCP-HT800 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) Measurements were performed at five randomly selected locations on the metal vapor deposition layer, and the average values ​​are shown in Table 2.

[0094] (Reflectivity test after stretching) A decorative vapor-deposited sheet cut to a size of 100 mm wide and 100 mm long was laminated to a PET-G film (Peteres (trademark), manufactured by Mitsubishi Chemical Corporation) with a thickness of approximately 100 micrometers to prepare a test sample. This test sample was attached to a biaxial stretching machine (manufactured by KARO Itochu Machine Technos Corporation) and stretched at a temperature of 160°C by 1.5 times in the length direction and 1.5 times in the width direction to an area magnification of 300%. The reflectance of the cover resin layer side at approximately the center of the stretched test sample was measured using a LAMBDA 1050 (manufactured by PerkinElmer Japan Co., Ltd.). Five measurements were performed, and the average values ​​are shown in Table 2. Reflectance was not measured for the metal vapor-deposited layers of the decorative vapor-deposited sheets of Comparative Examples 1 and 2 because defects such as cracks occurred during stretching.

[0095] (Outgassing resistance test) A decorative vapor deposition sheet cut to a size of 50 mm wide and 50 mm long was laminated to a polycarbonate substrate (PC1600, manufactured by Partec Co., Ltd.) or an acrylic substrate (Acrylite™ EX001, manufactured by Mitsubishi Chemical Corporation) approximately 5 mm thick to prepare a test sample. The resulting test sample was left to stand in a 65°C oven for 24 hours, after which its appearance was visually observed. A sample with no air pockets (foaming) of 2 mm or more in maximum length was rated as "good," and a sample with air pockets of 2 mm or more in maximum length was rated as "poor." The results are shown in Table 2. Here, "PC substrate" and "AC substrate" in Table 2 refer to "polycarbonate substrate" and "acrylic substrate."

[0096] [Table 2]

[0097] It will be apparent to those skilled in the art that the above-described embodiments and examples may be modified in various ways without departing from the basic principles of the present invention, and that various improvements and modifications of the present invention may be made without departing from the spirit and scope of the present invention. [Explanation of symbols]

[0098] 100 Decorative vapor deposition sheet 101 Cover resin layer 103 Metal deposited layer 105 Adhesive layer 107 Base material 110 Goods Some embodiments of the present disclosure are described in [Item 1] to [Item 11] below. [Item 1] A decorative vapor-deposited sheet including a cover resin layer and a metal vapor-deposited layer, the cover resin layer has a thickness of 50 micrometers or more, the metal vapor deposition layer exhibits a granular structure; The decorative vapor deposition sheet has a breaking elongation of 120% or more at 20°C, and The decorative vapor deposition sheet has a breaking elongation of 350% or more at 160 ° C. Decorative vapor deposition sheet. [Item 2] Item 2. The decorative vapor deposition sheet according to item 1, wherein the metal vapor deposition layer has a structure in which part or the whole of the layer is discontinuous in a cross section in the thickness direction. [Item 3] The surface resistance of the metal vapor deposition layer is 8.0 × 10 10 3. The decorative vapor deposition sheet according to item 1 or 2, having a resistivity of Ω / □ or more. [Item 4] 4. The decorative vapor-deposited sheet according to any one of items 1 to 3, wherein the optical density of the metal vapor-deposited layer is 1.0 to 1.9. [Item 5] 5. The decorative vapor deposition sheet according to any one of items 1 to 4, wherein the cover resin layer contains at least one selected from the group consisting of urethane, polyvinylidene fluoride, and (meth)acrylic. [Item 6] 6. The decorative vapor-deposited sheet according to any one of items 1 to 5, wherein the metal vapor-deposited layer contains at least one selected from indium and tin. [Item 7] 7. The decorative vapor-deposited sheet according to any one of items 1 to 6, wherein an adhesive layer is disposed below the metal vapor-deposited layer disposed below the cover resin layer. [Item 8] 8. The decorative vapor deposition sheet according to any one of items 1 to 7, which is used for vacuum forming. [Item 9] An article in which the decorative vapor deposition sheet according to any one of items 1 to 7 is adhered to a substrate. [Item 10] 10. The article of item 9, having a three-dimensional shape. [Item 11] A method for producing an article having a three-dimensional shape, comprising applying the decorative vapor deposition sheet according to any one of items 1 to 8 to a substrate, and then vacuum forming the applied sheet.

Claims

1. A decorative vapor-deposited sheet including a cover resin layer and a metal vapor-deposited layer, the cover resin layer has a thickness of 50 micrometers or more, contains at least one selected from urethane and (meth)acrylic, and does not contain polyvinylidene fluoride; the metal vapor-deposited layer has a granular structure and is vapor-deposited on the cover resin layer directly or via a bonding layer, and the metal vapor-deposited layer has an optical density of 1.0 to 1.9; an adhesive layer is disposed under the metal vapor deposition layer disposed under the cover resin layer; No decorative layer is included under the metal vapor deposition layer, The decorative vapor deposition sheet has a breaking elongation of 120% or more at 20°C, and The decorative vapor deposition sheet has a breaking elongation of 350% or more at 160°C. Decorative vapor deposition sheet.

2. 2. The decorative vapor deposition sheet according to claim 1, wherein the metal vapor deposition layer is partially or entirely discontinuous in a cross section in the thickness direction.

3. The surface resistance of the metal vapor deposition layer is 8.0 × 10 １０ The decorative vapor deposition sheet according to claim 1 or 2, having a resistivity of Ω / □ or more.

4. 4. The decorative vapor deposition sheet according to claim 1, wherein the metal vapor deposition layer contains at least one selected from the group consisting of indium and tin.

5. The decorative vapor deposition sheet according to any one of claims 1 to 4, which is used for vacuum forming.

6. An article comprising the decorative vapor deposition sheet according to any one of claims 1 to 5 adhered to a substrate.

7. The article of claim 6 having a three-dimensional shape.

8. A method for producing an article having a three-dimensional shape, comprising applying the decorative vapor deposition sheet according to any one of claims 1 to 5 to a substrate, and then vacuum forming the applied substrate.

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