Metal-style decorative laminate and urethane-based adhesive

Abstract

The invention provides a metal-style decorative laminate, a metal-style molded body, an injection molded body, a method for manufacturing the metal-style decorative laminate, a method for manufacturing the metal-style molded body, a method for manufacturing the injection molded body, and a urethane adhesive. The present invention relates to a metal-style decorative laminate comprising a first polycarbonate layer, a first adhesive layer, a metal layer laminate comprising a metal layer, a second adhesive layer, and a second polycarbonate layer in this order, the first adhesive layer and the second adhesive layer being configured to have a specific composition. According to the present invention, defects in the appearance of a metallic molded article caused by erosion can be improved without impairing the appearance design and moldability, and hydrolysis resistance can be satisfied.

Description

TECHNICAL FIELD

[0001] The present application relates to a metal style decorative laminate, a metal style molded body, an injection molded body, a method for manufacturing the metal style decorative laminate, a method for manufacturing the metal style molded body, a method for manufacturing the injection molded body, and a urethane-based adhesive. BACKGROUND

[0002] A manufacturing method is known in which, when a molded resin body is molded, a metal style decorative laminate is inserted into a mold, and a molten resin is injected into the mold. The resin molded body manufactured by this manufacturing method can add a metal style appearance design with a high-class feeling at the time of molding. Furthermore, it is possible to achieve process saving, low cost, weight reduction, and the like, and thus it is used for various purposes such as parts for interior and exterior decoration of an automobile.

[0003] As such a metal style decorative laminate for a metal style molded body, for example, there is a laminate that sequentially has a transparent or translucent surface film layer, an adhesive layer, a metal layer holding laminate layer having a metal layer on at least one side, an adhesive layer, and a base film layer (Patent Document 1).

[0004] In addition, a metal style molded body is also known that has the same high-class feeling and brilliance as when glass is used by injection molding a transparent polycarbonate resin as an injection molded resin to the surface side of a metal style decorative laminate (Patent Document 2). By using a polycarbonate resin in this way, it is possible to simultaneously achieve weight reduction and safety at the time of a collision compared to the case where glass is used.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT DOCUMENTS

[0007] Patent Document 1: Japanese Patent Application Publication No. 2004-001243

[0008] Patent Document 2: Japanese Patent Application Publication No. 2022-048656 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] The present application relates to a metal style decorative laminate, a metal style molded body, an injection molded body, a method for manufacturing the metal style decorative laminate, a method for manufacturing the metal style molded body, a method for manufacturing the injection molded body, and a urethane-based adhesive.

[0011] SOLUTION TO PROBLEM

[0012] The present inventors made intensive studies in order to solve the above problems, and as a result, [1] to [7] described below were provided.

[0013] [1] A metal style decorative laminate comprising, in order, a first polycarbonate layer, a first adhesive layer, a metal layer laminate comprising a metal layer, a second adhesive layer, and a second polycarbonate layer, the first adhesive layer and the second adhesive layer containing a polyester diol, a polycarbonate diol, and a reaction product of an aliphatic isocyanate, a carbodiimide, and a silane coupling agent having an epoxy group, the content of a structure derived from the polyester diol in the first adhesive layer and the second adhesive layer being 13.80 parts by mass or more and 14.25 parts by mass or less, the content of a structure derived from the polycarbonate diol being 0.75 parts by mass or more and 1.20 parts by mass or less, the content of a structure derived from the aliphatic isocyanate being 3.20 parts by mass or more and 4.00 parts by mass or less, the content of a structure derived from the carbodiimide being 0.08 parts by mass or more and 0.20 parts by mass or less, and the content of a structure derived from the silane coupling agent being 0.50 parts by mass or more and 0.80 parts by mass or less.

[0014] [2] A metal style molded body provided with the metal style decorative laminate described in [1].

[0015] [3] An injection molded body provided with a resin layer injection molded on a surface of the first polycarbonate layer and / or a surface of the second polycarbonate layer of the metal style molded body described in [2].

[0016] [4] A method for manufacturing the metal style decorative laminate described in [1], comprising: applying the urethane-based adhesive on the first polycarbonate layer and / or the metal layer laminate, and bonding the first polycarbonate layer and the metal layer laminate via the adhesive after drying the urethane-based adhesive; and applying the urethane-based adhesive on the metal layer laminate and / or the second polycarbonate layer, and bonding the metal layer laminate and the second polycarbonate layer by lamination after drying the urethane-based adhesive.

[0017] [5] A method for manufacturing a metal style molded body, comprising a molding step of bringing the metal style decorative laminate described in [1] having a surface temperature of 150°C or higher and 200°C or lower into close contact with a mold to obtain a molded body provided with a metal style decoration.

[0018] [6] A method for manufacturing an injection-molded body, comprising an injection-molding step of forming a resin layer by injecting a resin between a surface of the first polycarbonate layer and / or a surface of the second polycarbonate layer of the metal-style molded body obtained by the method for manufacturing a metal-style molded body according to [5] and an injection-molding die to obtain an injection-molded body in which the metal-style molded body and the resin layer are integrated.

[0019] [7] A urethane-based adhesive containing a polyester diol, a polycarbonate diol, an aliphatic isocyanate, a carbodiimide, and a silane coupling agent having an epoxy group, a content of a structure derived from the polyester diol being 13.80 parts by mass or more and 14.25 parts by mass or less, a content of a structure derived from the polycarbonate diol being 0.75 parts by mass or more and 1.20 parts by mass or less, a content of a structure derived from the aliphatic isocyanate being 3.20 parts by mass or more and 4.00 parts by mass or less, a content of a structure derived from the carbodiimide being 0.08 parts by mass or more and 0.20 parts by mass or less, and a content of a structure derived from the silane coupling agent being 0.50 parts by mass or more and 0.80 parts by mass or less.

[0020] Inventive Effects

[0021] According to the present application, it is possible to provide a metal-style decorative laminate, a metal-style molded body, an injection-molded body, a method for manufacturing a metal-style decorative laminate, a method for manufacturing a metal-style molded body, a method for manufacturing an injection-molded body, and a urethane-based adhesive, which can improve the appearance defect of a metal-style molded product caused by erosion without impairing the appearance design and moldability and which satisfy hydrolysis resistance. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 is a cross-sectional view schematically showing a metal-style decorative laminate (A) according to an embodiment of the present application.

[0023] Figure 2 is a cross-sectional view schematically showing a metal-style decorative laminate (B) according to an embodiment of the present application.

[0024] Figure 3 is a front view ((A)) and side views ((B), (C)) showing the dimensions of an injection-molded body manufactured in an example.

[0025] Figure 4 is a schematic view of an injection-molded body (A) with erosion and an injection-molded body (B) without erosion. DETAILED DESCRIPTION

[0026] The surface film layer of the above-described conventional metal style molded product as a metal style decorative laminate needs to be obtained with adhesion to the injection-molded resin, and therefore the same polycarbonate resin as that used for the injection-molded resin is used. More specifically, the layer structure has, in order, a transparent polycarbonate layer, an adhesive layer, a metal layer retaining laminate layer having a metal layer on at least one side, an adhesive layer, and a base film layer.

[0027] However, in the case of using a polycarbonate resin, the molding temperature reaches a high temperature of 300 to 320°C. Therefore, in the case of the conventional metal style decorative laminate, during injection molding, the uncured adhesive in the metal style decorative laminate in the vicinity of the injection gate melts (erodes), and the appearance of the metal style molded product is deteriorated by the melting.

[0028] In addition, a metal style decorative laminate for interior and exterior decoration of a vehicle seeks high resistance to hydrolysis (hereinafter, described as hydrolysis resistance). Conventionally, as a test for confirming that the required characteristics are satisfied, a hydrolysis test in which the metal style decorative laminate is left to stand for 10 days under conditions of a temperature of 50°C and a relative humidity of 95% RH is performed. It is required that no abnormality such as peeling is confirmed in the adhesive layer in the metal style decorative laminate after the hydrolysis test.

[0029] However, there is an increasing demand for a metal style decorative laminate having higher hydrolysis resistance. As a hydrolysis test as a test for confirming that the required characteristics are satisfied, it is also necessary to change to a hydrolysis test in which the metal style decorative laminate is left to stand for 72 hours under conditions of a temperature of 90°C and a relative humidity of 95% RH. It is required that no abnormality such as peeling of the adhesive layer of the metal style decorative laminate is confirmed before and after the hydrolysis test. When the conventional metal style decorative laminate is subjected to the hydrolysis test based on the conditions, the adhesive layer between the surface film layer and the metal layer retaining laminate layer in the metal style decorative laminate layer is hydrolyzed and peeled, and the metal style decorative laminate cannot pass the hydrolysis test. As described above, the metal style decorative laminate seeks higher hydrolysis resistance, and improvement of the metal style decorative laminate so that it can also pass the new hydrolysis test as an index thereof is sought.

[0030] As described later, the metal style decorative laminate of the present disclosure can obtain a metal style decorative laminate having a specific layer structure, and by providing the first adhesive layer and the second adhesive layer with specific compositions, it is possible to improve the appearance deterioration of the metal style molded product caused by erosion without impairing the appearance design property and the moldability, and to satisfy the hydrolysis resistance.

[0031] Furthermore, an intermediate laminate, a multi-layer laminate, a decorative laminate, a metal style article each having the metal style decorative laminate as a constituent element, and a manufacturing method of the intermediate laminate and a manufacturing method of the decorative laminate can be provided.

[0032] Hereinafter, a metal-style decorative laminate, a metal-style molded body, an injection-molded body, a method for manufacturing a metal-style decorative laminate, a method for manufacturing a metal-style molded body, a method for manufacturing an injection-molded body, and a urethane-based adhesive according to the present application will be described. Furthermore, the present application is not limited to the following examples.

[0033] Furthermore, in the present disclosure, the thickness direction 100 refers to a direction of lamination of the metal-style decorative laminate or the metal-style article as shown in Figure 1 the drawing, and the width direction 110 refers to a direction orthogonal to the length direction 120 of the metal-style decorative laminate or the metal-style article, which is different from the thickness direction. For example, in the case where the intermediate laminate described later is manufactured by roll-to-roll, the length direction 120 corresponds to the flow direction (MD: machine direction), and the width direction 110 corresponds to the TD (transverse direction) orthogonal to the MD.

[0034] Hereinafter, an embodiment of the present disclosure (hereinafter, sometimes referred to as "the present embodiment") will be described. Furthermore, in the present disclosure, the values involved in the description of the numerical range can be arbitrarily combined.

[0035] In addition, the provisions considered to be preferable can be arbitrarily adopted. That is, one provision considered to be preferable can be adopted in combination with another provision or provisions considered to be preferable. It can be said that the combination of the preferable provisions with each other is more preferable.

[0036] [metal-style decorative laminate]

[0037] The metal-style decorative laminate of the present embodiment needs to include, in order, a first polycarbonate layer 10, a first adhesive layer 20, a metal layer laminate 1 including a metal layer 30, a second adhesive layer 50, and a second polycarbonate layer 60. Details of each layer will be described later.

[0038] The metal-style decorative laminate of the present embodiment can be used for decorating a resin part and a metal part or the like (hereinafter, also simply referred to as "article") of a bumper or the like for a vehicle by film decoration methods such as insert molding or over molding. In addition, a multilayer laminate including the metal-style decorative laminate can also be used for decorating the surface of the article via an adhesive layer or an adhesive layer, for example, can be used as a surface layer of an automobile exterior decoration such as a pillar for a car, a door weather strip, a roof trim, a door whole surface, a roof whole surface, or the like. In addition, the metal-style decorative laminate of the present embodiment exhibits an excellent appearance design of a metal style, and has excellent hydrolysis resistance, and thus is preferably used outdoors, and has excellent chemical resistance, and thus is preferably used for decoration of a four-wheeled vehicle, a two-wheeled vehicle, a pump, or the like using lubricating oil.

[0039] Further, as described in detail later, the metal style decorative laminate of the present embodiment is excellent in mass productivity because it is easy to manufacture, and thus is preferred.

[0040] In terms of the layer thickness of the metal style decorative laminate of the present embodiment, in order to improve the design property and the hydrolysis resistance, it is preferably 200 μm or more, more preferably 230 μm or more, further preferably 250 μm or more, and still further preferably 280 μm or more, and in order to improve the moldability and the improvement of the appearance defect, it is preferably 500 μm or less, more preferably 400 μm or less, further preferably 360 μm or less, and still further preferably 320 μm or less. In some cases, the irradiation light of a YAG laser or the like is irradiated from the first polycarbonate layer side of the metal style decorative laminate to the metal layer, and the metal layer is burned to reveal the design, and in this case, it is preferred that the layer thickness of the first polycarbonate layer be reduced, and thus, it is preferred that the upper limit value of the layer thickness of the metal style decorative laminate be set to be low.

[0041] In order to achieve a balance of the design property, the moldability, the improvement of the appearance defect, and the hydrolysis resistance, it is preferably 200 μm or more and 500 μm or less, more preferably 230 μm or more and 400 μm or less, further preferably 250 μm or more and 360 μm or less, and still further preferably 280 μm or more and 320 μm or less.

[0042] In the present disclosure, the "design property" refers to a property of revealing a metal style design of an article by using the metal style decorative laminate of the present disclosure for the article.

[0043] In the present disclosure, the "moldability" refers to a property of easy manufacturing when a metal style article is manufactured using the metal style decorative laminate of the present disclosure. In terms of the moldability, by thickening the layer thickness, it is possible to suppress breakage or the like during molding, and by reducing the layer thickness, it is also possible to decorate a fine portion of the article. For example, it is possible to evaluate by the method described in the examples.

[0044] In the present disclosure, the "improvement of the appearance defect" refers to suppression of a situation in which, during injection molding for manufacturing an injection-molded body mainly using the metal style decorative laminate of the present disclosure, the uncured adhesive in the metal style decorative laminate near the injection gate is melted (eroded), and the appearance of the metal style molded product is defective due to the melting.

[0045] The layer thickness of the metal style decorative laminate of the present embodiment can be adjusted according to the layer thickness of the layers constituting the laminate.

[0046] The metal style decorative laminate of the present embodiment can include only the first polycarbonate layer, the first adhesive layer, the metal layer laminate including the metal layer, the second adhesive layer, and the second polycarbonate layer, and can also include other resin layers described later.

[0047] In the case where the metal style decorative laminate of the present embodiment is provided on an article to produce a metal style molded body described later, the first polycarbonate layer is preferably located on the article side, and the second polycarbonate layer is preferably the most surface side of the metal style molded body.

[0048] 〈Metal Layer Laminate〉

[0049] The metal layer laminate 1 of the present embodiment preferably includes a metal layer and a metal layer holding layer that holds the metal layer. The metal layer holding layer can have the metal layer on only one side, or can have the metal layer on both sides, but from the viewpoint of ease of production while exhibiting design properties, the metal layer holding layer preferably has the metal layer on only one side.

[0050] More specifically, the metal style decorative laminate (A) 2 of the present embodiment preferably includes, in order from the first polycarbonate layer 10, the first adhesive layer 20, the metal layer 30, the metal layer holding layer 40, the second adhesive layer 50, and the second polycarbonate layer 60, and can also include other layers described later. The metal style decorative laminate (B) 3 of the present embodiment preferably includes, in order from the first polycarbonate layer 10, the first adhesive layer 20, the metal layer holding layer 40, the metal layer 30, the second adhesive layer 50, and the second polycarbonate layer 60, and can also have other layers described later.

[0051] The metal style decorative laminate of the present embodiment can be exemplified by the following laminate structures, for example, from the article side. In addition, the symbol " / " indicates the boundary of each layer.

[0052] (1) First polycarbonate layer 10 / First adhesive layer 20 / Metal layer 30 / Metal layer holding layer 40 / Second adhesive layer 50 / Second polycarbonate layer 60

[0053] (2) First polycarbonate layer 10 / First adhesive layer 20 / Metal layer holding layer 40 / Metal layer 30 / Second adhesive layer 50 / Second polycarbonate layer 60

[0054] (3) First polycarbonate layer 10 / First adhesive layer 20 / Metal layer 30 / Metal layer holding layer 40 / Second adhesive layer 50 / Design layer / Second polycarbonate layer 60

[0055] (4) First polycarbonate layer 10 / First adhesive layer 20 / Metal layer holding layer 40 / Metal layer 30 / Second adhesive layer 50 / Design layer / Second polycarbonate layer 60

[0056] Preferably, a structure in which a design layer is laminated as the design layer by printing or a method in which a metal foil is laminated as the design layer.

[0057] (Metal layer holding layer)

[0058] An existing resin sheet can be used as the metal layer retaining layer 40. For example, a sheet containing polycarbonate polyurethane and a silicone surfactant can be used. The mass ratio of the polycarbonate polyurethane to the silicone surfactant is preferably 2.5 parts by mass or more and 5.0 parts by mass or less of the silicone surfactant per 100 parts by mass of the polycarbonate polyurethane.

[0059] In addition, the polycarbonate-based polyurethane may also contain a reactant of an isocyanate, a cyclohexane-free linear hydrocarbon polyol, and a cyclohexane-containing polyol, and the amount of the linear hydrocarbon polyol that does not contain cyclohexane is preferably from 0.60 to 0.80 parts by mass, and the amount of the cyclohexane-containing polyol is preferably from 0.70 to 0.90 parts by mass, relative to 1.00 parts by mass of the isocyanate.

[0060] By using the polycarbonate-based polyurethane as the metal layer retaining layer, the viscosity can be reduced. Sometimes the metal layer retaining layer is wound up as an intermediate before forming the metal layer. Even in the case of winding up, the metal layer retaining layer can be easily wound up due to the low viscosity.

[0061] The metal layer retaining layer can be formed by applying a mixture containing polycarbonate-based polyurethane and a silicone surfactant to the release resin layer and drying it. By ensuring that the ratios of the polycarbonate-based polyurethane isocyanate, the cyclohexane-free linear hydrocarbon polyol, and the cyclohexane-containing polyol are within appropriate ranges, even when the metal layer retaining layer is thinly applied to the release resin layer to a dry film thickness of approximately 10 μm to 25 μm, repulsion is suppressed, allowing the formation of a film of uniform thickness.

[0062] Furthermore, by ensuring that the ratio of the polycarbonate-based polyurethane isocyanate, the cyclohexane-free linear hydrocarbon polyol, and the cyclohexane-containing polyol is within an appropriate range, a uniform metal layer can be formed. Specifically, if the ratio of the polycarbonate-based polyurethane isocyanate, the cyclohexane-free linear hydrocarbon polyol, and the cyclohexane-containing polyol is outside the aforementioned range, lumps may form on the formed metal layer retaining layer. Furthermore, when the metal layer retaining layer is unwound before vapor deposition, static electricity may be generated, increasing the charged voltage of the metal layer retaining layer and preventing the formation of a uniform metal layer, or causing discharge marks on the metal layer.

[0063] Further, it is preferable that the metal layer holding layer has a 100% tensile stress at 100°C of 3 N or less and a breaking elongation at 100°C of 210% or more.

[0064] Here, the tensile stress and the breaking elongation can be measured in accordance with JIS K 7127. That is, the tensile stress can be measured as follows. First, a film of the metal layer holding layer having a width of 10 mm and a length of 150 mm is used as a test sample for measurement, and two parallel lines are set at a distance of 50 mm from the center of the test sample. Then, the stress at the time of stretching the test sample for measurement by 100% (i.e., stretching the length of the distance between the lines to 100 mm) is measured, and this is taken as the 100% tensile stress. Further, the breaking elongation is a value indicating the length dimension at the time of breaking the film of the metal layer holding layer when stretched in the length direction to the breaking point, with respect to the length dimension before stretching. As a test sample for measuring the breaking elongation, for example, a film having a width of 10 mm and a length of 150 mm can be used.

[0065] Since the tensile stress and the breaking elongation of the metal layer holding layer are within the ranges described above, the moldability of the metal style decorative laminate manufactured using this metal layer laminate is good, and even if the metal layer laminate attempts to recover the original shape after molding, peeling can be suppressed.

[0066] Further, the metal layer holding layer preferably also contains a carbodiimide, and preferably 10 parts by mass or more and 25 parts by mass or less of the carbodiimide with respect to 100 parts by mass of the polycarbonate-based polyurethane. Thus, the hydrolysis resistance of the metal style decorative laminate manufactured using this metal layer laminate can be improved to suppress white turbidity and the like.

[0067] Further, in the metal layer holding layer, as the isocyanate, cyclohexyl isocyanate can be used, and 4,4' methylenebis(cyclohexyl isocyanate) can be preferably used. Further, as the linear hydrocarbon-based polyol not containing cyclohexane, n-pentane dimethyl carbonate, n-heptane dimethyl carbonate can be used, and n-hexane dimethyl carbonate can be preferably used. Further, as the polyol containing cyclohexane, cyclohexane diethyl carbonate can be used, and cyclohexane dimethyl carbonate can be preferably used.

[0068] Further, in the metal layer holding layer, the average thickness is 10 μm or more and 25 μm or less, and the thickness is preferably within a range of the average thickness - 0.5 μm or more and the average thickness + 0.5 μm or less.

[0069] By keeping the thickness of the metal layer holding layer within the range, the coiling length of the metal layer holding layer can be increased, and the amount of production (one batch) can be increased. In addition, by keeping the thickness of the metal layer holding layer within the range, in a subsequent process using the metal layer holding layer, the generation of defects such as wrinkling or breaking is suppressed, and the handleability of the metal layer laminate can be improved. In addition, by keeping the thickness of the metal layer holding layer within the range, the tensile stress of the metal layer holding layer can be sufficiently reduced, and the formability of a decorative sheet using the metal layer laminate is good.

[0070] In addition, the thickness of the metal layer holding layer is preferably within a range of -0.5 μm from the average thickness to 0.5 μm above the average thickness. That is, since the metal layer holding layer is formed to have a uniform thickness, a metal layer laminate of stable quality and a metal style decorative laminate manufactured using the metal layer laminate of stable quality can be obtained.

[0071] In addition, the metal layer holding layer preferably has a total light transmittance of 90% or more and a haze of 1.3% or less. By setting the total light transmittance and the haze to this range, the transparency of a metal style decorative laminate manufactured using the metal layer laminate is higher, and the metal style decorative laminate can be sufficiently given a metal style design property, and a desired design property can be obtained. By appropriately adjusting the material of the metal layer holding layer and the thickness of the layer, the total light transmittance can be made to be a desired total light transmittance.

[0072] The metal layer holding layer as described above can be formed using, for example, a polycarbonate-based polyurethane dispersion (water-based polycarbonate-based polyurethane dispersion) in which a polyurethane resin is dispersed in a water-based solvent such as water. As the polyurethane dispersion, for example, polyurethane dispersion UW5002, UW5502 (manufactured by Ube Industries, Ltd.), or the like can be used.

[0073] In addition, in the metal layer holding layer, a single polyurethane resin can be used, or two or more polyurethane resins having different structures can be used in mixture. For example, polyurethane dispersion UW5002, UW5502 (manufactured by Ube Industries, Ltd.), or the like can be used in mixture so that the metal layer holding layer has the above-described properties.

[0074] In addition, in order to give a desired design property, the metal layer holding layer can be subjected to matte processing, etching processing, hairline processing, or the like. In addition, in order to obtain a desired color tone, the metal layer holding layer can contain a pigment or a dye.

[0075] In addition, the metal layer holding layer can contain, in addition to the above-described materials, a stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, an antistatic agent, or the like.

[0076] (Metal Layer)

[0077] The metal layer is held by the metal layer holding layer, and by using the metal layer laminate, the metal style decoration laminate can be given a metal style design property.

[0078] The metal layer can be a uniform layer, or a layer in which an island structure of metal is continuously present. The island structure is held by the first adhesive layer or the second adhesive layer. Since the metal layer is an island structure in which metal particles are separated from each other and have gaps, even if deep drawing is performed, the metal luster can be maintained by preventing a blushing phenomenon, and thus is preferable.

[0079] The amount of metal per unit area and the thickness of the metal layer can be adjusted according to the conditions at the time of manufacturing the metal layer, and the like. Details are described later.

[0080] The thickness of the metal layer is not particularly limited as long as the desired design property is exhibited, and is preferably 5 nm or more and 100 nm or less, more preferably 10 nm or more and 80 nm or less, further preferably 20 nm or more and 70 nm or less, and still further preferably 40 nm or more and 60 nm or less. The thickness of the metal layer is preferably the lower limit value or more, in order to form a uniform layer and exhibit an excellent metal style design property, and thus is preferable. In addition, by setting the thickness of the metal layer to the upper limit value or less, the manufacturing cost can be suppressed while sufficiently exhibiting the design property, and thus is preferable.

[0081] In addition, the metal style decoration laminate exhibits a metal style design property due to reflection of external light by the metal layer. Therefore, in the absence of external light or in the presence of weak external light at night or the like, the metal style design property is not exhibited. Therefore, there is a method in which a backlight is provided on the article side of the metal style decoration laminate, and the design property is exhibited by transmitted light from the backlight. In order to exhibit this effect, the thickness of the metal layer is preferably thinned, and is preferably in the range of 5 nm or more and 50 nm or less.

[0082] In addition, the metal constituting the metal layer is not particularly limited as long as the desired design property is exhibited, and can be appropriately selected according to the desired design property, and the like. As the metal constituting the metal layer, a metal in which one or two or more metals or alloys having excellent ductility are combined, and which can impart sufficient metal luster to the metal style decoration laminate, is preferable. Specifically, one or two or more selected from the group consisting of aluminum, indium, chromium, zinc, gallium, nickel, tin, silver, gold, silicon, chromium, titanium, platinum, palladium, nickel, stainless steel, Hastelloy, and alloys of these is preferable.

[0083] In addition, the metal layer can be formed, for example, by vapor deposition of the above-described metal on the metal layer holding layer. In addition, the metal layer can be formed, for example, by a sputtering method or an ion plating method.

[0084] In addition, the width direction dimension of the metal layer laminate of the present embodiment is not particularly limited, and is only required to be an industrially producible width, and is preferably, for example, 1,000 mm or more and 2,000 mm or less. Further, in the metal layer holding layer, by using the above-described polycarbonate-based polyurethane, a metal layer holding layer having a uniform layer thickness can be stably formed, and is suitable for the industrial production of the metal layer laminate.

[0085] In the case where the metal layer laminate is transported or stored in a state as an intermediate such as a metal style decoration laminate, in order to prevent contamination or damage, a protective film can be further laminated on the metal layer side of the metal layer laminate, or a release resin layer can be further laminated on the side opposite to the metal layer of the metal layer holding layer.

[0086] In addition, in the metal layer holding layer, by using the above-described polycarbonate-based polyurethane, a metal layer holding layer having a uniform layer thickness can be formed. In addition, by suppressing the generation of static electricity in the metal layer holding layer, the caking of the metal layer holding layer can be suppressed. Thereby, the formation of discharge marks and the like in the metal layer is suppressed, and in addition, a metal layer having a uniform layer thickness can be formed on the metal layer holding layer. In addition, by producing a metal style decoration laminate using this metal layer laminate, a metal style decoration laminate having the same appearance design as a conventional decoration sheet using a modified polyethylene terephthalate can be obtained.

[0087] As for the metal layer laminate, the metal layer can be laminated on the first adhesive layer side of the metal layer holding layer as in the metal style decoration laminate A as shown in Figure 1 In addition, the metal layer can be laminated on the second polycarbonate layer side of the metal layer holding layer as in the metal style decoration laminate B as shown in Figure 2

[0088] <First Polycarbonate Layer>

[0089] The first polycarbonate layer is a layer disposed on the lowermost layer of the metal style decoration laminate (the article side of the injection-molded body). The first polycarbonate layer is preferably a layer that is resistant to the temperature at the time of decoration using the metal style decoration laminate. As described above, the metal style decoration laminate exhibits a metal style appearance design by the reflection of external light by the metal layer, and thus the transparency and the color tone with respect to the first polycarbonate layer located on the article side are less strictly required than the metal layer. However, in the case where the color is recognized by a visual recognizer observing the article, the transparency and the color tone can be appropriately adjusted.

[0090] ​In view of such an influence on the color tone or transparency, the raw material for forming the first polycarbonate layer can be appropriately selected from polycarbonate resins in consideration of heat resistance with respect to the temperature at the time of molding, compatibility of an injection molding resin with an extrusion resin in insert injection molding or extrusion lamination, and the like, depending on the use.

[0091] For example, in the case where high transparency is required, a first polycarbonate layer using a polycarbonate resin, which is excellent in transparency and has high injection adhesion, as a raw material can be used.

[0092] The layer thickness of the first polycarbonate layer can be set to a thickness generally for a decorative sheet, but in the case where lamination processing with a metal layer laminate is performed, in order to suppress the generation of defects such as wrinkles, it is preferably set to be equal to or greater than a lower limit value, and in order to suppress the breakage of the metal style decorative laminate at the time of molding processing and improve the moldability of the metal style decorative laminate, it is preferably equal to or less than an upper limit value, and is preferably equal to or greater than 20 μm and equal to or less than 500 μm, more preferably equal to or greater than 50 μm and equal to or less than 300 μm, further preferably equal to or greater than 80 μm and equal to or less than 200 μm, and still further preferably equal to or greater than 100 μm and equal to or less than 150 μm.

[0093] <First adhesive layer>

[0094] The first adhesive layer is a layer that adheres the metal layer laminate and the first polycarbonate layer.

[0095] The first adhesive layer needs to contain a reaction product of a polyester-based diol, a polycarbonate-based diol, and an aliphatic isocyanate, a carbodiimide, and a silane coupling agent having an epoxy group. Each component is described later.

[0096] For example, the first adhesive layer can be formed by applying a urethane-based adhesive described later on the metal layer laminate and / or the first polycarbonate layer and further curing it. The urethane-based adhesive is an adhesive that is useful in view of transparency or adhesion, heat resistance against the temperature at the time of molding, and the like. As a standard of transparency, for example, light transmittance or haze can be used as an index.

[0097] The method of forming the first adhesive layer with the urethane-based adhesive is not particularly limited. For example, the first adhesive layer can be formed by applying an appropriate amount of the urethane-based adhesive with a publicly known device such as a gravure coater, a reverse coater, a knife coater, a roll coater, and the like, and drying it as necessary.

[0098] Further, the layer thickness of the first adhesive layer can be set to a layer thickness generally for a metal-style decoration laminate. In order to improve moldability and appearance defects, it is preferable to be thin, and in order to improve hydrolysis resistance, it is preferable to be thick, and it is preferable to be 1 μm or more and 30 μm or less, more preferably 3 μm or more and 25 μm or less, further preferably 5 μm or more and 20 μm or less, still further preferably 7 μm or more and 15 μm or less, and even more preferably 8 μm or more and 12 μm or less. In some cases, an irradiation light such as a YAG laser is irradiated from the first polycarbonate layer side of the metal-style decoration laminate to the metal layer, and the metal layer is burned to reveal the appearance design, and in this case, it is preferable to thin the layer thickness of the first polycarbonate layer.

[0099] <Second Adhesive Layer>

[0100] The second adhesive layer is a layer that adheres the second polycarbonate layer and the metal layer laminate.

[0101] The second adhesive layer needs to contain a reaction product of a polyester diol, a polycarbonate diol, and an aliphatic isocyanate, a carbodiimide, and a silane coupling agent having an epoxy group. Each component is described later.

[0102] For example, the second adhesive layer can be formed by applying a urethane-based adhesive described later on the metal layer laminate and / or the second polycarbonate layer. The urethane-based adhesive is a useful adhesive in consideration of transparency or adhesiveness, heat resistance against temperature during molding, and the like. As a standard for transparency, for example, light transmittance or haze can be used as an index. The adhesive used for the second adhesive layer can be the same as the adhesive used for the first adhesive layer.

[0103] The method of forming the second adhesive layer with an adhesive is not particularly limited. For example, the second adhesive layer can be formed by applying an appropriate amount of adhesive with a known device such as a gravure coater, a reverse coater, a knife coater, a roll coater, and the like, and drying it as necessary.

[0104] Further, the layer thickness of the second adhesive layer can be set to a layer thickness generally for a metal-style decoration laminate. In order to improve moldability and appearance defects, it is preferable to be thin, and in order to improve hydrolysis resistance, it is preferable to be thick, and it is preferable to be 1 μm or more and 30 μm or less, more preferably 3 μm or more and 25 μm or less, further preferably 5 μm or more and 20 μm or less, still further preferably 7 μm or more and 15 μm or less, and even more preferably 8 μm or more and 12 μm or less. The second adhesive layer can also be set to the same layer thickness as the first adhesive layer.

[0105] The first adhesive layer and the second adhesive layer are preferably cured products of urethane-based adhesives. The same urethane-based adhesive can be cured to form the first adhesive layer and the second adhesive layer. In addition, the first adhesive layer and the second adhesive layer can be formed by the same conditions with respect to the coating amount or curing conditions of the urethane-based adhesive.

[0106] <Second Polycarbonate Layer>

[0107] The second polycarbonate layer is a layer disposed on the uppermost layer of the metal-style decoration laminate (on the side opposite to the article in the injection-molded body, the side visible to the viewer). The second polycarbonate layer is preferably a layer having transparency to enable the viewer to visually recognize the reflected light from the metal layer, and to withstand the temperature during decoration using the metal-style decoration laminate. In addition, it is preferable to function as a protective layer for the metal layer laminate.

[0108] The second polycarbonate layer can contain various pigments or dyes, etc. in order to adjust the transparency or color tone, etc., and can also be dyed with a dye. Furthermore, the second polycarbonate layer can be previously printed as desired. In this case, it can be printed on the surface of the second polycarbonate layer that contacts the outside, but by printing on the surface opposite to the surface that contacts the outside, i.e., the surface that contacts the second adhesive layer, the durability of the printing can be improved, and thus it is preferable.

[0109] As the material of the second polycarbonate layer, a polycarbonate-based resin having excellent processability, heat resistance to the temperature during molding, moldability, transparency, impact resistance, and high adhesion can be appropriately selected as the material of the second polycarbonate layer.

[0110] The thickness of the second polycarbonate layer can be set to the general thickness of a decoration sheet, but in order to suppress the occurrence of defects such as wrinkles during the lamination process with the metal layer laminate, it is preferable to be set to be greater than or equal to the lower limit value, and in order to suppress the breakage of the metal-style decoration laminate during the molding process and to improve the moldability of the metal-style decoration laminate, it is preferable to be less than or equal to the upper limit value, preferably 20 μm or more and 500 μm or less, more preferably 50 μm or more and 300 μm or less, further preferably 80 μm or more and 200 μm or less, and still further preferably 100 μm or more and 150 μm or less.

[0111] (Urethane-based Adhesive)

[0112] The first adhesive layer and the second adhesive layer need to contain 13.80 mass parts or more and 14.25 mass parts or less of a reactant of a polyester diol, a polycarbonate diol, and an aliphatic isocyanate, 0.75 mass parts or more and 1.20 mass parts or less of a content derived from the structure of the polycarbonate diol, 3.20 mass parts or more and 4.00 mass parts or less of a content derived from the structure of the aliphatic isocyanate, 0.08 mass parts or more and 0.20 mass parts or less of a content derived from the structure of the carbodiimide, and 0.50 mass parts or more and 0.80 mass parts or less of a content derived from the structure of the silane coupling agent. For details, description is made in the item of [urethane-based adhesive].

[0113] The metal-style decorative laminate of the present embodiment is preferably excellent in hydrolysis resistance. The specific conditions of the hydrolysis test for evaluating the hydrolysis resistance are that the metal-style decorative laminate is left to stand under conditions of a temperature of 90°C and a relative humidity of 95% RH for 72 hours.

[0114] Further, the standard of excellent hydrolysis resistance is that the total light transmittance of the metal-style decorative laminate is 10% or more and 20% or less, the haze is 5.5% or less, and the peeling force of the first adhesive layer and the second adhesive layer obtained from the 180-degree peeling test based on JIS K 6854-2 is 20 N / 25 mm or more before and after the hydrolysis test.

[0115] Since the total light transmittance is 10% or more and 20% or less, the metal-style decorative laminate has the following advantages: while obtaining sufficient appearance design of the metal style, in the case where illumination is turned on from the back surface of the metal-style decorative laminate, light emitted from the illumination can be transmitted through the metal-style decorative laminate. By this function, the appearance of the metal-style decorative laminate in the daytime bright environment when the illumination is not turned on becomes the appearance design of the metal style, and in the nighttime dark environment by turning on the illumination from the back surface of the metal-style decorative laminate, light can be transmitted to be visible. When the total light transmittance is 10% or more, light is not blocked by the metal-style decorative laminate, and sufficient emission can be obtained, and thus it is preferred. In addition, when the total light transmittance is 20% or less, in the case where light is transmitted, the evaporation unevenness of the metal of the metal layer is not visually recognized, and excellent appearance design is exhibited, and thus it is preferred.

[0116] Second, since the haze is 5.5% or less, the sheet does not have a color cast or haze due to a low degree of diffusion of light transmitted through the metal style decorative laminate, and excellent design properties of the metal style can be satisfied. If the haze is 5.5% or less, the effect of the degree of diffusion of light transmitted through the metal style decorative laminate on the color cast or haze of the sheet is not confirmed, and the design properties of the metal style can be satisfied, and thus is preferable. In addition, the smaller the haze, the more the color cast or haze of the sheet is suppressed, and thus the lower limit value is not particularly limited.

[0117] Further, the peeling force of the first adhesive layer 20 and the second adhesive layer 50 obtained from the 180-degree peeling test based on JIS K 6854-2 is 20 N / 25 mm or more, which is a standard for maintaining the peeling force and adhesion due to non-hydrolysis of the first adhesive layer 20 and the second adhesive layer 50. That is, it can be said that, in the case where the peeling force is 20 N / 25 mm or more, peeling of the adhesive layer due to hydrolysis does not occur. In addition, the upper limit of the peeling force is not particularly limited, and in the 180-degree peeling test, it becomes a result that the adhesive layer is broken when the peeling force is strong, and thus the breakage of the adhesive layer can be regarded as the upper limit.

[0118] The metal style decorative laminate of the present embodiment is preferably not cracked in 200% elongation. The metal style decorative laminate is sometimes used without elongation processing, and on the other hand, is sometimes molded into a desired shape and processed into a metal style molded body described later, and in the molding processing, the metal style decorative laminate is sometimes elongated and molded. Not being cracked in 200% elongation becomes a standard that the portion elongated when the metal style decorative laminate is elongated by the molding processing is not cracked. That is, it can be said that, if not cracked in 200% elongation, there is no need to worry about the elongation processing portion of the metal style molded body being cracked.

[0119] The metal style decorative laminate preferably has the first adhesive layer and the second adhesive layer not fused at a temperature of 300°C to 320°C.

[0120] In the case where the metal style decorative laminate is used to manufacture a metal style injection molded body, for example, a polycarbonate resin is melted and injected between the surface of the first polycarbonate layer and / or the surface of the second polycarbonate layer and an injection molding mold, to form a resin layer. The molding temperature of the polycarbonate resin at the time of injection molding is a high temperature of 300°C to 320°C. Therefore, when the first adhesive layer and the second adhesive layer are fused at a temperature of 300°C or more and 320°C or less, erosion occurs, and the appearance of the metal style injection molded body can be poor due to the erosion.

[0121] Here, the erosion specifically refers to a phenomenon in which at least either one of the first adhesive layer and the second adhesive layer is melted due to heat of the polycarbonate resin at the time of injection molding, and as a result, the metal layer of the surface of the metal-look injection molded body near the gate of the mold disappears.

[0122] However, if the first adhesive layer and the second adhesive layer do not melt at a temperature of 300°C or higher and 320°C or lower, the erosion does not occur, and thus, generation of appearance defects of the metal-look injection molded body due to the erosion can be prevented.

[0123] [metal-look molded body]

[0124] The metal-look molded body of the present embodiment is a molded body of the metal-look decorative laminate (300A or 300B). The metal-look decorative laminate will be described below.

[0125] The metal-look molded body is, for example, a molded body manufactured from the metal-look decorative laminate by the manufacturing method described below, and is a molded body molded into a desired shape according to a purpose. For example, the metal-look molded body is used for a housing of a smartphone, a mobile phone, an automobile door mirror housing, a front grille, a door handle, a wheel center cover, a badge, a decoration, a trim, a light reflector, a center console, a mounting panel, and the like, a housing or a decorative portion of a personal computer or a TV, a housing or a decorative portion of a household appliance, a housing or a decorative portion of a pinball machine, a pachinko machine, a game machine, or the like, or is used for a travel bag or a travel case or the like for general purposes, and can impart a decorative or an appearance design of a metal look instead of plating or a metal material.

[0126] The metal-look molded body can have other structures in addition to the above-described structure. For example, during use of the metal-look molded body, the surface of the protective layer or the base material layer is maintained in a clean state, and dirt is prevented from adhering, and thus, a release paper or a protective film or the like can be provided on the surface of the protective layer or the base material layer.

[0127] The metal-look molded body sometimes exhibits a decorative or an appearance design by transmitting light through the metal layer using a structure of a backlight. In this case, the metal-look molded body is required to be transparent. The light transmittance or the haze as a standard of the transparency will be described below, and thus, the description is omitted.

[0128] [injection molded body]

[0129] The injection-molded body of the present embodiment has an injection-molded resin layer on the surface of the first polycarbonate layer and / or the surface of the second polycarbonate layer of the metal-style molded body of the present embodiment. The injection-molded body can be further processed for use in housings of smartphones, mobile phones, exterior housings of automobile door mirrors, front grilles, door handles, wheel center covers, emblems, ornaments, trim, light reflectors, center consoles, instrument panels, and the like, housings or ornamental parts of personal computers or TVs, home appliances. As for the metal-style molded body, the description is omitted as described above.

[0130] The thickness of the resin layer is not particularly limited and can be, for example, 100 μm or more and 20 mm or less. In addition, as the resin used, polycarbonate as a thermoplastic resin can be used.

[0131] [Method for manufacturing metal-style decorative laminate]

[0132] The method for manufacturing the metal-style decorative laminate of the present embodiment includes the first bonding process and the second bonding process described later. Hereinafter, an example of the method for manufacturing the metal-style decorative laminate will be described. Further, the metal-style decorative laminate (B) 3 can be manufactured with reference to the method for manufacturing the metal-style decorative laminate (A) 2.

[0133] The method for manufacturing the decorative sheet of the present embodiment includes a first laminate forming process in which a mixture containing an aqueous polycarbonate-based polyurethane dispersion and a silicone surfactant is formed into a film with an average dry film thickness of 10 μm or more and 25 μm or less on the surface of a release resin layer, to obtain a first laminate in which the release resin layer and a metal layer holding layer are laminated; an unwinding process in which the wound product of the first laminate is unwound; and an evaporation process in which a metal layer is evaporated on the metal layer holding layer after the unwinding process, to obtain a second laminate including a metal layer laminate including the metal layer holding layer and the metal layer. Further, the unwinding process and the evaporation process are usually performed continuously.

[0134] Hereinafter, the method for manufacturing the decorative sheet 300A will be described in the order of the first laminate forming process, the unwinding process, the evaporation process, the first bonding process, and the second bonding process.

[0135] (First laminate forming process)

[0136] In the first laminate forming process, the mixture containing the aqueous polycarbonate-based polyurethane dispersion and the silicone surfactant is formed into a film with an average dry film thickness of 10 μm or more and 25 μm or less. Specifically, the metal layer holding layer 40 is formed by applying the mixture to the release resin layer using, for example, a die coater and drying it. Thus, the metal layer holding layer 40 is formed without being stretched, to obtain the first laminate.

[0137] Since the mixture of raw materials of the metal layer holding layer 40 contains the organosilicon surfactant, wettability can be improved, cissing at the time of forming the metal layer holding layer 40 can be suppressed, and the metal layer holding layer 40 can be uniformly formed when the metal layer holding layer 40 is formed by casting.

[0138] In addition, the mixture can also contain carbodiimide. In the case where the solvent resistance of the metal layer holding layer 40 is insufficient, whitening of the metal layer holding layer 40 and reduction in the glossiness of the metal finish layered body (A) 2 can sometimes occur at the time of applying the urethane-based adhesive. Since the mixture of raw materials of the metal layer holding layer 40 contains carbodiimide, the solvent resistance of the metal layer holding layer 40 can be improved to suppress whitening even in the case where the urethane-based adhesive contains a solvent.

[0139] The mixture of raw materials of the metal layer holding layer 40 can also contain water. Since the mixture contains water, the volatility of the solvent is improved, and in addition, the viscosity of the mixture of raw materials can be reduced to suppress foaming of the mixture of raw materials. In addition, the caking of the metal layer holding layer 40 can be suppressed.

[0140] Further, in the first layered body forming step, in order to obtain a uniform film of the metal layer holding layer 40, each raw material can be supplied to a filter for filtration when the mixture of raw materials is prepared. As a filter for filter filtration, for example, a filter having a pore size of 1 μm can be used, and the material of the filter can be variously selected in accordance with each raw material.

[0141] In addition, the drying treatment after applying the mixture of raw materials can be set to a condition in which the solvent and the like contained in the mixture of raw materials is sufficiently removed to form a film of the metal layer holding layer 40. For example, at a temperature of about 150°C, it can be set to about 3 minutes.

[0142] The size of the release resin layer is not particularly limited, and for example, in consideration of industrial production, it can be set to a width of 1000 mm or more and 2000 mm or less and a length of 300 m or more and 500 m or less. Such a release resin layer is usually in a state of being wound (winding article), and the first layered body is obtained by unwinding the winding article while applying the mixture of raw materials of the metal layer holding layer and drying it.

[0143] (Unwinding step)

[0144] The first layered body is usually continuously produced in a long strip shape, and is wound together with the formation of the metal layer holding layer 40, and is temporarily stored in a state of being wound as a winding article before the metal layer 30 is formed. The unwinding step is a step of unwinding such a winding article of the first layered body before the metal layer 30 is formed.

[0145] (Vapor deposition step)

[0146] The vapor deposition step is a step of vapor depositing the metal layer 30 on the metal layer holding layer 40 after the uncoiling step. By the vapor deposition step, the metal layer laminate 1 provided with the metal layer holding layer 40 and the metal layer 30 is obtained.

[0147] Further, the metal layer laminate provided with the metal layer laminate 1 can be circulated or stored as an intermediate of the metal style decoration laminate (A) 2 or the metal style decoration laminate (B) 3.

[0148] (First adhesion step)

[0149] The first adhesion step is a step of adhering the first polycarbonate layer 10 and the metal layer laminate 1 by lamination after applying the urethane-based adhesive on the first polycarbonate layer 10 and / or the metal layer laminate 1 and drying the urethane-based adhesive.

[0150] In the case of manufacturing the metal style decoration laminate (A) 2, after the vapor deposition step, the metal layer 30 and the first polycarbonate layer 10 are adhered by lamination after applying the urethane-based adhesive on the metal layer 30 of the second laminate provided with the metal layer laminate 1 and / or the first polycarbonate layer 10 and drying the urethane-based adhesive. In addition, by this adhesion, the first adhesion layer 20 is formed.

[0151] That is, in the first adhesion step, as long as the urethane-based adhesive is applied on at least one of the metal layer 30 of the metal layer laminate 1 and the first polycarbonate layer 10, it can be applied on either one or both.

[0152] In addition, in the case of manufacturing the metal style decoration laminate (B) 3, after the vapor deposition step, the metal layer holding layer 40 and the first polycarbonate layer 10 are adhered by lamination after applying the urethane-based adhesive on the metal layer holding layer 40 of the second laminate provided with the metal layer laminate 1 and / or the first polycarbonate layer 10 and drying the urethane-based adhesive. In addition, by this adhesion, the first adhesion layer 20 is formed.

[0153] That is, in the first adhesion step, as long as the urethane-based adhesive is applied on at least one of the metal layer holding layer 40 of the metal layer laminate 1 and the first polycarbonate layer 10, it can be applied on either one or both.

[0154] (Second adhesion step)

[0155] The second bonding step is a step of bonding the metal layer laminate 1 and the second polycarbonate layer 60 by lamination after applying a urethane-based adhesive to the metal layer laminate 1 and / or the second polycarbonate layer 60 and drying the urethane-based adhesive.

[0156] In the case of manufacturing the metal style decorative laminate (A) 2, after the vapor deposition step, the metal layer holding layer 40 and the second polycarbonate layer 60 are bonded by lamination after applying a urethane-based adhesive to the metal layer holding layer 40 of the second laminate provided with the metal layer laminate 1 and / or the second polycarbonate layer 60 and drying the urethane-based adhesive. In addition, by this bonding, the second bonding layer 50 is formed.

[0157] That is, in the second bonding step, as long as a urethane-based adhesive is applied to at least one of the metal layer holding layer 40 of the metal layer laminate 1 and the second polycarbonate layer 60, it can be applied to either one or both.

[0158] In addition, in the case of manufacturing the metal style decorative laminate (B) 3, after the vapor deposition step, the metal layer 30 and the second polycarbonate layer 60 are bonded by lamination after applying a urethane-based adhesive to the metal layer 30 of the second laminate provided with the metal layer laminate 1 and / or the second polycarbonate layer 60 and drying the urethane-based adhesive. In addition, by this bonding, the second bonding layer 50 is formed.

[0159] That is, in the second bonding step, as long as a urethane-based adhesive is applied to at least one of the metal layer 30 of the metal layer laminate 1 and the second polycarbonate layer 60, it can be applied to either one or both.

[0160] Furthermore, the order of these bonding steps is not particularly limited, and the first bonding step can be performed first, the second bonding step can be performed first, the first bonding step and the second bonding step can be performed simultaneously, or the second bonding step can be performed first and the first bonding step can be performed subsequently.

[0161] In addition, in the manufacturing method of the decorative sheet of the present embodiment, a roll of the laminate (first laminate) of the release resin layer and the metal layer holding layer 40 is used, but the metal layer 30 can be laminated without rolling the first laminate.

[0162] [Manufacturing method of metal style molded body]

[0163] The manufacturing method of the metal style molded body of the present embodiment includes a molding step of bringing the metal style decorative laminate of the present embodiment, whose surface temperature is 150°C or higher and 200°C or lower, into close contact with a mold to obtain a molded body of the metal style decorative laminate.

[0164] (Molding step)

[0165] In order to thermoform the metal style decorative laminate, the surface temperature of the metal style decorative laminate is 150°C or higher and 200°C or lower, whereby in the forming, the metal style decorative laminate does not shrink, nor does it undergo whitening or the like, and thus good formability can be satisfied. Since the surface temperature is 150°C or higher, the metal style decorative laminate is sufficiently softened, and does not undergo sagging deformation due to shrinkage, which makes it difficult to process or form. In addition, since the surface temperature is 200°C or lower, it is possible to prevent the metal style decorative laminate from being excessively softened due to becoming a molten state, which makes it difficult to form or causes the metal style decorative laminate to easily undergo whitening or the like.

[0166] The shape of the mold to which the metal style decorative laminate is tightly adhered can be set to any shape, so that the metal style formed body can be formed into a desired shape. For example, a mold such as a male mold or a female mold in which the surface of brass is plated with chromium can be used. In addition, the temperature of the mold can be set to any temperature, taking into account the control of the surface temperature of the metal style decorative laminate or the control of the cooling conditions of the metal style formed body after the forming process.

[0167] As a method of tightly adhering the metal style decorative laminate to the mold, any method can be adopted, taking into account the ease of forming or the cost of forming such as direct forming using a female mold, hot sheet drape forming using a male mold, plunger-assisted forming using a plunger (auxiliary mold), or the like. In addition, a vacuum forming method in which the metal style decorative laminate is attracted to the mold or a pressurization forming method in which the metal style decorative laminate is tightly adhered to the mold by the pressure of compressed air can be adopted. For example, by tightly adhering the metal style decorative laminate to the mold using vacuum and / or pressurization, the adhesion of the metal style decorative laminate to the mold is improved, and thus a more precise shape can be processed.

[0168] (Clamping Process)

[0169] The metal style formed body manufacturing method of the present embodiment can include a clamping process of clamping the metal style decorative laminate before the forming process. By this process, the metal style decorative laminate can be adjusted so as not to sag and fixed at the time of forming. The clamping can be performed by gripping both ends of the metal style decorative laminate using a plurality of gripping units that can grip both surfaces of the metal style decorative laminate, for example. The gripping of the metal style decorative laminate is not limited to both ends of the metal style decorative laminate, and any portion of the metal style decorative laminate can be gripped. Typically, in the case of continuously producing metal style formed bodies, both end portions in the width direction of the metal style decorative laminate can be gripped. In addition, in the case of producing metal style formed bodies in batches using a quadrangular member in which the metal style decorative laminate is cut to a predetermined length, the end portions of the four sides can be gripped by upper and lower frames.

[0170] (heating step)

[0171] Further, the manufacturing method of the metal style molded body according to the embodiment can include a heating step of heating the metal style decoration laminate after the clamping step. For example, after the metal style decoration laminate at room temperature is clamped and adjusted so as not to be slack, a plurality of heaters or the like can be used as a heating unit, and these heaters or the like can be arranged above and below the metal style decoration laminate to uniformly heat both surfaces of the metal style decoration laminate at the same time. By this heating step, the surface temperature of the metal style decoration laminate can be controlled to be 150°C or higher and 200°C or lower.

[0172] (other steps)

[0173] The manufacturing method of the metal style molded body can include other steps in addition to the steps described above. For example, during a period until the metal style molded body is processed in the next step, the surface of the protective layer or the base material layer is maintained in a clean state to prevent dirt from adhering, and thus, a sticking step of sticking a protective film or the like to the surface of the protective layer or the base material layer can be included. Also, after the metal style molded body is inserted into an injection molding mold, insert injection molding of a resin can be performed, and the surface of the injection molded product can be decorated.

[0174] [manufacturing method of injection molded body]

[0175] The manufacturing method of the injection molded body according to the embodiment includes an injection molding step of forming a resin layer by injecting a resin between the surface of the first polycarbonate layer 10 and / or the surface of the second polycarbonate layer 60 of the metal style molded body obtained by the manufacturing method of the metal style molded body according to the embodiment and an injection molding mold using the injection molding mold to obtain an injection molded body in which the metal style molded body and the resin layer are integrated. Regarding the metal style molded body, the description is omitted as described above.

[0176] The injection molding step can be performed using a general injection molding machine. As the resin used, polycarbonate as a thermoplastic resin can be used. The polycarbonate can be melted and injected between the surface of the first polycarbonate layer 10 and / or the surface of the second polycarbonate layer 60 and the injection molding mold to form the resin layer.

[0177] Further, as the manufacturing method of the injection molded body, a trimming step of trimming the metal style molded body into an arbitrary shape before the injection molding step, a cooling step of cooling the molded product after the injection molding step, a taking-out step of taking out the molded product from the injection molding mold after the cooling step, or the like can be further included.

[0178] [urethane-based adhesive]

[0179] The urethane-based adhesive of the present embodiment is a urethane-based adhesive for a metal finish decoration laminate of the present embodiment, which is a reaction product of a polyester-based diol, a polycarbonate-based diol, and an aliphatic isocyanate, and contains a carbodiimide and a silane coupling agent having an epoxy group.

[0180] Generally, as a urethane-based adhesive for a metal finish decoration laminate, an adhesive composed of only a polyester-based diol as a main agent, an aliphatic isocyanate as a curing agent, and a solvent in which they are dissolved is used. This urethane-based adhesive forms urethane bonds by reacting a polyester-based diol with an aliphatic isocyanate, and exhibits adhesiveness. However, if this adhesive is used, as described above, it cannot pass the hydrolysis test under more severe test conditions, and does not satisfy the hydrolysis resistance. In addition, in the case where a polycarbonate resin is used as a resin for an injection-molded body, appearance defects of a metal finish molded product caused by erosion of the adhesive can occur.

[0181] Therefore, in the present embodiment, the main agent is replaced from only a polyester-based diol to a polycarbonate-based diol instead of a part of the polyester-based diol, and a polyester-based diol and a polycarbonate-based diol are used. Furthermore, by adding an aliphatic isocyanate, the heat resistance of the first adhesive layer and the second adhesive layer can be improved. As a result, erosion can be prevented, and the occurrence of appearance defects of a metal finish molded product can be prevented.

[0182] The urethane-based adhesive of the present embodiment, in addition to using a polyester-based diol and a polycarbonate-based diol in combination and adding an aliphatic isocyanate, further adds a carbodiimide and a silane coupling agent. Thereby, it can pass the hydrolysis test under more severe test conditions, and the adhesive strength is improved by performing the hydrolysis test compared to before the test. In addition, the increase in the haze value caused by the hydrolysis test can be suppressed, and a result that excellent metal finish appearance designability can be satisfied before and after the hydrolysis test is achieved.

[0183] To achieve the aforementioned erosion prevention and hydrolysis resistance, it is important that the polyester diol, polycarbonate diol, aliphatic isocyanate, carbodiimide, and silane coupling agent are compatible, and the proportions of these components are also important. The urethane adhesive of this embodiment requires that the content of the structure derived from the polyester diol be 13.80 parts by mass to 14.25 parts by mass, the content of the structure derived from the polycarbonate diol be 0.75 parts by mass to 1.20 parts by mass, the content of the structure derived from the aliphatic isocyanate be 3.20 parts by mass to 4.00 parts by mass, the content of the structure derived from the carbodiimide be 0.08 parts by mass to 0.20 parts by mass, and the content of the structure derived from the silane coupling agent be 0.50 parts by mass to 0.80 parts by mass.

[0184] Polyester diols have the advantage of excellent adhesion to urethane adhesives containing them and other layers, but on the other hand, heat resistance and hydrolysis resistance are sometimes very poor. Furthermore, adhesive layers containing polycarbonate diols have the advantages of excellent chemical resistance, hydrolysis resistance, and heat resistance, but on the other hand, adhesion may be reduced. When the balance of adhesion, hydrolysis resistance, and heat resistance is optimized, the above content is achieved. Furthermore, when the amount of polyester diol is high, heat resistance and hydrolysis resistance are very poor, while when the amount of polycarbonate diol is high, adhesion is reduced.

[0185] In this disclosure, "structure derived from" refers to components used in the production of urethane adhesives and components derived from their reactions, and also refers to units derived from components contained in the polymer. This is essentially the same as the amount of each component used in the production of urethane adhesives. Here, "substantially" means excluding amounts removed during the production process.

[0186] Hereinafter, the preferred amount of each component is described as 13.80 parts by mass or more and 14.25 parts by mass or less relative to the structure derived from the polyester diol.

[0187] Furthermore, an erosion prevention effect was confirmed by setting the polycarbonate diol-derived structure to 0.75 parts by mass or greater. However, if it is greater than 1.2 parts by mass, the adhesive layer using this structure may have a whitish appearance and the adhesive liquid viscosity may increase, making it difficult to handle. Therefore, in the above mass ratio, the polycarbonate diol is set to 0.75 parts by mass or greater and 1.20 parts by mass or less.

[0188] Further, the amount of the structure derived from the aliphatic isocyanate can be determined based on a calculation method in which the isocyanate group and the hydroxyl group in a general urethane resin are made equivalent. That is, the amount can be optimized in accordance with the total OH value (mg / KOH g) of the polyester diol and the polycarbonate diol and the NCO content of the aliphatic isocyanate. When the amount of the structure derived from the aliphatic isocyanate is small, sufficient urethane bonds cannot be formed, and the performance as an adhesive can not be satisfied. Further, when the amount of the structure derived from the aliphatic isocyanate is large, since the isocyanate readily reacts with water, whitening occurs, the adhesive layer becomes cloudy and milky white, and the haze value or the total light transmittance as a metal-style decorative laminate can increase or be poor.

[0189] In the above mass ratio, by setting the structure derived from the carbodiimide to 0.08 parts by mass or more and 0.20 parts by mass or less, an effect of improving the hydrolysis resistance can be obtained. In the case where the structure derived from the carbodiimide is less than 0.08 parts by mass, the effect of improving the hydrolysis resistance is sometimes insufficient, and even if it exceeds 0.20 parts by mass, the effect of improving the hydrolysis resistance does not increase, so as long as 0.20 parts by mass is set as the upper limit, the effect can be obtained.

[0190] As the carbodiimide, a commercially available carbodiimide dissolved in a solvent can be used, and a carbodiimide in which the NCO group is 0 mass% or more and 0.50 mass% or less can be used.

[0191] In the above mass ratio, by setting the structure derived from the silane coupling agent to 0.50 parts by mass or more and 0.80 parts by mass or less, the hydrolysis resistance can be satisfied by being used in combination with the carbodiimide, and in a hydrolysis test under a more severe test condition, the laminate can be qualified. By setting the structure derived from the silane coupling agent to 0.50 parts by mass or more, an effect of sufficiently improving the hydrolysis resistance can be obtained. Further, if the structure derived from the silane coupling agent is 0.80 parts by mass or less, the silane coupling agent is inhibited from condensing and whitening, and as a metal-style decorative laminate, the increase in the haze value or the poor total light transmittance can be inhibited.

[0192] As the silane coupling agent, a coupling agent having an epoxy group as an organic functional group can be used. For example, 3-glycidoxypropyltrimethoxysilane can be used.

[0193] Further, the metal-style decorative laminate has the following use example: illumination is lit from the back surface, and light emitted from the illumination is transmitted through the metal-style decorative laminate. By this use example, in a bright environment during the day, the appearance of the metal-style decorative laminate when the illumination is not lit becomes the appearance design of the metal style of the metal layer, and in a dark environment at night, by lighting the illumination from the back surface of the metal-style decorative laminate, the appearance design in which the metal layer and the transmitted light are combined is obtained.

[0194] Examples

[0195] Hereinafter, the present embodiment is more specifically described using examples. However, the present application is not limited by any of the following examples.

[0196] (Evaluation method)

[0197] [Evaluation of metal style decorative laminate]

[0198] 1. Film thickness of adhesive layer (film thickness of adhesive layer in Tables 4 to 7)

[0199] The film thickness of the adhesive layer was measured by slicing the cross section of the metal style decorative laminate with a microtome and observing the thickness with a microscope. In addition, the film thickness of the first adhesive layer and the second adhesive layer was the same.

[0200] 2. Appearance evaluation

[0201] The appearance of the metal style decorative laminate was visually observed, and the presence or absence of defects in the appearance such as brightness sensation, unevenness, blur, and the like was evaluated. In the case where there were no defects in the appearance such as brightness sensation, unevenness, blur, and the like, A indicating that it was acceptable was recorded, and in the case where there were defects in the appearance such as brightness sensation, unevenness, blur, and the like, B indicating that it was unaccepted was recorded.

[0202] 3. Optical properties

[0203] With respect to the manufactured metal style decorative laminate, the total light transmittance and the haze value before and after the hydrolytic resistance test were measured. The case where the total light transmittance was 10 to 20% or more and the haze was 5.5% or less was determined to be acceptable, and the case other than this was determined to be unaccepted.

[0204] The measurement of the total light transmittance and the haze was performed using a Haze Meter NDH 7000SP II (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7105.

[0205] The hydrolytic resistance test was a test in which the metal style decorative laminate was left to stand in a constant temperature and humidity chamber at a temperature of 90°C and a relative humidity of 95% RH for 72 hours. After the end of the hydrolytic resistance test, the metal style decorative laminate was taken out of the constant temperature and humidity chamber and left to stand at 25°C for 1 hour, and then the total light transmittance and the haze value were measured. The "optical properties" in Tables 4 to 7 refer to each value before the hydrolytic resistance test, and the "optical properties after hydrolysis" refer to each value after the hydrolytic resistance test.

[0206] 4. Adhesion

[0207] The adhesion of the adhesive layer of the metal exterior trim laminate manufactured was evaluated before and after the hydrolysis test by the 180-degree peeling test based on JIS K 6854-2. Specifically, in the case of testing the adhesion of the adhesive layer between the polycarbonate layer and the metal layer holding layer, a test piece was prepared by making a cut in the metal exterior trim laminate in a manner that the polycarbonate layer and the metal layer holding layer could be gripped by the upper chuck and the lower chuck, respectively, and the peeling test was performed. In addition, in the case of testing the adhesion of the adhesive layer between the polycarbonate layer and the metal layer, a test piece was prepared by making a cut in the metal exterior trim laminate in a manner that the polycarbonate layer and the metal layer could be gripped by the upper chuck and the lower chuck, respectively, and the peeling test was performed.

[0208] The case where the peeling force of the first adhesive layer and the second adhesive layer was 20 N / 25 mm or more was determined to be acceptable, and the case where it was less than 20 N / 25 mm was determined to be unacceptable.

[0209] The hydrolysis test was a test in which the metal exterior trim laminate was left to stand in a constant temperature and humidity chamber under conditions of a temperature of 90°C and a relative humidity of 95% RH for 72 hours. After the end of the hydrolysis test, the test piece was taken out of the constant temperature and humidity chamber, left to stand at 25°C for 1 hour, and then the adhesion of the metal exterior trim laminate was evaluated by the 180-degree peeling test based on JIS K 6854-2. The "adhesion" in Tables 4 to 7 refers to each value before the hydrolysis test, and the "adhesion after hydrolysis" refers to each value after the hydrolysis test.

[0210] [Evaluation of Injection Molded Body]

[0211] 5. Evaluation of Optical Properties

[0212] With respect to the injection molded body manufactured, the total light transmittance and the haze value before and after the hydrolysis test were measured. The case where the total light transmittance was 10% to 20% or more and the haze was 5.5% or less was determined to be acceptable, and the case other than this was determined to be unacceptable.

[0213] The measurement of the total light transmittance and the haze was performed using a Haze Meter NDH 7000 SPII (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7105.

[0214] The hydrolysis test involved placing the injection-molded articles in a constant temperature and humidity chamber at 90°C and 95% relative humidity for 72 hours. After the hydrolysis test, the articles were removed from the chamber and allowed to stand at 25°C for 1 hour. The total light transmittance and haze values ​​were then measured. The "Optical Properties of Injection-Molded Articles" in Tables 4-7 refer to the values ​​before the hydrolysis test, and the "Optical Properties of Injection-Molded Articles After Hydrolysis" refer to the values ​​after the hydrolysis test.

[0215] 6. Evaluation of the appearance of injection molded products

[0216] The appearance of the metallic decorative laminate at the corners and corners of the injection-molded article was visually observed. Through pre-molding and injection molding, the metallic decorative laminate was stretched at these corners and corners to an extent equivalent to 200% of its pre-stretching stretch. The metallic layer retaining layer, first polycarbonate layer, and second polycarbonate layer of the metallic decorative laminate were easily stretched, so no abnormalities were observed in these layers at the corners and corners of the injection-molded article. However, since the first and second adhesive layers used adhesives cross-linked by urethane bonds, the stretchability was insufficient due to the adhesive blending. As a result, the corners and corners of the injection-molded article could not withstand the stretching, sometimes cracking and resulting in a turbid appearance. Injection-molded articles that showed such turbidity were considered defective products, so the presence of turbidity was visually evaluated in this evaluation. Injection-molded articles with no turbidity and no abnormalities were designated as "A," indicating acceptance; those with turbidity or significant cracking were designated as "B," indicating failure.

[0217] <Confirmation of the presence of erosion>

[0218] The appearance of the injection-molded article near the gate was visually observed to confirm the presence or absence of erosion. Figure 3 Injection molded body 1100 ( Figure 4 (A)) and the eroded injection molded body 1200 ( Figure 4 (B) is a schematic diagram of the injection molded body 1100, 1200. The protruding portion is the gate portion 1110, 1210 formed by the polycarbonate injected into the mold solidifying inside the gate. Figure 4 (A) and (B) schematically show the gate portions 1110 and 1210 and a portion of the injection molded bodies 1100 and 1200 in the vicinity thereof. In the injection molded body 1200, an erosion portion 1220 ( Figure 4 (B)). On the other hand, in the injection molded body 1100, no abnormality such as erosion was confirmed in the metallic decorative laminate around the gate portion 1110 ( Figure 4(A)). In addition, the shape of the erosion is not limited to the elliptical shape like the erosion portion 1220, and can be various shapes. Figure 3 The injection molded body 1100 shown in (A) in which no abnormality was confirmed in the gate portion 1110 and its surroundings in the metallic decorative laminate was designated as A, indicating that the product was qualified. Figure 4 The injection molded body 1200 shown in (B) in which the metallic decorative laminated body was dissolved and missing around the gate portion 1210 was marked as B, indicating failure.

[0219] The evaluation results are shown in Tables 3 to 7. In Tables 3 to 7, the PU-PC item shows the peel strength of the adhesive layer between the metal layer holding layer and the polycarbonate layer, and the PC-In item shows the peel strength of the adhesive layer between the polycarbonate layer and the metal layer.

[0220] [Manufacturing of Metal-Style Decorative Laminated Body]

[0221] <Manufacturing of polycarbonate layer>

[0222] A polycarbonate resin (S2000 manufactured by Mitsubishi Engineering-Plastics Corporation) was extruded to produce a film having a thickness of 125 μm. This film was cut into A3 size (297 mm×420 mm) and used as the first and second polycarbonate layers.

[0223] <Manufacturing of Metal Layer Laminate>

[0224] A mixture containing polycarbonate polyurethane and a silicone surfactant, obtained by mixing 21 parts of an aqueous polyurethane dispersion (UW5002 (manufactured by Ube Industries)), 9 parts of an aqueous polyurethane dispersion (UW5502 (manufactured by Ube Industries)), 0.3 parts of a silicone surfactant (BYK-345 (manufactured by BYK)), and 6 parts of water, was applied to a release resin layer (PET film (G2000 (manufactured by Toyobo)) and dried at 150°C for 3 minutes. The release resin layer was then peeled off to produce a metal layer retaining layer having a dry film thickness of 20 μm. Indium was vacuum-deposited on the metal layer retaining layer to form a metal layer having a thickness of 50 nm, thereby producing a metal layer laminate. A laminate obtained by cutting the metal layer laminate into an A3 size (297 mm × 420 mm) was used as the metal layer laminate.

[0225] <Attachment of polycarbonate layer and metal layer laminate>

[0226] A urethane adhesive for metallic decorative laminates is prepared by mixing a base agent consisting of a mixture of polyester diol, polycarbonate diol, carbodiimide, an epoxy-containing silane coupling agent, and ethyl acetate (EtAC) with a curing agent consisting of an aliphatic isocyanate.

[0227] Here, TM-K51 (manufactured by Toyo Morton Co., Ltd.) was used as the polyester diol, DURANOL T5652 (manufactured by Asahi Kasei Corporation) was used as the polycarbonate diol, CAT-RT85 (manufactured by Toyo Morton Co., Ltd.) was used as the aliphatic isocyanate, CARBODILITE V-07 (manufactured by Nisshinbo Chemical Co., Ltd.) was used as the carbodiimide, and KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent having an epoxy group (silane coupling agent in the table).

[0228] Tables 1 to 3 show the blending amounts of the urethane adhesives for metallic decorative laminates in Examples 1 to 7 and Comparative Examples 1 to 11.

[0229] [Table 1]

[0230] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Polyester diol 14.25 14.25 13.80 13.80 13.80 13.80 14.25 Polycarbonate diol 0.75 0.75 0.75 1.20 1.20 1.20 1.20 Aliphatic isocyanate 3.21 3.21 3.21 3.21 3.21 3.21 4.00 Carbodiimide 0.17 0.17 0.08 0.08 0.20 0.20 0.20 Silane coupling agent 0.50 0.80 0.50 0.50 0.50 0.80 0.50 EtAc 11.00 11.00 11.00 11.00 11.00 11.00 11.00

[0231] [Table 2]

[0232] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Polyester diol 15.00 14.25 14.25 14.25 14.50 14.25 Polycarbonate diol 0.00 0.75 0.75 0.75 0.50 0.75 Aliphatic isocyanate 2.25 3.21 3.21 3.21 3.21 3.21 Carbodiimide 0.00 0.10 0.17 0.34 0.17 0.17 Silane coupling agent 0.00 0.00 0.00 0.00 0.50 0.30 EtAc 10.00 11.00 11.00 11.00 11.00 11.00

[0233] [Table 3]

[0234] Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Polyester diol 14.25 14.25 13.80 14.25 14.25 Polycarbonate diol 0.75 0.75 1.20 0.75 1.20 Aliphatic isocyanate 3.21 3.21 4.50 4.50 4.50 Carbodiimide 0.00 0.00 0.20 0.20 0.20 Silane coupling agent 0.50 0.80 0.80 0.50 0.50 EtAc 11.00 11.00 11.00 11.00 11.00

[0235] A urethane adhesive was applied to the surface of the metal layer of the metal layer laminate using a bar coater so that the dry film thickness of the first adhesive layer was 10 μm. The applied product was dried at 60°C for 1 minute, and then laminated with the metal layer and the polycarbonate layer. A urethane adhesive was applied to the surface of the metal layer retaining layer of the metal layer laminate using a bar coater so that the dry film thickness of the second adhesive layer was 10 μm. The applied product was dried at 60°C for 1 minute, and then laminated with the metal layer retaining layer and the polycarbonate layer. The laminate was then cured at 30°C for 10 days to produce a metallic decorative laminate.

[0236] Lamination was performed using a die laminator (EXCELAM II-355Q, manufactured by GMP) with the temperature of the pressure roller on the polycarbonate layer side set to 130° C. and the sheet feeding speed set to 0.3 m / min.

[0237] The metal style decoration laminate of Examples 1 to 7 and Comparative Examples 1 to 11 was manufactured as above. Further, in Examples 1 to 7 and Comparative Examples 1 to 11, the urethane-based adhesive was different in composition, and other conditions were the same. In addition, in Examples 1 to 7 and Comparative Examples 1 to 11, the same polycarbonate layer was used for the first polycarbonate layer and the second polycarbonate layer, and the film was not different, and the same urethane-based adhesive was used for the first adhesive layer and the second adhesive layer, and the adhesive was not different.

[0238] [Manufacture of metal style molded body]

[0239] After the metal style decoration laminate was clamped using a compression air molding machine, the metal style decoration laminate was preformed at a preforming temperature of 200°C, a compression air pressure of 6 bar, and in a mold suitable for an injection molded body. The unnecessary portion protruding from the mold was trimmed and cut, and a metal style molded body was obtained.

[0240] [Manufacture of injection molded body]

[0241] The metal style molded body was embedded in a mold of an injection molding machine, and polycarbonate (IUPILON S-2000R535 manufactured by Mitsubishi Engineering-Plastics Corporation) was injected and injection molded by embedding to produce an injection molded body having a size of 104 mm x 78.5 mm x 9.3 mm, a wall thickness of 3 mm, and a curvature radius of 5 mm at the corners and the corner portions. The injection resin temperature of the polycarbonate at the time of injection molding was set to 300°C. Figure 2 The front view and the side view showing the size of the injection molded body 1000 manufactured are shown in FIGS. 1 and 2. Figure 2 (A) is a front view of the injection molded body 1000, Figure 2 (B) is a side view of the injection molded body 1000, Figure 2 (A) is a side view of the injection molded body 1000, Figure 2 (C) is a side view of the injection molded body 1000, Figure 2 (A) is a side view of the injection molded body 1000.

[0242] [Table 4]

[0243]

[0244] [Table 5]

[0245]

[0246] [Table 6]

[0247]

[0248] [Table 7]

[0249]

[0250] [Results]

[0251] According to the results of Examples 1 to 7 shown in Tables 4 and 5, the visual appearance was good, the design property was satisfied, the molding of the metal style molded body and the injection molded body was not defective, no haze or cracks were generated, and no erosion was generated, and the moldability was good. Furthermore, the total light transmittance and the haze value were not abnormal before and after the hydrolysis test under the conditions problematic in the existing products, and the adhesion was also good. In addition, the result regarding the adhesion was that the adhesion performance after the hydrolysis test was improved.

[0252] That is, it was confirmed that, by using the content of the structure derived from the polyester diol of 13.8 parts by mass or more and 14.25 parts by mass or less, the content of the structure derived from the polycarbonate diol of 0.75 parts by mass or more and 1.2 parts by mass or less, the content of the structure derived from the aliphatic isocyanate of 3.2 parts by mass or more and 4.0 parts by mass or less, the content of the structure derived from the carbodiimide of 0.08 parts by mass or more and 0.2 parts by mass or less, and the content of the structure derived from the silane coupling agent of 0.5 parts by mass or more and 0.8 parts by mass or less, the hydrolysis resistance can be satisfied without impairing the design property and the moldability, and the appearance defect of the metal style molded product caused by erosion can be improved.

[0253] According to the results of Comparative Examples 1 to 11 shown in Tables 6 and 7, erosion was generated since the polycarbonate diol was not contained (Comparative Examples 1, 5). The optical properties were reduced since the carbodiimide was not contained, and in addition, the adhesion force after the hydrolysis test was reduced (Comparative Examples 1, 7, 8). Furthermore, the adhesion force after the hydrolysis test was reduced when the carbodiimide was excessive (Comparative Example 4). The adhesion force after the hydrolysis test was reduced when the epoxy group-containing silane coupling agent was not contained or the epoxy group-containing silane coupling agent was insufficient (Comparative Examples 1 to 4, 6). When the aliphatic isocyanate was excessive, cracks or haze were confirmed at the corner and the corner portion of the injection molded body, the appearance was defective, and in addition, the adhesion force after the hydrolysis test was reduced (Comparative Examples 9 to 11).

[0254] [Summary]

[0255] As described above, it is clear that the present application can provide a metal style decorative laminate, a metal style molded body, an injection molded body, a method for manufacturing a metal style decorative laminate, a method for manufacturing a metal style molded body, a method for manufacturing an injection molded body, and a urethane-based adhesive, which can satisfy the hydrolysis resistance without impairing the design property and the moldability and improve the appearance defect of the metal style molded product caused by erosion. Therefore, it is understood that the present application is industrially useful.

[0256] Explanation of Reference Signs

[0257] 1: Metal layer laminate,

[0258] 2: Metal style decoration laminate (A),

[0259] 3: Metal style decoration laminate (B),

[0260] 10: First polycarbonate layer,

[0261] 20: First adhesive layer,

[0262] 30: Metal layer,

[0263] 40: Metal layer holding layer,

[0264] 50: Second adhesive layer,

[0265] 60: Second polycarbonate layer,

[0266] 100: Thickness direction,

[0267] 110: Width direction,

[0268] 120: Length direction,

[0269] 1000: Injection-molded body,

[0270] 1100: Injection-molded body,

[0271] 1110: Gate portion,

[0272] 1200: Injection-molded body,

[0273] 1210: Gate portion,

[0274] 1220: Erosion portion.

Claims

1. A metal-style decorative laminate, comprising: a first polycarbonate layer; a first adhesive layer; a metal layer stack comprising a metal layer; a second adhesive layer; as well as The second polycarbonate layer, The first adhesive layer and the second adhesive layer contain a reaction product of polyester diol, polycarbonate diol and aliphatic isocyanate, carbodiimide, and a silane coupling agent having an epoxy group. The content of the structure derived from the polyester diol in the first adhesive layer and the second adhesive layer is 13.8 parts by mass or more and 14.25 parts by mass or less, the content of the structure derived from the polycarbonate diol is 0.75 parts by mass or more and 1.2 parts by mass or less, the content of the structure derived from the aliphatic isocyanate is 3.20 parts by mass or more and 4.00 parts by mass or less, the content of the structure derived from the carbodiimide is 0.08 parts by mass or more and 0.20 parts by mass or less, and the content of the structure derived from the silane coupling agent is 0.50 parts by mass or more and 0.80 parts by mass or less.

2. The metallic decorative laminate according to claim 1, wherein the metallic decorative laminate is subjected to a hydrolysis test in which the metallic decorative laminate is allowed to stand for 72 hours at a temperature of 90° C. and a relative humidity of 95% RH. The total light transmittance is 10% or more and 20% or less. The haze is below 5.5%. The peeling force of the first adhesive layer and the second adhesive layer obtained by a 180-degree peel test in accordance with JIS K 6854-2 is 20 N / 25 mm or more. 3 . A metallic molded body comprising the metallic decorative laminate according to claim 1 . 4 . An injection-molded article comprising an injection-molded resin layer on a surface of the first polycarbonate layer and / or a surface of the second polycarbonate layer of the metallic molded article according to claim 3 .

5. The method for manufacturing the metallic decorative laminate according to claim 1 or 2, comprising: Applying a urethane adhesive on the first polycarbonate layer and / or the metal layer laminate, drying the urethane adhesive, and then bonding the first polycarbonate layer and the metal layer laminate via the first adhesive layer by laminating; as well as A urethane adhesive is applied to the metal layer laminate and / or the second polycarbonate layer, and after the urethane adhesive is dried, the metal layer laminate and the second polycarbonate layer are bonded together by lamination via the second adhesive layer.

6. A method for producing a metallic-style molded body, comprising a molding step of bringing the metallic-style decorative laminate according to claim 1 or 2 having a surface temperature of 150°C to 200°C into close contact with a mold to obtain a molded body of the laminate having a metallic-style decoration.

7. A method for manufacturing an injection-molded body, comprising an injection molding step: using an injection molding mold, injecting resin between the surface of the first polycarbonate layer and / or the surface of the second polycarbonate layer of the metal-style molded body obtained by the method for manufacturing a metal-style molded body according to claim 6 and the injection molding mold to form a resin layer, thereby obtaining an injection-molded body in which the metal-style molded body and the resin layer are integrated.

8. A urethane adhesive comprising a polyester diol, a polycarbonate diol, an aliphatic isocyanate, a carbodiimide, and a silane coupling agent having an epoxy group, wherein the content of a structure derived from the polyester diol is from 13.80 parts by mass to 14.25 parts by mass, the content of a structure derived from the polycarbonate diol is from 0.75 parts by mass to 1.20 parts by mass, the content of a structure derived from the aliphatic isocyanate is from 3.20 parts by mass to 4.00 parts by mass, the content of a structure derived from the carbodiimide is from 0.08 parts by mass to 0.20 parts by mass, and the content of a structure derived from the silane coupling agent is from 0.50 parts by mass to 0.80 parts by mass.

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