Decorative laminate for three-dimensional molding processing and method of producing the same

Abstract

Provided are a decorative laminate for three-dimensional molding processing excellent in corrosion resistance, impact resistance, adhesion, and opening resistance after three-dimensional molding processing, and a method of producing the decorative laminate. Solution Means A method of producing a decorative laminate for three-dimensional molding processing according to an embodiment of the present disclosure includes: preparing a metal layer; applying a primer layer containing at least one selected from the group consisting of an organosilicon compound and a (meth)acrylic resin to the metal layer; applying a two-component curable polyurethane precursor layer containing a polyol and an isocyanate directly to the primer layer; and causing the two-component curable polyurethane precursor layer to react to form a polyurethane layer.

Description

[0001] DECORATIVE LAMINATE FOR THREE-DIMENSIONAL MOLDING PROCESSING AND METHOD OF PRODUCING THE SAME

[0002] Technical Field

[0003] The present disclosure relates to a decorative laminate to be subjected to a three-dimensional molding processing and a method of producing the same.

[0004] Background

[0005] In recent years, for example, a decorative laminate including a polyurethane resin layer has been developed and used in a wide range of fields such as exterior goods.

[0006] Patent Document 1 (JP H05-155976 A) describes that a laminate including a specific polyurethane resin layer and a heat-sensitive adhesive layer is used as an interior and exterior film.

[0007] Patent Document 2 (JP 2007-297569 A) discloses a decorative layer-forming film including a top coat layer formed of a polyurethane resin, and a carrier film provided on a surface side of the top coat layer, wherein the polyurethane resin is formed of a polyurethane resin composition including (1) a polyisocyanate containing 0.5 equivalents or more of an isocyanurate or adduct body of isophorone diisocyanate or both thereof, based on the total polyisocyanate, and (2) a polyol formed of a caprolactone diol, a polycarbonate diol, or a mixture thereof, and containing 0.4 equivalents or more of a polyester polyol with an average molecular weight of 1000 or less, based on the total polyol, and an equivalent ratio between the polyisocyanate and the polyol is from 0.7 to 2.0.

[0008] Summary of Invention

[0009] Technical Problem

[0010] Metal substrates may corrode when exposed to wind, rain, chemicals, and the like. In order to prevent such corrosion, a resin layer may be applied to a metal substrate. Among resin layers, a polyurethane resin layer is excellent in impact resistance, and thus, defects such as cracking of the resin layer after receiving an impact can be suitably prevented. However, since the polyurethane resin layer has poor adhesion to the metal substrate, it is necessary to use an adhesive layer (for example, a heatsensitive adhesive layer) when the polyurethane resin layer is applied to the metal substrate. Since the adhesive layer is typically thicker and more flexible than a primer layer, when a laminate including a metal substrate, an adhesive layer, and a polyurethane resin layer is subjected to three-dimensional molding processing, for example, the polyurethane resin layer may be broken, or even when the polyurethane resin layer is not broken, if a cut is formed in the polyurethane resin layer, an opening phenomenon in which the cut opens with time may occur. For example, when the polyurethane resin layer is stretched at the time of molding processing such as deep drawing, and in this state, the polyurethane resin layer is cut and heated, the polyurethane resin layer tends to return to its original state. Since the flexible adhesive layer cannot restrain the return of the polyurethane resin layer, an opening phenomenon in which a cut opens is likely to occur. The present disclosure provides a decorative laminate for three-dimensional molding processing that is excellent in corrosion resistance, impact resistance, adhesion, and opening resistance after three-dimensional molding processing, and a method of producing the decorative laminate.

[0011] Solution to Problem

[0012] According to an embodiment of the present disclosure, there is provided a method of producing a decorative laminate for three-dimensional molding processing, the method including: preparing a metal layer; applying a primer layer containing at least one selected from the group consisting of an organosilicon compound and a (meth)acrylic resin to the metal layer; applying a two-component curable polyurethane precursor layer containing a polyol and an isocyanate directly to the primer layer; and causing the two-component curable polyurethane precursor layer to react to form a polyurethane layer.

[0013] According to another embodiment of the present disclosure, there is provided a decorative laminate for three-dimensional molding processing, the laminate including a metal layer, a primer layer, and a polyurethane layer in this order, the primer layer containing at least one selected from the group consisting of an organosilicon compound and a (meth)acrylic resin, the polyurethane layer containing a cured reaction product of a two-component curable polyurethane resin composition containing a polyol and an isocyanate, in which the polyurethane layer is applied directly to the primer layer, when the polyurethane layer of the laminate is subjected to a Water Resistance Test below, the polyurethane layer achieves 90 / 100 or more in terms of the number of remaining squares, and when the polyurethane layer of the laminate is subjected to a Heat Resistance Test below, the polyurethane layer exhibits an opening width or a peeling width of 0.5 mm or less at most:

[0014] Water Resistance Test

[0015] A decorative laminate for three-dimensional molding processing is immersed in 40°C water for 240 hours, the laminate is taken out, the moisture is wiped off, and the laminate is allowed to stand for 1 hour. Then, a total of 100 squares of 10 x 10 squares of 1 mm square are formed on the polyurethane layer of the laminate by a cutter, and immediately after Sellotape (tradename) is applied to the 100 squares, the Sellotape (tradename) is peeled off, and the number of remaining squares where the polyurethane layer is not peeled off is checked.

[0016] Heat Resistance Test

[0017] By using No. 517 DuPont-type Falling Impact Tester, a decorative laminate for three- dimensional molding processing is placed on a die having a recess such that the recess of the die is covered and the metal layer of the laminate is a top surface. With a hemispherical punch having a halfinch-diameter tip being in contact with the top surface of the metal layer, a weight of 1 kg is dropped from a height of 50 cm into the punch to deform the laminate into a convex shape. In the polyurethane layer that has been deformed into the convex shape, a cross cut is made with a cutter blade, and an opening width and a peeling width of the polyurethane layer at the cut portion is checked after Heat Cycle below is applied to the laminate: (Heat Cycle)

[0018] (1) Raise the temperature from 23 °C to 80°C over 1 hour

[0019] (2) Keep the temperature at 80°C for 18 hours

[0020] (3) Lower the temperature to -30°C over 1 hour

[0021] (4) Keep the temperature at -30°C for 4 hours

[0022] (5) Raise the temperature to 80°C over 1 hour

[0023] (6) Keep the temperature at 80°C for 18 hours

[0024] Repeat the operations (3) to (6) described above 9 times

[0025] (7) Lower the temperature to -30°C over 1 hour

[0026] (8) Keep the temperature at -30°C for 4 hours

[0027] (9) Raise the temperature from -30°C to 23°C over 1 hour

[0028] According to another embodiment of the present disclosure, there is provided a decorative article including the above-described decorative laminate having a three-dimensional shape.

[0029] According to another embodiment of the present disclosure, there is provided a method of producing a decorative article including pressing or roll forming the above-described decorative laminate.

[0030] Advantageous Effects of Invention

[0031] According to the present disclosure, it is possible to provide a decorative laminate for three- dimensional molding processing that is excellent in corrosion resistance, impact resistance, adhesion, and opening resistance after three-dimensional molding processing, and a method of producing the decorative laminate.

[0032] The above description should not be construed as disclosing all embodiments of the present invention and all advantages relating to the present invention.

[0033] Brief Description of Drawings

[0034] FIG. 1 is a diagram that represents a section of a known decorative laminate.

[0035] FIG. 2 is a diagram that represents a section of a decorative laminate for three-dimensional molding processing of an embodiment of the present disclosure.

[0036] FIG. 3(a) is an diagram of a decorative article (automobile molding member) of Examples 1 to 4 obtained by three dimensionally molding a decorative laminate for three-dimensional molding processing of an embodiment of the present disclosure, FIG. 3(b) is an diagram of a decorative article (automobile molding member) of Example 7 obtained by three dimensionally molding a decorative laminate for three-dimensional molding processing of another embodiment of the present disclosure, and FIG. 3(c) is an diagram of a decorative article (automobile molding member) of Example 8 obtained by three dimensionally molding a decorative laminate for three-dimensional molding processing of another embodiment of the present disclosure. FIG. 4(a) is a perspective view schematically illustrating a test with No. 517 DuPont-type Falling Impact Tester, and FIG. 4(b) is a sectional view schematically illustrating the states before and after the test.

[0037] FIG. 5(a) is a schematic diagram of a convex portion formed on a decorative laminate for three-dimensional molding processing, and FIG. 5(b) is a schematic diagram of the convex portion formed on the decorative laminate for three-dimensional molding processing in a state where a crossshaped cut is made by a cutter in a polyurethane layer of the convex portion.

[0038] FIG. 6 is a diagram when a decorative laminate for three-dimensional molding processing of an embodiment of the present disclosure is pressed into a hat-like shape.

[0039] Description of Embodiments

[0040] Hereinafter, representative embodiments of the present invention will be described in more detail with reference to the drawing, as necessary, for the purpose of illustration, but the present invention is not limited to these embodiments. Regarding the reference numbers in the drawings, constituents labeled with similar numbers across different drawings are similar or corresponding constituents.

[0041] In the present disclosure, “three-dimensional molding processing” is intended to mold an object into a three-dimensional shape, and “three-dimensional shape” is intended to mean a three-dimensional shape obtained by adding a Z axis to a two-dimensional shape (planar shape having only an X axis and a Y axis). Here, “three-dimensional shape” in the present disclosure may include, for example, a curved surface shape.

[0042] In the present disclosure, “over”, for example in the sentence “a primer layer is disposed over a metal layer”, means that the primer layer is directly disposed on the upper side of the metal layer, or that the primer layer is indirectly disposed on the upper side of the metal layer via another layer.

[0043] In the present disclosure, “under”, for example in the sentence “a metal layer is disposed under a primer layer”, means that the metal layer is directly disposed on the lower side of the primer layer, or that the metal layer is indirectly disposed on the lower side of the primer layer via another layer.

[0044] In the present disclosure, “transparent” refers to an average transmittance in a visible light region (wavelength of 400 nm to 700 nm) measured in accordance with JIS K 7375 of approximately 80% or more, and the average transmittance may be desirably approximately 85% or more, or approximately 90% or more. An upper limit of the average transmittance is not particularly limited, and can be, for example, approximately less than 100%, approximately 99% or less, or approximately 98% or less.

[0045] In the present disclosure, “translucent” refers to an average transmittance in a visible light region (wavelength of 400 nm to 700 nm) measured in accordance with JIS K 7375 of approximately less than 80%, and the average transmittance may be desirably approximately less than or equal to 75%, and “translucent” is intended to mean that an underlying layer is not completely hidden.

[0046] In the present disclosure, “(meth)acrylic” means acrylic or methacrylic. In the present disclosure, the term “sheet” encompasses members referred to as “films”.

[0047] Hereinafter, a decorative laminate for three-dimensional molding processing (it may be simply referred to as “laminate” or “decorative laminate”) and a method of producing the same according to the present disclosure will be described with reference to the drawings as necessary.

[0048] A known decorative laminate 100 illustrated in FIG. 1 includes a metal layer 101, a primer layer 103, an adhesive layer 105, and a polyurethane layer 107. Meanwhile, in a decorative laminate of the present invention, as illustrated in FIG. 2, a metal layer 201 and a polyurethane layer 207 may be bonded by a primer layer 203 without using an adhesive layer.

[0049] In a known decorative laminate, since a cured polyurethane layer is applied to the metal layer, for example, in the form of a film, sufficient adhesive strength cannot be obtained only by the primer layer, and an adhesive layer such as a heat-sensitive polyurethane adhesive is additionally required. Meanwhile, the method of producing a decorative laminate of the present disclosure includes: preparing a metal layer; applying a primer layer containing at least one selected from the group consisting of an organosilicon compound and a (meth)acrylic resin to the metal layer; applying a two- component curable polyurethane precursor layer containing a polyol and an isocyanate directly to the primer layer; and causing the two-component curable polyurethane precursor layer to react to form a polyurethane layer. That is, in the method of producing a decorative laminate of the present disclosure, unlike known production methods, a cured polyurethane layer is not applied to a primer layer, but an uncured polyurethane layer (polyurethane precursor layer) before curing is directly applied to a primer layer, and then the polyurethane layer (polyurethane precursor layer) is caused to undergo a curing reaction. Through such a process, the adhesive strength between the polyurethane layer and the primer layer improves, and thus, the polyurethane layer and the metal layer can be suitably bonded to each other without using an adhesive layer made of heat-sensitive polyurethane adhesive or the like that has been used in a known production method.

[0050] Since the decorative laminate of the present disclosure does not use a typically flexible adhesive layer such as a heat-sensitive polyurethane adhesive layer, it is possible to reduce or prevent breakage of the polyurethane layer after three-dimensional molding processing or an opening phenomenon with time due to a cut formed in the polyurethane layer, as compared with a known decorative laminate. Thus, the decorative laminate of the present disclosure can be suitably used for three-dimensional molding processing.

[0051] Since an adhesive layer, such as a heat-sensitive polyurethane adhesive layer, is typically a flexible layer, the decorative laminate becomes soft when a polyurethane layer is applied over such an adhesive layer. As a result, for example, when the decorative laminate is pressed from the surface, a defect such as an indentation or a scratch may occur on the surface of the decorative laminate. Since the decorative laminate of the present disclosure does not use a typically flexible adhesive layer such as a heat-sensitive polyurethane adhesive layer, the hardness of the entire decorative laminate can be improved, and a defect such as an indentation or a scratch can be reduced or prevented. In addition, according to the production method of the present disclosure, since it is not necessary to use an adhesive layer such as a heat-sensitive polyurethane adhesive layer, it is possible to contribute to a reduction in production cost of the decorative laminate.

[0052] The metal layer that may be used in the method of producing a decorative laminate of the present disclosure is not particularly limited, and the metal layer may be, for example, a layer containing a metal selected from aluminum, nickel, gold, silver, copper, platinum, chromium, iron, steel, stainless steel, tin, indium, titanium, lead, zinc, germanium, and the like, or an alloy or a compound thereof. The metal layer may have a single layer structure or a laminated structure. Of these, stainless steel is preferable from the viewpoint of three-dimensional molding processability and corrosion resistance.

[0053] The thickness of the metal layer is not particularly limited as long as three-dimensional molding processing can be performed. The thickness of the metal layer may be, for example, about 100 micrometers or more, about 150 micrometers or more, about 200 micrometers or more, about 250 micrometers or more, about 300 micrometers or more, or about 350 micrometers or more, and may be about 3 mm or less, about 2 mm or less, about 1 mm or less, about 800 micrometers or less, or about 500 micrometers or less. The thickness of each layer in the decorative laminate of the present disclosure may be defined, for example, as an average value of thicknesses of at least any five points on the metal layer measured with a thickness gauge (PC-465N available from TECLOCK). When the layer constituting the laminate is thin and it is difficult to measure the thickness with a thickness gauge, a section in a thickness direction of the laminate configuration is measured using a scanning electron microscope, and the thickness may be defined as an average value of thicknesses of at least any five points in a target layer of the laminate configuration, for example, a primer layer.

[0054] Usually, the surface of the metal layer may be contaminated by oil or the like. Thus, a surface treatment such as degreasing or cleaning may be applied to the surface of the metal layer. Examples of such a surface treatment method include a method of wiping off the surface of the metal layer using an organic solvent such as alcohol, an alkaline aqueous solution such as sodium hydroxide, or another cleaning liquid (these may be collectively and simply referred to as “cleaning agent”), a method of immersing the metal layer in a cleaning agent, and a method of spraying a cleaning agent at high pressure. The surface of the metal layer may be subjected to surface treatment such as corona treatment or plasma treatment. When a primer layer is applied to the metal layer subjected to such surface treatment, the adhesion between the polyurethane layer and the metal layer can be further improved.

[0055] The primer layer that may be used in the method of producing a decorative laminate of the present disclosure contains at least one selected from the group consisting of an organosilicon compound and a (meth)acrylic resin. The blending amounts of the organosilicon compound and the (meth)acrylic resin may be appropriately determined so that a desired adhesive strength is obtained. For example, each of these components may be contained in a range of about 50 mass% or more, about 60 mass% or more, about 70 mass% or more, or about 80 mass% or more, and about 100 mass% or less, or less than about 100 mass% with respect to the total amount of the primer layer. In the present disclosure, a primer containing an organosilicon compound may be referred to as a silane-based primer, and a primer containing a (meth)acrylic resin may be referred to as an acrylic primer.

[0056] The primer layer may be applied directly to the metal layer. From the viewpoint of adhesion between the polyurethane layer and the metal layer, the primer layer is preferably applied directly to the metal layer. When an optional layer such as a decorative layer is interposed between the metal layer and the primer layer, it is preferable that the optional layer is partially applied to the metal layer so that a portion where the metal layer and the primer layer are in direct contact with each other is formed. The primer layer may be applied by a well-known coating method or the like. When the primer layer is applied to the metal layer, as necessary, additional steps such as a drying step (for example, drying at room temperature) and a heating step (for example, heating in an oven or with infrared rays) may be appropriately employed.

[0057] The primer layer can improve the adhesion after the curing reaction of the uncured polyurethane layer (polyurethane precursor layer) applied on the primer layer.

[0058] Among the materials constituting the primer layer, an organosilicon compound is preferable. Since an adhesive layer such as a heat-sensitive adhesive layer used in a known decorative laminate and a primer layer containing a (meth)acrylic resin are inferior in weather resistance, a polyurethane layer applied on these layers needs to be colored in black to block light in some cases. Since the organosilicon compound is excellent in weather resistance, when a primer layer containing an organosilicon compound is employed, the polyurethane layer does not need to be limited in terms of coloring, and a transparent polyurethane layer can be employed. As a result, decorative performance such as metallic luster possessed by the metal layer itself can be visually recognized.

[0059] As the organosilicon compound, a compound having an alkoxysilyl group having a silicon atom and 1 to 3 alkoxy groups covalently bonded to the silicon atom may be employed. From the viewpoint of adhesion between the polyurethane layer and the metal layer, a compound including a structure in which two or more alkoxy groups are covalently bonded to a silicon atom is preferable, and a compound including a structure in which three alkoxy groups are covalently bonded to a silicon atom is more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, and a t-butoxy group. Of these, a methoxy group and an ethoxy group are preferable from the viewpoint of adhesion between the polyurethane layer and the metal layer. The organosilicon compound may have an epoxy group, a methacryl group, an acryl group, an amino group, or a styryl group. Of these, from the viewpoint of adhesion between the polyurethane layer and the metal layer, it is preferable that the organosilicon compound has an amino group. The organosilicon compound can be used alone, or in combination of two or more types thereof. In general, an agent called a silane coupling agent can be used as the organosilicon compound.

[0060] Specific examples of the organosilicon compound include y-aminopropyltriethoxy silane, N-f- (aminoethyl)-y-aminopropyltriethoxysilane, N-P-(aminoethyl)-N'-P-(aminoethyl)-y- aminopropyltriethoxysilane, y-anilinopropyltriethoxysilane, y-glycidoxypropyltriethoxysilane, P-(3 ,4- epoxycyclohexyl)ethyltriethoxysilane, vinyltriethoxysilane, N-P-(N-vinylbenzylaminoethyl)-y- aminopropyltriethoxysilane, y-methacryloxypropyltrimethoxysilane, y-chloropropyltrimethoxysilane, y-mercaptopropyltrimethoxysilane, and y-isocyanatepropyltriethoxysilane.

[0061] The (meth)acrylic resin is not particularly limited, and for example, a commercially available (meth)acrylic resin used as a primer may be employed. As the primer containing a (meth)acryl resin, for example, KBS17A / B available from Konishi Co., Ltd. (Osaka-shi, Osaka, Japan), Hamatite (tradename) A-l 100F available from Sika Japan Ltd. (Minato-ku, Tokyo, Japan), and the like, which are commercially available as acryl primers, may be used.

[0062] The thickness of the primer layer may be about 10 micrometers or less, less than about 10 micrometers, about 8 micrometers or less, or about 6 micrometers or less. From the viewpoint of the adhesion between the metal layer and the polyurethane layer, the opening resistance, the hardness of the entire decorative laminate, and the like, the thickness of the primer layer is preferably about 5 micrometers or less, about 4 micrometers or less, or about 3 micrometers or less. The lower limit of the thickness of the primer layer is not particularly limited, and it may be, for example, about 0.05 micrometers or more, about 0.5 micrometers or more, or about 1 micrometers or more.

[0063] In some embodiments, the primer layer may contain, for example, a fdler, a reinforcing material, an antioxidant, a flame retardant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a flame retardant, a dispersant, a plasticizer, a flow improver, a tackifier, a leveling agent, a catalyst, a pigment, a dye, a thickener, a binder resin other than an organosilicon compound and a (meth)acrylic resin, and the like as an optional component depending on use application and the like. The optional components can be used alone, or in combination of two or more types thereof.

[0064] The method of producing a decorative laminate of the present disclosure includes directly applying a two-component curable polyurethane precursor layer (it may be simply referred to as a “precursor layer”) containing a polyol and an isocyanate to the above-described primer layer, and causing the two-component curable polyurethane precursor layer to react to form a polyurethane layer. Here, “directly applying a two-component curable polyurethane precursor layer to the primer layer” may include not only directly applying the two-component curable polyurethane precursor layer to the entire surface of the primer layer but also directly applying the two-component curable polyurethane precursor layer to a part of the primer layer. The two-component curable polyurethane precursor layer can be applied by a known coating method, lamination method, or the like. When the two-component curable polyurethane precursor layer is applied to the primer layer, or when the two-component curable polyurethane precursor layer is caused to react to form the polyurethane layer, additional steps such as a drying step (for example, drying at room temperature) and a heating step (for example, heating in an oven or with infrared rays) may be appropriately employed as necessary.

[0065] The two-component curable polyurethane precursor layer may have a single layer structure or a laminated structure (for example, a colored layer and a clear surface layer). In the case of a laminated structure, at least the layer applied directly to the primer layer is a two-component curable polyurethane precursor layer. In the case of a laminated structure, from the viewpoint of adhesion between the polyurethane layer and the metal layer, layers other than the layer directly applied to the primer layer are also preferably two-component curable polyurethane precursor layers, and curing reaction is preferably performed after all the precursor layers are laminated on the primer layer.

[0066] In the present disclosure, “two -component curable polyurethane precursor layer” refers to a polyurethane layer in an uncured state that is not completely cured. Whether the polyurethane layer is in an uncured state or a completely cured state can be evaluated using, for example, a Fourier- transform infrared spectrometer (FT-IR Nicolet iS5, available from Yamato Scientific Co., Ltd., Chuo- ku, Tokyo, Japan). Specifically, when the polyurethane layer is measured by such an apparatus, when the N=C=O inverse symmetric stretching peak existing in the vicinity of the 2270 cm'1can be observed, it can be evaluated that the curing is not completed, and when the wave length region is almost flat and the peak cannot be observed, it can be evaluated that the curing is completed. Alternatively, it is also possible to indirectly evaluate whether the polyurethane layer when directly applied to the primer layer in the method of producing a decorative laminate of the present disclosure was a polyurethane precursor layer in an uncured state, from the evaluation results of a water resistance test and a heat resistance test described below performed on the obtained decorative laminate. That is, when the evaluation results of the water resistance test and the heat resistance test are at a passing level, it can be regarded that the polyurethane precursor layer in an uncured state is directly applied to the primer layer, and when the evaluation results are at a fail level, it can be regarded that the polyurethane layer in a completely cured state is directly applied to the primer layer.

[0067] The two-component curable polyurethane precursor layer may be, for example, an uncured polyurethane sheet or an uncured polyurethane coating layer. The uncured state and the cured state of the two-component curable polyurethane can be controlled by adjusting, for example, the temperature condition, the curing reaction time, or the blending amount of a catalyst. In some embodiments, as a method of preparing an uncured polyurethane layer (a polyurethane layer that is dried but has isocyanate groups remaining), the following method can be exemplified. After the two-component curable polyurethane resin composition is applied to a substrate or the like, the polyurethane layer is dried so as to substantially eliminate the solvent content without foaming. At this time, it is preferable that the clear surface polyurethane layer has such softness that the polyurethane layer can be laminated with a PET film without air inclusion in a state where the isocyanate group remains, the polyurethane layer is not in a state where the polyurethane layer flows by the pressure at the time of lamination, and when the polyurethane layer is touched with a fingertip and the fingertip is immediately removed therefrom, the polyurethane layer has a fingerprint but does not adhere to the finger. For the colored polyurethane layer, it is preferred that the surface of the polyurethane layer is not sticky in the presence of residual isocyanate groups. Here, from the viewpoint of evaporating the solvent component without foaming, the temperature at the time of drying may be, for example, about 60°C or more, about 70°C or more, or about 80°C or more, and about 150°C or less, about 130°C or less, or about 110°C or less. The curing reaction time may vary depending on the temperature to be applied or the blending amount of the catalyst to be described later, and the time may be, for example, about 1 minute or more, about 2 minutes or more, or about 3 minutes or more, and about 1 hour or less, about 30 minutes or less, or about 10 minutes or less. The catalyst to be added does not have to be blended in the case of an acrylic polyol or the like which reacts rapidly. In the case of a polycaprolactone polyol or the like having a slower reaction than an acrylic polyol, it is preferable to blend a catalyst. The catalyst may be blended in an amount of about 0.01 mass% or more, about 0.02 mass% or more, or about 0.04 mass% or more, and about 0.4 mass% or less, about 0.2 mass% or less, or about 0. 1 mass% or less with respect to the solid content of the polyurethane layer (in particular, the clear polyurethane layer). The uncured polyurethane precursor layer can maintain the uncured state for about one week under a temperature atmosphere of room temperature (about 20°C ± about 15°C) or less, for example, and can maintain the uncured state for about several weeks at about 0°C. Thus, even an uncured polyurethane sheet that has been stored for several days can be suitably used as the two-component curable polyurethane precursor layer of the present disclosure.

[0068] The polyurethane precursor layer directly applied to the primer layer may be cured to form a polyurethane layer, for example, by further controlling the above-described temperature conditions and curing reaction time, or by controlling the storage temperature and storage time. Here, as the storage temperature and storage time, for example, a period of about 10 days or more, about 2 weeks or more, about 3 weeks or more, or about 30 days or more may be employed at room temperature.

[0069] The polyurethane layer of the present disclosure is prepared using a two-component curable polyurethane resin composition containing a polyol and an isocyanate. Here, “isocyanate” in the present disclosure includes isocyanate referred to as polyisocyanate in addition to isocyanate as a monomer.

[0070] Examples of the polyol include polyether polyols; polymer polyols having a carbon-carbon bond in the main chain skeleton, such as (meth)acrylic polyols, polybutadiene diols, and hydrogenated polybutadiene polyols; and polyester polyols such as polycaprolactone polyols and polycarbonate polyols. Of these, a polyester polyol is preferable, a polycarbonate polyol and a polycaprolactone polyol are more preferable, and a polycaprolactone polyol is particularly preferable because the elongation at break, particularly the elongation at break at a high temperature can be improved. Examples of the polycarbonate polyol may include polycarbonate diol, and examples of the polycaprolactone polyol may include polycaprolactone diol and polycaprolactone triol. From the viewpoint of adhesion between the polyurethane layer and the metal layer, it is preferable that a polycarbonate polyol, a polycaprolactone polyol, or both of them are contained at a ratio of about 40% or more, about 50% or more, about 60% or more, about 70% or more, about 80% or more, or about 90% or more in terms of equivalent with respect to all polyols. The polyol can be used alone, or in combination of two or more types thereof. When coloring is performed by dispersing a pigment, (meth)acrylic polyol is preferable.

[0071] In some embodiments, the polyol contains about 0.4 equivalents or more of a polyester polyol having an average molecular weight of about 1,000 or less with respect to all polyols. When the polyester polyol having an average molecular weight of about 1,000 or less is contained in an amount of about 0.4 equivalent or more, the elongation at break at a high temperature can be improved. Also from the viewpoint of elongation at break at a high temperature, polycarbonate polyols and poly caprolactone polyols are preferable. Here the weight average molecular weight of the polyol refers to a number average molecular weight based on polystyrene measured by gel permeation chromatography (GPC).

[0072] Specific examples of the polyester polyol include polycaprolactone diols such as TONE (tradename) 0201 (available from Dow Chemical Co., Midland, Mich., USA; average molecular weight 530), PLACCEL (tradename) 205 (available from DAICEL CORPORATION; average molecular weight 530), PLACCEL (tradename) 205H (available from DAICEL CORPORATION; average molecular weight 530), PLACCEL (tradename) 208 (available from DAICEL CORPORATION; average molecular weight 850), and PLACCEL (tradename) 210 (available from DAICEL CORPORATION; average molecular weight 1000); and polycaprolactone triols such as TONE (tradename) 0301 (available from Dow Chemical Co., Ltd.; average molecular weight 300), TONE (tradename) 1303 (available from Dow Chemical Co., Ltd.; average molecular weight 425), TONE (tradename) 0305 (available from Dow Chemical Co., Ltd.; average molecular weight 540), PLACCEL (tradename) 305 (available from DAICEL CORPORATION; average molecular weight 550), and PLACCEL (tradename) 308 (available from DAICEL CORPORATION; average molecular weight 850); and polycarbonate diols such as NIPPOLLAN (tradename) 981 and NIPPOLLAN (tradename) 983 (available from Tosoh Corporation; average molecular weight 1000), T4671, T4691, and T5651 (available from Asahi Kasei Corporation (Minato-ku, Tokyo, Japan); average molecular weight 1000).

[0073] When polycaprolactone diol and polycarbonate diol are used in combination in the polyester polyol, these diols can be used in various quantitative ratios. Lor example, the equivalent ratio of the polycaprolactone diol and the polycarbonate diol may be set to about 1 : about 9, about 2 : about 8, about 3 : about 7, about 4 : about 6, about 5 : about 5, about 6 : about 4, about 7 : about 3, about 8 : about 2, or about 9 : about 1. When these diols are mixed in such a ratio, the average molecular weight in that state can be about 1,000 or less, preferably about 850 or less, more preferably about 750 or less, and most preferably from about 500 to about 600.

[0074] When polycaprolactone diol is used alone, its average molecular weight can be set to about 700 or less, and preferably in the range of from about 500 to about 600.

[0075] Examples of the isocyanate include at least one selected from the group consisting of an isocyanate having a cyclohexane structure, an isocyanate having no carbon-carbon double bond, and an isocyanate having a branched structure. Examples of the isocyanate having a branched structure include a trimer, a biuret, and an adduct of isocyanate.

[0076] In some embodiments, an isocyanate can be used that contains, for example, a trimer, a biuret, an adduct of isophorone diisocyanate (IPDI) or l,3-bis(isocyanatomethyl)cyclohexane (H6XDI), or a mixture of two or three of these, in an amount of at least about 0.5 equivalents with respect to all isocyanates. Such an isocyanate is more preferably a trimer or an adduct of isophorone diisocyanate or l,3-bis(isocyanatomethyl)cyclohexane because it can improve the elongation at break, particularly the elongation at break at a high temperature. The trimer, adduct, or mixture thereof of isophorone diisocyanate or l,3-bis(isocyanatomethyl)cyclohexane is preferably contained at a ratio of about 50% or more, about 60% or more, about 70% or more, about 80% or more, or about 90% or more in terms of equivalent with respect to all isocyanates because the elongation at break, particularly the elongation at break at a high temperature can be improved.

[0077] The trimer of isophorone diisocyanate is available, for example, under the trade name “Desmodur (tradename) Z4370” from Sumika Covestro Urethane Co., Ltd. (Amagasaki-shi, Hyogo, Japan) or under the trade name “VESTNAT (tradename) T1890” from Evonik Japan Co., Ltd. (Shinjuku-ku, Tokyo, Japan). The adduct of isophorone diisocyanate is an adduct of isophorone diisocyanate with trimethylolpropane, trimethylolethane, pentaerythriol, or the like, and the adduct with trimethylolpropane is available from Takeda Pharmaceutical Co., Ltd. (Chuo-ku, Tokyo, Japan) as “TAKENATE (tradename) D-140N”, for example. The trimer of 1,3- bis(isocyanatomethyl)cyclohexane is available, for example, from Mitsui Chemicals, Inc. (Chuo-ku, Tokyo, Japan) under the trade name “D-127N” The adduct of l,3-bis(isocyanatomethyl)cyclohexane is available from, for example, Mitsui Chemicals, Inc. (Chuo-ku, Tokyo, Japan) under the trade name “D- 120N”

[0078] The equivalent ratio between isocyanate and polyol in the polyurethane resin composition may be appropriately adjusted so as to obtain desired performance (for example, protective performance) as the polyurethane layer. For example, the equivalent ratio between isocyanate and polyol (isocyanate / polyol) may be in the range of about 0.7 or more, about 0.8 or more, about 0.9 or more, or about 1.0 or more, and about 2.0 or less, about 1.8 or less, about 1.6 or less, or about 1.5 or less. When the equivalent ratio between isocyanate and polyol is within this range, adhesion between the polyurethane layer and the metal layer is excellent, and elongation at break, particularly elongation at break at a high temperature, weather resistance, chemical resistance, and scratch resistance can also be improved.

[0079] With respect to the polyurethane resin composition containing an isocyanate and a polyol, a polyurethane resin may be prepared by appropriately using a known method. For example, polymerization may be performed in a state where a catalyst is added to the polyurethane resin composition. As such a catalyst, a common catalyst may be used, for example, a dibutyltin dilaurate (DBTDL) catalyst, zinc naphthenate, zinc octenate, triethylenediamine, or the like is used. The amount of the catalyst may be set to from about 0.005 mass% to about 0.5 mass% with respect to 100 mass% of the resin composition.

[0080] The polyurethane layer obtained by reacting the two-component curable polyurethane precursor layer may have a single layer structure or a laminated structure. In the case of a laminated structure, for example, the polyurethane layer may be a laminate of a fdm formed from the polyurethane resin composition, or may be a multilayer coating of the resin composition. The polyurethane layer may be colored or colorless. The polyurethane layer may be opaque, semitransparent, or transparent. The polyurethane layer may have an uneven shape such as an embossed pattern on the entire surface or a part of the surface. The polyurethane layer may be formed, for example, by applying the polyurethane resin composition to the primer layer by a known coating method such as knife coating or bar coating. Alternatively, the polyurethane layer may be formed by coating a release liner with the resin composition to form a polyurethane precursor fdm, and then laminating the fdm on the primer layer and curing the fdm. Alternatively, the polyurethane layer may be formed by laminating an uncured polyurethane precursor fdm formed into a fdm shape in advance by extrusion, stretching, or the like on the primer layer and then curing the fdm.

[0081] The thickness of the polyurethane layer may be appropriately adjusted depending on desired performance (for example, protective performance) and the like. Such a thickness may be, for example, about 1 micrometer or more, about 3 micrometers or more, about 5 micrometers or more, about 7 micrometers or more, or about 10 micrometers or more, about 50 micrometers or less, about 40 micrometers or less, about 30 micrometers or less, or about 20 micrometers or less.

[0082] The polyurethane layer of the present disclosure may contain, as an optional component, a fdler, a matting agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a flame retardant, a hard coat material, a gloss imparting agent, a dispersant, a plasticizer, a flow improver, a surfactant, a leveling agent, a silane coupling agent, a catalyst, a pigment, a dye, and the like as long as the effect of the present disclosure is not adversely affected. The optional components can be used alone, or in combination of two or more types.

[0083] According to the method of producing a decorative laminate of the present disclosure, the two- component curable polyurethane precursor layer is directly applied to the primer layer, and then the precursor layer is caused to react to form the polyurethane layer. Thus, the decorative laminate is excellent in adhesion and opening resistance. This, in the decorative laminate of the present disclosure, the polyurethane layer can achieve 90 / 100 or more, 95 / 100 or more, or 97 / 100 or more and 100 / 100 or less, or 99 / 100 or less in the number of remaining squares when subjected to the water resistance test described below, and the polyurethane layer can exhibit an opening width and / or peeling width of at most about 0.5 mm or less, about 0.4 mm or less, about 0.3 mm or less, about 0.2 mm or less, or about 0. 1 mm or less, about 0 mm or more, or more than about 0 mm when subjected to the heat resistance test described below. Here, regarding the configuration of each layer of the decorative laminate of the present disclosure (for example, the material, the thickness, and the like of each layer), the configuration described above in the method of producing a decorative laminate of the present disclosure may be employed in the same manner. Water Resistance Test

[0084] A decorative laminate is immersed in 40°C water for 240 hours, the laminate is taken out, the moisture is wiped off, and the laminate is allowed to stand for 1 hour. Then, a total of 100 squares of 10 x 10 squares of 1 mm square are formed on the polyurethane layer of the laminate by a cutter, and immediately after Sellotape (tradename) CT-24 (available from NI CHIB AN Co., Ltd. (Bunkyo-ku, Tokyo, Japan)) is applied to the 100 squares, the Sellotape (tradename) is peeled off, and the number of remaining squares where the polyurethane layer is not peeled off is checked. Heat Resistance Test

[0085] By using No. 517 DuPont-type Falling Impact Tester (available from YASUDA SEIKI SEISAKUSHO, LTD., (Nishinomiya-shi, Hyogo, Japan)), a decorative laminate is placed on a die having a recess such that the recess of the die is covered, and the metal layer of the laminate is a top surface, as illustrated in FIG. 4. With a hemispherical punch having a half-inch-diameter tip being in contact with the top surface of the metal layer, a weight of 1 kg is dropped from a height of 50 cm into the punch to deform the laminate into a convex shape (FIG. 5(a)). Next, as illustrated in FIG. 5(b), a cross-shaped cut is made in the polyurethane layer of the laminate that has been deformed into the convex shape with a cutter blade, the laminate having the cut is subjected to the following Heat Cycle, and the opening width and peeling width of the polyurethane layer at the cut portion are checked. Here, “height” of “a height of 50 cm” refers to a distance from the lowest end of the weight to the uppermost surface of the punch as illustrated on the left side of FIG. 4(a) or FIG. 4(b). The following Heat Cycle is typically performed sequentially: (Heat Cycle)

[0086] (1) Raise the temperature from 23 °C to 80°C over 1 hour

[0087] (2) Keep the temperature at 80°C for 18 hours

[0088] (3) Lower the temperature to -30°C over 1 hour

[0089] (4) Keep the temperature at -30°C for 4 hours

[0090] (5) Raise the temperature to 80°C over 1 hour

[0091] (6) Keep the temperature at 80°C for 18 hours Repeat the operations (3) to (6) described above 9 times

[0092] (7) Lower the temperature to -30°C over 1 hour

[0093] (8) Keep the temperature at -30°C for 4 hours

[0094] (9) Raise the temperature from -30°C to 23°C over 1 hour

[0095] Unlike a known product, the decorative laminate of the present disclosure does not have an adhesive layer such as a heat-sensitive polyurethane adhesive layer, which is a flexible layer applied between the polyurethane layer and the metal layer, and thus, the hardness of the entire decorative laminate can be improved. In some embodiments, the decorative laminate of the present disclosure can achieve a pencil hardness of B or more, HB or more, or F or more in a pencil hardness test described below. The upper limit of the pencil hardness is not particularly limited, and it may be, for example, 3H or less, 2H or less, or H or less.

[0096] Since the decorative laminate of the present disclosure includes the polyurethane layer, the decorative laminate has excellent corrosion resistance and impact resistance. Thus, the decorative laminate of the present disclosure can achieve a passing level in the weather resistance test and the chemical resistance test described below. In particular, a decorative laminate produced using a two- component curable polyurethane resin composition containing at least one polyol selected from the group consisting of a polycaprolactone polyol and a polycarbonate polyol and at least one isocyanate selected from the group consisting of an isocyanate having a cyclohexane structure, an isocyanate having no carbon-carbon double bond, and an isocyanate having a branched structure can further improve impact resistance. In some embodiments, the decorative laminate of the present disclosure can exhibit impact resistance of having no cracking or peeling in the polyurethane layer deformed into a convex shape when, by using No. 517 DuPont-type Falling Impact Tester (available from YASUDA SEIKI SEISAKUSHO, LTD., (Nishinomiya-shi, Hyogo, Japan)), the laminate is placed on a die having a recess such that the recess of the die is covered and the metal layer of the laminate is a top surface; with a hemispherical punch having a half-inch-diameter tip being in contact with the top surface of the metal layer, a weight of 1 kg is dropped from a height of 50 cm into the punch.

[0097] In some embodiments, the decorative laminate of the present disclosure optionally includes an additional layer other than the layers described above to the extent that the effect of the present invention is not adversely affected. Examples of such an additional layer include at least one selected from the group consisting of colored layers, decorative layers (e.g., pattern layers and relief layers), brightening layers, adhesive layers, and release liners. The additional layer may be applied to the entire surface or a part of the surface of the laminate. For example, when a colored layer, a decorative layer, and a brightening layer are applied between the polyurethane layer and the primer layer, these layers may be applied to a part of the polyurethane layer and / or the primer layer as long as the adhesion between the polyurethane layer and the primer layer is not inhibited. Here, when the colored layer and the decorative layer are formed using the two-component curable polyurethane resin composition in the same manner as the above-described polyurethane layer, these layers may be regarded as a part of the polyurethane layer having the above-described laminated structure, and in this case, these layers may be formed by applying the composition to the entire surface of the polyurethane layer and / or the primer layer and following the above-described method of producing a decorative laminate of the present disclosure. The adhesive layer as an additional layer is intended to be a layer for bonding the decorative laminate of the present disclosure to a support member or the like, and the adhesive layer may be applied to the entire surface or a part of the surface of the metal layer opposite to the surface to which the polyurethane layer is applied. The additional layer may have a three-dimensional shape such as an emboss pattern on its surface.

[0098] The decorative laminate of the present disclosure may be, for example, a sheet-like article, a rolled body wound in a roll shape, or an article having a three-dimensional shape. Here, examples of the article having a three-dimensional shape include a laminate processed into a curved shape and a laminate pressed into a predetermined shape. The decorative laminate of the present disclosure has excellent performance such as adhesion between the metal layer and the polyurethane layer, and is less likely to cause problems such as peeling and breakage even when subjected to three-dimensional molding processing. Thus, the decorative laminate can be suitably used for three-dimensional molding processing.

[0099] An article including the decorative laminate of the present disclosure having a three- dimensional shape formed by processing the decorative laminate of the present disclosure may be referred to as a decorative article in the present disclosure. Such a decorative article may be produced by forming the decorative laminate of the present disclosure using a known forming method, for example, pressing or roll forming. Examples of the pressing include press forming, bending, and deep drawing. These methods can be used alone, or in combination of two or more types thereof.

[0100] As the press forming, for example, a method can be employed in which the metal layer side of the decorative laminate of the present disclosure is disposed in a female die of a press die, and then a male die is pressed from the polyurethane layer side of the decorative laminate to plastically deform the metal layer. In addition, it is also possible to employ a method in which the polyurethane layer side of the decorative laminate of the present disclosure is disposed in a female die of a press die, and then a male die is pressed from the metal layer side of the decorative laminate to plastically deform the metal layer.

[0101] The roll forming can be performed using a roll forming machine, which is also called a tube mill. For example, multiple rolls on a machine can be used to sequentially process the decorative laminate of the present disclosure into a curved shape, for example, in the form of a tube.

[0102] The bending can be performed by, for example, fixing a part of the decorative laminate of the present disclosure and bending the unfixed part at an any angle starting from the boundary between the fixed part and the unfixed part by applying a die to the unfixed part or manually striking the unfixed part.

[0103] A resin material or a rubber material may be injected into the decorative laminate having a three-dimensional shape after processing by using an extrusion method or the like to integrate the laminate with such a material.

[0104] In some embodiments, a support member may be applied to a decorative laminate of the present disclosure having a three-dimensional shape to provide a decorative article having a three- dimensional shape including a support member and a decorative laminate adhered to the support member.

[0105] The material for the support member is not particularly limited, and examples thereof include resin raw materials (e.g., polyolefin resins, polyester resins, (meth)acrylic resins, polycarbonate resins, and acrylonitrile-butadiene-styrene copolymers), inorganic raw materials (e.g., glass, ceramic, concrete, gypsum, calcium silicate, natural stone, and asphalt), rubber raw materials, cloth materials (e.g., woven fabrics, knitted fabrics, and nonwoven fabrics), metal or metal alloy materials (e.g., iron, aluminum, and stainless steel), and woody raw materials including paper and the like.

[0106] The shape or structure of the support member is not particularly limited. The shape may be, for example, a film shape, a plate shape, or a three-dimensional shape, and the structure may be a singlelayer structure, a laminated structure, or a composite structure in which a plurality of members having different shapes or materials are combined.

[0107] The decorative article including the decorative laminate of the present disclosure can be used in a variety of applications. Examples of such an application include signboards; street signs; various interior or exterior articles, for example, interior or exterior articles of vehicles such as automobiles, railways, aircrafts, and ships (e.g., front members such as roof members, pillar members, door trim members, instrument panel members, and bonnets, bumper members, fender members, side sill members, and interior panel members), and interior or exterior articles of buildings (e.g, window glasses, doors, sashes, roof members such as tiles, outer wall members, and wall papers); electrical appliances such as personal computers, smartphones, mobile phones, refrigerators, and air conditioners; stationeries; furniture; desks; and various containers such as cans. Of these, the decorative article including the decorative laminate of the present disclosure can be suitably used as an interior article or an exterior article of a vehicle or a building because the decorative laminate of the present disclosure is excellent in decorative performance such as metallic luster.

[0108] The method of applying the decorative laminate of the present disclosure to the support member (adherend) constituting the decorative article is not particularly limited, and a known method may be appropriately used. Examples of the method include hand application, injection molding methods such as an insert injection molding method, an in-mold method, a two-color injection molding method, a core back injection molding method, and a sandwich injection molding method.

[0109] Examples

[0110] In the following examples, specific embodiments of the present disclosure will be illustrated, but the present invention is not limited to these examples. All 'part' and 'percent' are based on mass unless otherwise specified. A numerical value essentially includes an error originated from a measurement principle and a measuring device. The numerical value is generally indicated by a significant digit that is rounded.

[0111] The products used in this example are indicated in Table 1 below.

[0112] Table 1 Experimental Example 1

[0113] In Experimental Example 1, the impact resistance, moldability, and weather resistance of the test sample were evaluated.

[0114] Preparation of Two-Component Curable Polyurethane Resin Composition BM for Colored Laver (Blue Metallic Color)

[0115] A blue metallic color coating material was prepared by uniformly mixing 3 parts by mass of a pearlescent agent, 0.5 parts by mass of a black pigment, 0.2 parts by mass of a violet pigment, 30 parts by mass of Desmophen (tradename) A565 (acrylic polyol), 30.1 parts by mass of toluene, 13.9 parts by mass of ethyl acetate, 6.9 parts by mass of butyl acetate, 6 parts by mass of xylene, 5.3 parts by mass of ethylbenzene, and 4. 1 parts by mass of isobutyl acetate. A two-component curable polyurethane resin composition BM for a colored layer was prepared by uniformly mixing 100 parts by mass of the obtained blue metallic color coating material and 7 parts by mass of VESTNAT (tradename) T1890E. Preparation of Two-Component Curable Polyurethane Resin Composition GM for Colored Laver (Gold Metallic Color)

[0116] A gold metallic color coating material was prepared by uniformly mixing 5 parts by mass of aluminum brightening agent, 0.5 parts by mass of yellow pigment, 0.1 parts by mass of black pigment, 0.1 parts by mass of white pigment, 30 parts by mass of Desmophen (tradename) A565 (acrylic polyol), 29.2 parts by mass of toluene, 13.4 parts by mass of ethyl acetate, 6.9 parts by mass of butyl acetate, 5.9 parts by mass of xylene, 4.9 parts by mass of ethylbenzene, and 4 parts by mass of isobutyl acetate. A two-component curable polyurethane resin composition GM for a colored layer was prepared by uniformly mixing 100 parts by mass of the obtained gold metallic color coating material and 7 parts by mass of VESTNAT (tradename) T1890E.

[0117] Preparation of Two-Component Curable Polyurethane Resin Composition C for Surface Layer (Colorless)

[0118] A two-component curable polyurethane resin composition C for a surface layer was prepared by uniformly mixing 100 parts by mass of PLACCEL (tradename) 205H, 2.0 parts by mass of TINUVIN (tradename) 292, 2.0 parts by mass of TINUVIN (tradename) 99-2, 25.0 parts by mass of butyl acetate, 0.15 parts by mass of a catalyst, and 150 parts by mass of VESTNAT (tradename) T1890E. The solid content of the composition C was 74.9%. Preparation of Two-Component Curable Polyurethane Resin Composition BB for Surface Layer (Blue- Black Color)

[0119] A blue-black mill-base coating material was prepared by uniformly mixing 35 parts by mass of copper-iron-manganese pigment, 17.5 parts by mass of Desmophen (tradename) A565 (acrylic polyol), 21.4 parts by mass of xylene, 15.2 parts by mass of ethylbenzene, 6.8 parts by mass of butyl acetate, and 4.1 parts by mass of isobutyl acetate. Next, a two-component curable polyurethane resin composition BB for surface layer was prepared by uniformly mixing 100 parts by mass of PLACCEL (tradename) 205H, 2.0 parts by mass of TINUVIN (tradename) 292, 2.0 parts by mass of TINUVIN (tradename) 99-2, 25.0 parts by mass of butyl acetate, 0.15 parts by mass of catalysts, 150 parts by mass of VESTNAT (tradename) T1890E, and 8.0 parts by mass of the blue-black mill-base coating material. The solid content of the composition BB was 74.3%.

[0120] Preparation of Two-Component Curable Polyurethane Resin Composition RB for Surface Laver (Red- Black Color)

[0121] A red-black mill-base coating material was prepared by uniformly mixing 11.6 parts by mass of carbon black pigment, 11.6 parts by mass of Desmophen (tradename) A565 (acrylic polyol), 30.9 parts by mass of xylene, 26.2 parts by mass of ethylbenzene, 13.8 parts by mass of butyl acetate, and 5.9 parts by mass of isobutyl acetate. Next, a two-component curable polyurethane resin composition RB for surface layer was prepared by uniformly mixing 100 parts by mass of PLACCEL (tradename) 205H, 2.0 parts by mass of TINUVIN (tradename) 292, 2.0 parts by mass of TINUVIN (tradename) 99-2, 25.0 parts by mass of butyl acetate, 0.15 parts by mass of a catalyst, 150 parts by mass of VESTNAT (tradename) T1890E, and 0.8 parts by mass of the red-black mill-base coating material. The solid content of the composition RB was 74.8%.

[0122] Example 1

[0123] The two-component curable polyurethane resin composition C was applied to PK-002 using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes to dry the composition in an uncured state, whereby a colorless polyurethane precursor coating fdm having a thickness of about 0.05 mm was prepared. LUMIRROR (tradename) T60 was laminated on the coating fdm to produce a fdm having a three layer structure, and the fdm was allowed to stand at room temperature for 24 hours.

[0124] A silane coupling agent Z-6011 was diluted to 3% with alcohol, applied to a stainless steel plate (SUS430#8) as a metal substrate by wiping, and baked at 200°C for 5 minutes, whereby a primer layer having a thickness of about 1 micrometer was formed. PK-002 was peeled off from the fdm having a three layer structure while heat at the time of baking was remaining, and the uncured polyurethane precursor coating fdm surface was applied to the primer layer and allowed to stand at room temperature for 24 hours. After the obtained material was heated at 80°C for 1 hour, the LUMIRROR (tradename) T60 was removed, whereby a test sample of a decorative laminate was obtained.

[0125] Examples 2 to 6

[0126] Test samples of decorative laminates of Examples 2 to 6 were obtained in the same manner as in Example 1 except that the types of the metal substrate, the surface layer, and the PET fdm applied to the coating fdm of the surface layer were changed to those indicated in Table 2. Example 7

[0127] The two-component curable polyurethane resin composition BM for a colored layer was applied onto a biaxially stretched PET fdm (G2) using a bar coater, and then placed in a hot air oven at 80°C for 20 minutes to dry the composition in an uncured state, whereby a polyurethane precursor colored coating fdm having a thickness of about 20 micrometers was obtained. Next, the colored coating fdm was coated with the two-component curable polyurethane resin composition C for a surface layer using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes to dry the composition in an uncured state, whereby a colorless polyurethane precursor coating film having a thickness of about 0.05 mm was prepared. LUMIRROR (tradename) T60 was laminated on the coating film to produce a film having a four layer structure, and the film was allowed to stand at room temperature for 24 hours.

[0128] An acrylic primer KBS17A / B was diluted with MEK, applied to a stainless steel plate (SUS430BA) as a metal substrate by wiping, and baked at 200°C for 5 minutes, whereby a primer layer having a thickness of about 1 micrometer was formed. G2 was peeled off from the film having a four layer structure while heat at the time of baking was remaining, and the uncured polyurethane precursor colored coating film surface was applied to the primer layer and allowed to stand at room temperature for 24 hours. After the obtained material was heated at 80°C for 1 hour, the LUMIRROR (tradename) T60 was removed, whereby a test sample of a decorative laminate was obtained. Example 8

[0129] An acrylic primer KBS17A / B was diluted with MEK, applied to a stainless steel plate (SUS430BA) as a metal substrate by wiping, and baked at 200°C for 5 minutes, whereby a primer layer having a thickness of about 1 micrometer was formed. The two-component curable polyurethane resin composition GM for a colored layer was applied onto the primer layer using a bar coater, and then placed in a hot air oven at 80°C for 20 minutes to dry the composition in an uncured state, whereby a polyurethane precursor colored coating film having a thickness of about 20 micrometers was formed. Next, the colored coating film was coated with the two-component curable polyurethane resin composition C for a surface layer using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes to dry the composition in an uncured state, whereby a colorless polyurethane precursor coating film having a thickness of about 0.05 mm was prepared. LUMIRROR (tradename) T60 was laminated on the coating film, and the obtained material was allowed to stand at room temperature for 24 hours. After the obtained material was heated at 80°C for 1 hour, the LUMIRROR (tradename) T60 was removed, whereby a test sample of a decorative laminate was obtained. Comparative Examples 1 and 2

[0130] Coated plates 1 and 2 were used as test samples for Comparative Examples 1 and 2. Since the surface layers of the coated plates 1 and 2 are not polyurethane layers, the resin components constituting these surface layers are indicated in parentheses in Table 2. Physical Property Evaluation Test 1

[0131] The properties of each test sample were evaluated by the following tests. The results are indicated in Table 2.

[0132] Appearance Test: Decorativeness

[0133] The appearance such as gloss of the test samples before molding and after the three- dimensional moldability test described below (that is, after molding) was visually observed to evaluate the decorativeness. Impact Resistance Test: Impact Resistance

[0134] By using No. 517 DuPont-type Falling Impact Tester (available from YASUDA SEIKI SEISAKUSHO, LTD., (Nishinomiya-shi, Hyogo, Japan)), each test sample was placed on a die having a recess such that the recess of the die is covered and the metal layer of the laminate is a top surface. With a hemispherical punch having a half-inch-diameter tip being in contact with the top surface of the metal layer, a weight of 1 kg is dropped from a height of 50 cm into the punch. Whether there was any abnormality such as cracking or peeling was visually checked with respect to the polyurethane layer (surface layer, colored layer) that has been deformed into the convex shape.

[0135] Three-Dimensional Moldability Test: Moldability (Molding Shape)

[0136] The test sample was punched into a predetermined shape by using a press machine and a punching die so as to have the dimensional shape illustrated in FIG. 3(c) after molding, and then when the test sample was molded into the molding shape illustrated in FIG. 3(c) by using a press machine and a pressing die, whether there was any abnormality such as cracking or peeling in the polyurethane layer (surface layer, colored layer) was visually checked.

[0137] Weather Resistance Test: Weather Resistance

[0138] The mold-shaped test sample obtained in the above three-dimensional moldability test was placed for 2 years on an exposure table facing 45° south installed on a land approximately 1 km away from the coast of Numazu-shi, Shizuoka, Japan and then visually checked for abnormalities such as noticeable change in color and gloss, cracking, and peeling of the polyurethane layer (surface layer, colored layer) and rust of the metal substrate.

[0139] Table 2

[0140] Experimental Example 2

[0141] In Experimental Example 2, the impact resistance, opening resistance, adhesion, and hardness of the test sample were evaluated according to the presence or absence of the primer layer in the test sample and the presence or absence of the adhesive layer between the primer layer and the polyurethane layer.

[0142] Preparation of Polyester Adhesive Composition for Adhesive Laver

[0143] A polyester adhesive composition for an adhesive layer was prepared by uniformly mixing 30 parts by mass of ELITEL (tradename) UE3230, 70 parts by mass of MEK, and 2 parts by weight of Coronate (tradename) HL.

[0144] Preparation of Polyurethane Adhesive Composition for Adhesive Laver

[0145] A polyurethane adhesive composition for an adhesive layer was prepared by uniformly mixing 20 parts by mass of Desmocoll (tradename) 530, 80 parts by mass of MEK, and 0.2 parts by mass of Desmodur (tradename) RFE. Preparation of Two-Component Curable Polyurethane Resin Composition B for Surface Laver (Black (Concealing Property))

[0146] A black mill-base coating material was prepared by uniformly mixing 7.7 parts by mass of carbon black pigment, 1.9 parts by mass of titanium oxide pigment, 28.3 parts by mass of Desmophen (tradename) A565 (acrylic polyol), 25.9 parts by mass of xylene, 21.2 parts by mass of ethylbenzene, 9.8 parts by mass of butyl acetate, and 5.2 parts by mass of isobutyl acetate. Next, a two-component curable polyurethane resin composition B for surface layer was prepared by uniformly mixing 100 parts by mass of PLACCEL (tradename) 205H, 2.0 parts by mass of TINUVIN (tradename) 292, 2.0 parts by mass of TINUVIN (tradename) 99-2, 25.0 parts by mass of butyl acetate, 0.15 parts by mass of a catalyst, 150 parts by mass of VESTNAT (tradename) T1890E, and 40.0 parts by mass of the black mill-base coating material. The solid content of the composition B was 74.1%. Example 9

[0147] A test sample of the decorative laminate of Example 9 was obtained in the same manner as in Example 1. Examples 10 and 11

[0148] Test samples of decorative laminates of Examples 10 and 11 were obtained in the same manner as in Example 1 except that the metal substrate was changed to those indicated in Table 3. Comparative Example 3

[0149] The two-component curable polyurethane resin composition C was applied to PK-002 using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes to dry the composition in an uncured state, whereby a colorless polyurethane precursor coating fdm having a thickness of about 0.05 mm was prepared. LUMIRROR (tradename) T60 was laminated on the coating fdm to produce a fdm having a three layer structure, and the fdm was allowed to stand at room temperature for 24 hours. Next, the polyester adhesive composition for an adhesive layer was applied to PK-002 using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes, whereby a fdm having a two layer structure including an adhesive layer having a thickness of about 20 micrometers was prepared. After PK-002 was peeled off from the fdm having a three layer structure including the polyurethane precursor coating fdm, the fdm having a two layer structure was applied such that the adhesive layer was in contact with the polyurethane precursor coating fdm, whereby a fdm having a four layer structure including PK-002 / adhesive layer / polyurethane precursor coating fdm / T60 (PET fdm) was produced.

[0150] A silane coupling agent Z-6011 was diluted to 3% with alcohol, applied to a stainless steel plate (SUS430#8) as a metal substrate by wiping, and baked at 200°C for 5 minutes, whereby a primer layer having a thickness of about 1 micrometer was formed. PK-002 was peeled off from the fdm having a four layer structure while heat at the time of baking was remaining, and the adhesive layer was applied to the primer layer and allowed to stand at room temperature for 24 hours. After the obtained material was heated at 80°C for 1 hour, the LUMIRROR (tradename) T60 was removed, whereby a test sample of a decorative laminate was obtained. Comparative Examples 4 and 5

[0151] Test samples of decorative laminates of Comparative Examples 4 and 5 were obtained in the same manner as in Comparative Example 3 except that the metal substrate was changed to those indicated in Table 3.

[0152] Example 12

[0153] A silane-coupling agent Z-6011 was diluted to 3% with alcohol, applied to a stainless steel plate (SUS430BA) as a metal substrate by wiping, and baked at 200°C for 5 minutes, whereby a primer layer having a thickness of about 1 micrometer was formed. The two-component curable polyurethane resin composition C was applied onto the primer layer using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes to dry the composition in an uncured state, whereby a colorless polyurethane precursor coating fdm having a thickness of about 0.05 mm was prepared. LUMIRROR (tradename) T60 was laminated on the coating fdm, and the obtained material was allowed to stand at room temperature for 24 hours. After the obtained material was heated at 80°C for 1 hour, the LUMIRROR (tradename) T60 was removed, whereby a test sample of a decorative laminate was obtained.

[0154] Example 13

[0155] A test sample of the decorative laminate of Example 13 was obtained in the same manner as in Example 7.

[0156] Comparative Example 6

[0157] The two-component curable polyurethane resin composition BM for a colored layer was applied onto a biaxially stretched PET fdm (G2) using a bar coater, and then placed in a hot air oven at 80°C for 20 minutes to dry the composition in an uncured state, whereby a polyurethane precursor colored coating fdm having a thickness of about 20 micrometers was obtained. Next, the colored coating fdm was coated with the two-component curable polyurethane resin composition C for a surface layer using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes to dry the composition in an uncured state, whereby a colorless polyurethane precursor coating film having a thickness of about 0.05 mm was prepared. LUMIRROR (tradename) T60 was laminated on the coating film to produce a film having a four layer structure, and the film was allowed to stand at room temperature for 24 hours.

[0158] The polyurethane adhesive composition for an adhesive layer was applied to PK-002 using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes, whereby a film having a two layer structure including an adhesive layer, the film having a thickness of about 20 micrometers was produced. After the biaxially stretched PET film (G2) was peeled off from the film having a four layer structure including the colored layer, the film having a two layer structure was applied such that the adhesive layer was in contact with the colored layer, whereby a film having a five layer structure including PK-002 / adhesive layer / polyurethane precursor colored coating film / polyurethane precursor surface coating film / T60 (PET film) was produced, and the film was allowed to stand at room temperature for 24 hours.

[0159] An acrylic primer KBS17A / B was diluted with MEK, applied to a stainless steel plate (SUS430BA) as a metal substrate by wiping, and baked at 200°C for 5 minutes, whereby a primer layer having a thickness of about 1 micrometer was formed. PK-002 was peeled off from the film having a five layer structure while heat at the time of baking was remaining, and the adhesive layer was applied to the primer layer and allowed to stand at room temperature for 24 hours. After the obtained material was heated at 80°C for 1 hour, the LUMIRROR (tradename) T60 was removed, whereby a test sample of a decorative laminate was obtained. Comparative Example 7

[0160] A test sample of the decorative laminate of Comparative Example 7 was obtained in the same manner as in Comparative Example 6 except that the polyester adhesive composition for an adhesive layer was used instead of the polyurethane adhesive composition for an adhesive layer. Example 14

[0161] An acrylic primer KBS17A / B was diluted with MEK, applied to a stainless steel plate (SUS430BA) as a metal substrate by wiping, and baked at 200°C for 5 minutes, whereby a primer layer having a thickness of about 1 micrometer was formed. The two-component curable polyurethane resin composition B was applied onto the primer layer using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes to dry the composition in an uncured state, whereby a polyurethane precursor coating film with black concealing property having a thickness of about 0.05 mm was prepared. LUMIRROR (tradename) T60 was laminated on the coating film, and the obtained material was allowed to stand at room temperature for 24 hours. After the obtained material was heated at 80°C for 1 hour, the LUMIRROR (tradename) T60 was removed, whereby a test sample of a decorative laminate was obtained.

[0162] Comparative Example 8

[0163] The two-component curable polyurethane resin composition C for a surface layer was applied to PK-002 using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes to dry the composition in an uncured state, whereby a colorless polyurethane precursor coating film having a thickness of about 50 micrometers was prepared. LUMIRROR (tradename) T60 was laminated on the coating film to produce a film having a three layer structure, and the film was allowed to stand at room temperature for 24 hours.

[0164] A stainless steel plate (SUS304#8) as a metal substrate having no primer layer was heated to 200°C, and while heat was remaining, PK-002 was peeled off from the film having a three layer structure, and the uncured polyurethane precursor coating film surface was applied to the primer layer and allowed to stand at room temperature for 24 hours. After the obtained material was heated at 80°C for 1 hour, the LUMIRROR (tradename) T60 was removed, whereby a test sample of a decorative laminate was obtained.

[0165] Comparative Example 9

[0166] The two-component curable polyurethane resin composition C was applied to PK-002 using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes to dry the composition in an uncured state, whereby a colorless polyurethane precursor coating film having a thickness of about 0.05 mm was prepared. LUMIRROR (tradename) T60 was laminated on the coating film to produce a film having a three layer structure, and the film was allowed to stand at room temperature for 24 hours.

[0167] 3M (tradename) Adhesion Promoter 86A was diluted three times with isopropyl alcohol and applied to a stainless steel plate (SUS304#8) as a metal substrate by wiping, and then placed in a hot air oven at 200°C for 3 minutes, whereby an adhesive layer having a thickness of about 1 micrometer was formed. PK-002 was peeled off from the film having a three layer structure while heat was remaining, and the uncured polyurethane precursor coating film surface was applied to the adhesive layer and allowed to stand at room temperature for 24 hours. After the obtained material was heated at 80°C for 1 hour, the LUMIRROR (tradename) T60 was removed, whereby a test sample of a decorative laminate was obtained.

[0168] Physical Property Evaluation Test 2

[0169] The properties of each test sample were evaluated by performing the appearance test and the impact resistance test of the above-described physical property evaluation test 1 and the following tests. The results are indicated in Table 3.

[0170] Heat Resistance Test: Opening Resistance

[0171] By using No. 517 DuPont-type Palling Impact Tester (available from YASUDA SEIKI SEISAKUSHO, LTD., (Nishinomiya-shi, Hyogo, Japan)), the test sample was placed on a die having a recess such that the recess of the die is covered and the metal layer of the laminate is a top surface. With a hemispherical punch having a half-inch-diameter tip being in contact with the top surface of the metal layer, a weight of 1 kg is dropped from a height of 50 cm into the punch to deform the test sample into a convex shape. The polyurethane layer of the convexly deformed test sample was crosscut with a cutter blade and the following Heat Cycle was applied to the cut test sample. The opening width and the peeling width of the polyurethane layer at the cut portion were checked using a caliper. Here, in the present example, a case where both the opening width and the peeling width were 0.5 mm or less was evaluated as “passing”, and a case where any one of the opening width and the peeling width was more than 0.5 mm was evaluated as “fail”:

[0172] (Heat Cycle)

[0173] (1) Raise the temperature from 23 °C to 80°C over 1 hour

[0174] (2) Keep the temperature at 80°C for 18 hours

[0175] (3) Lower the temperature to -30°C over 1 hour

[0176] (4) Keep the temperature at -30°C for 4 hours

[0177] (5) Raise the temperature to 80°C over 1 hour

[0178] (6) Keep the temperature at 80°C for 18 hours

[0179] Repeat the operations (3) to (6) described above 9 times

[0180] (7) Lower the temperature to -30°C over 1 hour

[0181] (8) Keep the temperature at -30°C for 4 hours

[0182] (9) Raise the temperature from -30°C to 23°C over 1 hour

[0183] Water Resistance Test: Adhesion

[0184] The test sample was immersed in 40°C water for 240 hours, the test sample was taken out, the moisture was wiped off, and the test sample was allowed to stand for 1 hour. Then, a total of 100 squares (10 x 10 squares) of 1 mm square were formed on the polyurethane layer of the test sample using a cutter. Sellotape (tradename) was attached to the 100 squares, and immediately after that, the Sellotape (tradename) was forcefully peeled off, and the number of remaining squares where the polyurethane layer was not peeled off was checked. Here, when the number of remaining squares is 90 / 100 or more, the test sample can be regarded as “passing”, and when it is 89 / 100 or less, the test sample can be regarded as “fail”.

[0185] Pencil Hardness Test: Hardness

[0186] A pencil lead cut into a cylindrical shape and flattened with sandpaper was applied to the polyurethane layer of the test sample at an angle of 45°, and the pencil lead was moved 10 mm at a speed of 600 mm / min while a load of 750 g was applied to rub the polyurethane layer with the pencil lead. Different places were tested five times using pencils with hardnesses of 6B to HB, and the hardness of the test sample was determined from the hardness of the pencil used when the surfaces of the polyurethane layers were not scratched four or more times. Here, HB can be regarded as “passing”, and B or less can be regarded as “fail”. Table 3

[0187] Experimental Example 3

[0188] In Experimental Example 3, the chemical resistance, moldability, and weather resistance of the test sample were evaluated.

[0189] Example 15

[0190] A test sample of the decorative laminate of Example 15 was obtained in the same manner as in Example 1. Example 16

[0191] The two-component curable polyurethane resin composition C was applied to PK-002 using a bar coater, and then placed in a hot air oven at 80°C for 4 minutes to dry the composition in an uncured state, whereby a colorless polyurethane precursor coating fdm having a thickness of about 0.05 mm was prepared. LUMIRROR (tradename) T60 was laminated on the coating fdm to produce a fdm having a three layer structure, and the fdm was allowed to stand at room temperature for 24 hours.

[0192] A stainless steel plate (SUS430#8) as a metal substrate was subjected to plasma treatment in a nitrogen atmosphere, and then a silane coupling agent Z-6011 diluted with alcohol to 3% was applied to the plasma-treated surface of the metal substrate by wiping and baked at 200°C for 5 minutes, whereby a primer layer having a thickness of about 1 micrometer was formed. PK-002 was peeled off from the fdm having a three layer structure while heat at the time of baking was remaining, and the uncured polyurethane precursor coating fdm surface was applied to the primer layer and allowed to stand at room temperature for 24 hours. After the obtained material was heated at 80°C for 1 hour, the LUMIRROR (tradename) T60 was removed, whereby a test sample of a decorative laminate was obtained.

[0193] Example 17

[0194] A test sample of the decorative laminate of Example 17 was obtained in the same manner as in Example 14.

[0195] Comparative Example 10

[0196] As a test sample of Comparative Example 10, a stainless steel plate (SUS430#8) alone was used.

[0197] Physical Property Evaluation Test 3

[0198] The properties of each test sample were evaluated by the following tests. The results are indicated in Table 4.

[0199] Appearance Test: Decorativeness

[0200] The appearance such as gloss of the test samples before molding and after the three- dimensional moldability test described below (that is, after molding) was visually observed to evaluate the decorativeness.

[0201] Chemical Resistance Test: Chemical Resistance

[0202] Hydrochloric acid of 1 mass% was dropped onto the surface of the polyurethane layer in the test samples of Examples 15 to 17 and onto the surface of the metal substrate in the test sample of Comparative Example 9, and each sample was placed in a hot air oven at 40°C for 1 hour. Thereafter, the surface on which hydrochloric acid was dropped was washed with water, and a mark such as discolorment was visually observed.

[0203] Three-Dimensional Moldability Test: Moldability (Hat Shape)

[0204] Whether there was an abnormality such as cracking in the polyurethane layer or the metal substrate was visually checked when each test sample was cut into a circular shape having a diameter of about 135 mm and molded into a hat-like shape having a height of 45 mm and a diameter of 64 mm as illustrated in FIG. 5 by using a press machine and a press mold.

[0205] Weather Resistance Test: Weather Resistance

[0206] The hat-shaped test sample obtained in the above three-dimensional moldability test was placed for 2 years on an exposure table facing 45° south installed on a land approximately 1 km away from the coast of Numazu-shi, Shizuoka, Japan and then visually checked for abnormalities such as noticeable change in color and gloss, cracking, and peeling of the polyurethane layer and rust of the metal substrate.

[0207] Table 4

[0208] Various variations of the above-mentioned embodiments and examples will be apparent to those skilled in the art without departing from the basic principle of the present invention. In addition, it is apparent for a person skilled in the art that various modifications and variations of the present invention can be made without departing from the spirit and scope of the present invention.

[0209] Reference Signs List

[0210] 100, 200 Decorative laminate

[0211] 101, 201 Metal layer

[0212] 103, 203 Primer layer

[0213] 105 Adhesive layer

[0214] 107, 207 Polyurethane layer

[0215] 400 Weight

[0216] 401 Punch

[0217] 403 Test sample (decorative laminate)

[0218] 405 Die

[0219] Some of the embodiments of the present disclosure are described in Item 1 to Item 10 below. Item 1

[0220] A method of producing a decorative laminate for three-dimensional molding processing, the method including: preparing a metal layer; applying a primer layer containing at least one selected from the group consisting of an organosilicon compound and a (meth)acrylic resin to the metal layer; applying a two-component curable polyurethane precursor layer containing a polyol and an isocyanate directly to the primer layer; and causing the two-component curable polyurethane precursor layer to react to form a polyurethane layer.

[0221] Item 2

[0222] The method according to Item 1, in which the polyurethane precursor layer is an uncured polyurethane sheet or an uncured polyurethane coating layer.

[0223] Item 3

[0224] The method according to Item 1 or 2, in which the polyol is at least one selected from the group consisting of a polycaprolactone polyol and a polycarbonate diol, and the isocyanate is at least one selected from the group consisting of an isocyanate having a cyclohexane structure, an isocyanate having no carbon -carbon double bond, and an isocyanate having a branched structure.

[0225] Item 4

[0226] The method according to any one of Items 1 to 3, in which the primer layer has a thickness of about 5 micrometers or less. Item 5

[0227] A decorative laminate for three-dimensional molding processing, the laminate including a metal layer, a primer layer, and a polyurethane layer in this order, the primer layer containing at least one selected from the group consisting of an organosilicon compound and a (meth)acrylic resin, the polyurethane layer containing a cured reaction product of a two-component curable polyurethane resin composition containing a polyol and an isocyanate, in which the polyurethane layer is applied directly to the primer layer, when the polyurethane layer of the laminate is subjected to a Water Resistance Test below, the polyurethane layer achieves 90 / 100 or more in terms of the number of remaining squares, and when the polyurethane layer of the laminate is subjected to a Heat Resistance Test below, the polyurethane layer exhibits an opening width or a peeling width of 0.5 mm or less at most: Water Resistance Test

[0228] The laminate is immersed in 40°C water for 240 hours, the laminate is taken out, the moisture is wiped off, and the laminate is allowed to stand for 1 hour. Then, on the polyurethane layer of the laminate, a total of 100 squares (10 x 10) of 1 mm square are formed with a cutter, and immediately after Sellotape (tradename) is applied to the 100 squares, the Sellotape (tradename) is peeled off, and the number of remaining squares where the polyurethane layer is not peeled off is checked. Heat Resistance Test

[0229] By using No. 517 DuPont-type Falling Impact Tester, the laminate is placed on a die having a recess such that the recess of the die is covered and the metal layer of the laminate is a top surface; with a hemispherical punch having a half-inch-diameter tip being in contact with the top surface of the metal layer, a weight of 1 kg is dropped from a height of 50 cm into the punch to deform the laminate into a convex shape; in the polyurethane layer that has been deformed into the convex shape, a cross cut is made with a cutter blade, and an opening width and a peeling width of the polyurethane layer at the cut portion is checked after Heat Cycle below is applied to the laminate: (Heat Cycle)

[0230] (1) Raise the temperature from 23 °C to 80°C over 1 hour

[0231] (2) Keep the temperature at 80°C for 18 hours

[0232] (3) Lower the temperature to -30°C over 1 hour

[0233] (4) Keep the temperature at -30°C for 4 hours

[0234] (5) Raise the temperature to 80°C over 1 hour

[0235] (6) Keep the temperature at 80°C for 18 hours

[0236] Repeat the operations (3) to (6) are repeated 9 times

[0237] (7) Lower the temperature to -30°C over 1 hour

[0238] (8) Keep the temperature at -30°C for 4 hours

[0239] (9) Raise the temperature from -30°C to 23°C over 1 hour.

[0240] Item 6 The laminate according to Item 5, in which the polyol is at least one selected from the group consisting of a polycaprolactone polyol and a polycarbonate polyol, and the isocyanate is at least one selected from the group consisting of an isocyanate having a cyclohexane structure, an isocyanate having no carbon -carbon double bond, and an isocyanate having a branched structure. Item 7

[0241] The laminate according to Item 5 or 6, in which the primer layer has a thickness of about 5 micrometers or less.

[0242] Item 8

[0243] The laminate according to any one of Items 5 to 7, in which when, by using No. 517 DuPont- type Falling Impact Tester, the laminate is placed on a die having a recess such that the recess of the die is covered and the metal layer of the laminate is a top surface; with a hemispherical punch having a half-inch-diameter tip being in contact with the top surface of the metal layer, a weight of 1 kg is dropped from a height of 50 cm into the punch, the polyurethane layer deformed into the convex shape is not cracked or peeled.

[0244] Item 9

[0245] A decorative article including a laminate described in any one of Items 5 to 8, the decorative article having a three-dimensional shape.

[0246] Item 10

[0247] A method of producing a decorative article, the method including subjecting the laminate described in any one of Items 5 to 8 to pressing or roll forming.

Claims

Claims1. A method of producing a decorative laminate for three-dimensional molding processing, the method comprising: preparing a metal layer; applying a primer layer comprising at least one selected from the group consisting of an organosilicon compound and a (meth)acrylic resin to the metal layer; applying a two-component curable polyurethane precursor layer containing a polyol and an isocyanate directly to the primer layer; and causing the two-component curable polyurethane precursor layer to react to form a polyurethane layer.

2. The method according to claim 1, wherein the polyurethane precursor layer is an uncured polyurethane sheet or an uncured polyurethane coating layer.

3. The method according to claim 1 or 2, wherein the polyol is at least one selected from the group consisting of a polycaprolactone polyol and a polycarbonate polyol, and the isocyanate is at least one selected from the group consisting of an isocyanate having a cyclohexane structure, an isocyanate having no carbon-carbon double bond, and an isocyanate having a branched structure.

4. The method according to claim 1 or 2, wherein the primer layer has a thickness of 5 micrometers or less.

5. A decorative laminate for three-dimensional molding processing, the laminate comprising a metal layer, a primer layer, and a polyurethane layer in this order, the primer layer containing at least one selected from the group consisting of an organosilicon compound and a (meth)acrylic resin, the polyurethane layer containing a cured reaction product of a two- component curable polyurethane resin composition containing a polyol and an isocyanate, wherein the polyurethane layer is applied directly to the primer layer, when the polyurethane layer of the laminate is subjected to a Water Resistance Test, the polyurethane layer achieves 90 / 100 or more in terms of the number of remaining squares, and when the polyurethane layer of the laminate is subjected to a Heat Resistance Test, the polyurethane layer exhibits an opening width or a peeling width of 0.5 mm or less at most:

6. The laminate according to claim 5, wherein the polyol is at least one selected from the group consisting of a polycaprolactone polyol and a polycarbonate polyol, and the isocyanate is at least one selected from the group consisting of an isocyanate having a cyclohexane structure, an isocyanate having no carbon-carbon double bond, and an isocyanate having a branched structure.

7. The laminate according to claim 5 or 6. wherein the primer layer has a thickness of 5 micrometers or less.

8. The laminate according to claim 5 or 6. wherein when, by using No. 517 DuPont-type Falling Impact Tester, the laminate is placed on a die having a recess such that the recess of the die is covered and the metal layer of the laminate is a top surface, with a hemispherical punch having a half-inch- diameter tip is in contact with the top surface of the metal layer, a weight of 1 kg is dropped from a height of 50 cm into the punch, the polyurethane layer deformed into the convex shape is not cracked or peeled.

9. A decorative article comprising a laminate described in claim 5 or 6, the decorative article having a three-dimensional shape.

10. A method of producing a decorative article, the method comprising subjecting the laminate described in claim 5 or 6 to pressing or roll forming.

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