Decorative laminate for three-dimensional molding processing and method for manufacturing same

Abstract

The present invention provides a decorative laminate for three-dimensional molding processing and a method for manufacturing the same, the decorative laminate having excellent corrosion resistance, impact resistance, adhesion, and unsealing resistance after three-dimensional molding processing. A solution is that a method for manufacturing a decorative laminate for three-dimensional molding processing according to an embodiment of the present disclosure comprises: preparing a metal layer; applying a primer layer to the metal layer, the primer layer containing at least one selected from the group consisting of an organosilicon compound and a (meth) acrylic resin; applying a two-component curable polyurethane precursor layer containing a polyol and an isocyanate directly to the primer layer; and reacting the two component curable polyurethane precursor layer to form a polyurethane layer.

Description

Technical Field

[0001] This invention relates to a decorative laminate for three-dimensional molding and a method for manufacturing the same. Background Technology

[0002] In recent years, for example, decorative laminates comprising polyurethane resin layers have been developed and used in a wide range of fields such as interior furnishings.

[0003] Patent document 1 (JP H05-155976 A) describes using a laminate comprising a specific polyurethane resin layer and a heat-sensitive adhesive layer as an inner or outer membrane.

[0004] Patent document 2 (JP 2007-297569 A) discloses a decorative layer forming film comprising: a surface coating formed of a polyurethane resin and a carrier film disposed on the surface side of the surface coating, wherein the polyurethane resin is formed of a polyurethane resin composition comprising: (1) a polyisocyanate containing an adduct of isocyanurate or isophorone diisocyanate or both, based on a total amount of 0.5 equivalents or more of the polyisocyanate; and (2) a polyol formed of caprolactone diol, polycarbonate diol or a mixture thereof, and containing a polyester polyol with an average molecular weight of 1000 or less, based on a total amount of the polyol, and the polyisocyanate to polyol equivalent ratio is 0.7 to 2.0. Summary of the Invention

[0005] Technical issues

[0006] Metal substrates can corrode when exposed to wind, rain, chemicals, etc. To prevent this corrosion, a resin layer can be applied to the metal substrate. Among resin layers, polyurethane resin layers exhibit excellent impact resistance, thus effectively preventing defects such as cracking after impact. However, due to the poor adhesion of the polyurethane resin layer to the metal substrate, an adhesive layer (e.g., a heat-sensitive adhesive layer) is necessary when applying the polyurethane resin layer to the metal substrate. Since the adhesive layer is typically thicker and more flexible than the primer layer, the polyurethane resin layer may crack during, for example, three-dimensional molding of a laminate comprising a metal substrate, adhesive layer, and polyurethane resin layer; or even if the polyurethane resin layer does not crack, if a cut is formed within it, the cut may open over time. For example, when the polyurethane resin layer is stretched during molding processes such as deep drawing, and then cut and heated in this state, the polyurethane resin layer tends to revert to its original state. Since the flexible adhesive layer cannot suppress the reversion of the polyurethane resin layer, the opening of the cut is likely to occur.

[0007] This invention provides a decorative laminate for three-dimensional molding and a method for manufacturing the decorative laminate, which exhibits excellent corrosion resistance, impact resistance, sealing properties and tamper resistance after three-dimensional molding.

[0008] Solution to the problem

[0009] According to one embodiment of this disclosure, a method for manufacturing a decorative laminate for three-dimensional molding is provided, the method comprising: preparing a metal layer; applying a primer layer to the metal layer, the primer layer containing at least one selected from the group consisting of organosilicon compounds and (meth)acrylic resins; directly applying a two-component curable polyurethane precursor layer containing a polyol and an isocyanate to the primer layer; and reacting the two-component curable polyurethane precursor layer to form a polyurethane layer.

[0010] According to another embodiment of this disclosure, a decorative laminate for three-dimensional molding is provided, the laminate sequentially comprising a metal layer, a primer layer, and a polyurethane layer, the primer layer containing at least one selected from the group consisting of organosilicon compounds and (meth)acrylic resins, the polyurethane layer containing a curing reaction product of a two-component curable polyurethane resin composition comprising a polyol and an isocyanate, wherein the polyurethane layer is directly applied to the primer layer, and when the polyurethane layer of the laminate is subjected to the following water resistance test, the remaining square count of the polyurethane layer reaches 90 / 100 or more, and when the polyurethane layer of the laminate is subjected to the following heat resistance test, the polyurethane layer exhibits an opening width or peel width of at most 0.5 mm or less:

[0011] Waterproofing test

[0012] The decorative laminate used for 3D molding was immersed in water at 40°C for 240 hours. After removing the laminate, the moisture was wiped off, and the laminate was allowed to stand for 1 hour. Then, a total of 100 1mm square 10×10 grids were formed on the polyurethane layer of the laminate using a cutter. Sellotape (trade name) was applied to these 100 squares, and immediately afterward, the Sellotape (trade name) was peeled off. The number of remaining squares that were not peeled off from the polyurethane layer was then checked.

[0013] Heat resistance test

[0014] Using a DuPont No. 517 drop hammer impact testing machine, a decorative laminate for three-dimensional molding was placed on a grooved mold, with the groove covered and the metal layer of the laminate as the top surface. A 1 kg weight was dropped from a height of 50 cm into the top surface of the metal layer, causing the laminate to deform into a convex shape. A cross-cut was then made in the deformed polyurethane layer using a cutting blade, and after applying the following thermal cycles to the laminate, the opening width and peel width of the cut polyurethane layer were examined.

[0015] (Heat cycle)

[0016] (1) Raise the temperature from 23°C to 80°C within 1 hour.

[0017] (2) Maintain the temperature at 80℃ for 18 hours.

[0018] (3) Let the temperature drop to -30℃ in 1 hour.

[0019] (4) Maintain the temperature at -30°C for 4 hours.

[0020] (5) Raise the temperature to 80℃ in 1 hour.

[0021] (6) Maintain the temperature at 80℃ for 18 hours.

[0022] Repeat steps (3) to (6) above 9 times.

[0023] (7) Let the temperature drop to -30℃ in 1 hour.

[0024] (8) Maintain the temperature at -30°C for 4 hours.

[0025] (9) Raise the temperature from -30℃ to 23℃ within 1 hour.

[0026] According to another embodiment of this disclosure, a decorative article is provided, which includes the above-described decorative laminate having a three-dimensional shape.

[0027] According to another embodiment of this disclosure, a method for manufacturing decorative articles is provided, the method comprising pressing or rolling the aforementioned decorative laminate.

[0028] Beneficial effects of the invention

[0029] According to this disclosure, a decorative laminate for three-dimensional molding and a method for manufacturing the decorative laminate are provided, wherein the decorative laminate exhibits excellent corrosion resistance, impact resistance, sealing properties and tamper resistance after three-dimensional molding.

[0030] The above description should not be construed as disclosing all embodiments of the invention or all advantages associated with the invention. Attached Figure Description

[0031] Figure 1 This is a diagram showing the cross-section of a known decorative laminate.

[0032] Figure 2 This is a cross-sectional view showing an embodiment of the decorative laminate for three-dimensional molding.

[0033] Figure 3(a) is a diagram of decorative articles (car molded components) of Embodiments 1 to 4 obtained by three-dimensional molding of a decorative laminate for three-dimensional molding according to one embodiment of the present disclosure; Figure 3(b) is a diagram of decorative article (car molded component) of Embodiment 7 obtained by three-dimensional molding of a decorative laminate for three-dimensional molding according to another embodiment of the present disclosure; and Figure 3(c) is a diagram of decorative article (car molded component) of Embodiment 8 obtained by three-dimensional molding of a decorative laminate for three-dimensional molding according to another embodiment of the present disclosure.

[0034] Figure 4(a) is a perspective view schematically showing the test performed using a DuPont No. 517 drop hammer impact testing machine, and Figure 4(b) is a cross-sectional view schematically showing the state before and after the test.

[0035] Figure 5(a) is a schematic diagram of a raised portion formed on a decorative laminate for three-dimensional molding, and Figure 5(b) is a schematic diagram of a raised portion formed on a decorative laminate for three-dimensional molding with a cross-shaped cut made in the polyurethane layer of the raised portion by a cutter.

[0036] Figure 6 This is a diagram showing the shape of a hat when a decorative laminate for three-dimensional molding is pressed into an image according to an embodiment of this disclosure. Detailed Implementation

[0037] In the following description, representative embodiments of the invention will be described in more detail with reference to the accompanying drawings for purposes of illustration, but the invention is not limited to these embodiments. Regarding the reference numerals in the drawings, components labeled with similar numerals in different drawings are similar or corresponding components.

[0038] In this disclosure, "three-dimensional molding" refers to molding an object into a three-dimensional shape, and "three-dimensional shape" refers to a three-dimensional shape obtained by adding a Z-axis to a two-dimensional shape (a planar shape having only X and Y axes). Here, "three-dimensional shape" in this disclosure can include, for example, a curved surface shape.

[0039] In this disclosure, for example, the word "on" in "the primer layer is disposed on the metal layer" means that the primer layer is disposed directly on the upper side of the metal layer, or that the primer layer is disposed indirectly on the upper side of the metal layer via another layer.

[0040] In this disclosure, for example, the word "under" in "the primer layer is disposed under the metal layer" means that the primer layer is disposed directly on the underside of the metal layer, or that the primer layer is disposed indirectly on the underside of the metal layer via another layer.

[0041] In this disclosure, "transparent" means an average transmittance of about 80% or more, as measured according to JIS K 7375, in the visible light region (wavelength from 400 nm to 700 nm), and ideally, this average transmittance may be about 85% or more, or about 90% or more. There is no particular upper limit to the average transmittance, and it may be, for example, about less than 100%, about 99% or less, or about 98% or less.

[0042] In this disclosure, "semi-transparent" means that the average transmittance in the visible light region (wavelength from 400 nm to 700 nm) is less than 80% as measured according to JIS K7375, and the average transmittance is ideally less than or equal to 75%, and "semi-transparent" is intended to mean that the underlying layer is not completely hidden.

[0043] In this disclosure, "(meth)acrylic acid" means acrylic acid or methacrylic acid.

[0044] In this disclosure, the term "sheet" encompasses components referred to as "membrane".

[0045] In the following description, the decorative laminate (which may be simply referred to as "laminate" or "decorative laminate") for three-dimensional molding and its manufacturing method thereof will be described with reference to the accompanying drawings as needed.

[0046] Figure 1 The known decorative laminate 100 shown includes a metal layer 101, a primer layer 103, an adhesive layer 105, and a polyurethane layer 107. Meanwhile, in the decorative laminate of the present invention, such as... Figure 2 As shown, the metal layer 201 and the polyurethane layer 207 can be bonded together by the primer layer 203 without the use of an adhesive layer.

[0047] In known decorative laminates, because the cured polyurethane layer is applied to the metal layer, for example, in the form of a film, sufficient adhesive strength cannot be obtained by the primer layer alone, and an additional adhesive layer, such as a heat-sensitive polyurethane adhesive, is required. Meanwhile, the method for manufacturing a decorative laminate disclosed herein includes: preparing a metal layer; applying a primer layer to the metal layer, the primer layer containing at least one selected from the group consisting of organosilicon compounds and (meth)acrylic resins; directly applying a two-component curable polyurethane precursor layer containing a polyol and an isocyanate to the primer layer; and reacting the two-component curable polyurethane precursor layer to form a polyurethane layer. That is, the method for manufacturing a decorative laminate disclosed herein differs from known manufacturing methods in that instead of applying a cured polyurethane layer onto a primer layer, an uncured polyurethane layer (polyurethane precursor layer) is directly applied onto the primer layer before curing, and then the polyurethane layer (polyurethane precursor layer) undergoes a curing reaction. This process improves the adhesion strength between the polyurethane layer and the primer layer, thus enabling proper bonding of the polyurethane layer and the metal layer to each other without the need for an adhesive layer made of heat-sensitive polyurethane adhesive or similar materials used in known production methods.

[0048] Because the decorative laminate of this disclosure does not use typical flexible adhesive layers such as heat-sensitive polyurethane adhesive layers, it can reduce or prevent cracking of the polyurethane layer after three-dimensional molding, or opening over time due to cuts formed in the polyurethane layer, compared to known decorative laminates. Therefore, the decorative laminate of this disclosure is suitable for three-dimensional molding.

[0049] Because adhesive layers (such as thermosensitive polyurethane adhesive layers) are typically flexible layers, decorative laminates become soft when a polyurethane layer is applied to such adhesive layers. Therefore, for example, when the decorative laminate is pressed against a surface, defects such as indentations or scratches may sometimes appear on the surface of the decorative laminate. Since the decorative laminate of this disclosure does not use typical flexible adhesive layers such as thermosensitive polyurethane adhesive layers, the overall rigidity of the decorative laminate can be increased, and defects such as indentations or scratches can be reduced or prevented. Furthermore, according to the manufacturing method of this disclosure, since the use of adhesive layers such as thermosensitive polyurethane adhesive layers is not required, it is possible to help reduce the manufacturing cost of the decorative laminate.

[0050] The metal layer used in the method of manufacturing decorative laminates disclosed herein 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, etc., or alloys or compounds thereof. The metal layer may have a single-layer structure or a laminated structure. Among these, stainless steel is preferred from the perspective of three-dimensional molding processability and corrosion resistance.

[0051] The thickness of the metal layer is not particularly limited as long as three-dimensional molding is possible. The thickness of the metal layer can 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 can be about 3 millimeters or less, about 2 millimeters or less, about 1 millimeter or less, about 800 micrometers or less, or about 500 micrometers or less. The thickness of each layer in the decorative laminate of this disclosure can, for example, be defined as the average thickness of at least five points on the metal layer measured using a thickness gauge (PC-465N, purchased from TECLOCK). In cases where the layers constituting the laminate are thin and the thickness is difficult to measure with a thickness gauge, a scanning electron microscope is used to measure the cross-section of the laminate structure in the thickness direction, and the thickness can be defined as the average thickness of at least five points in the target layer (e.g., primer layer) of the laminate configuration.

[0052] Typically, the surface of the metal layer may be contaminated with oil or other substances. Therefore, the surface of the metal layer can be treated, such as by degreasing or cleaning. Examples of such surface treatment methods include wiping the surface of the metal layer with organic solvents such as alcohols, alkaline aqueous solutions such as sodium hydroxide, or other cleaning solutions (sometimes simply referred to as "cleaners"), immersing the metal layer in a cleaning agent, and spraying the cleaning agent under high pressure. Surface treatments such as corona treatment or plasma treatment can also be applied to the surface of the metal layer. When a primer layer is applied to a metal layer that has undergone such surface treatment, the adhesion between the polyurethane layer and the metal layer can be further improved.

[0053] The primer layer used in the method of manufacturing the decorative laminate disclosed herein contains at least one selected from the group consisting of a silicone compound and a (meth)acrylic resin. The blending amounts of the silicone compound and the (meth)acrylic resin can be suitably determined to obtain the desired adhesive strength. For example, each of these components may be included in the range of about 50% by mass or more, about 60% by mass or more, about 70% by mass or more, or about 80% by mass or more, and about 100% by mass or less, or less than about 100% by mass, relative to the total amount of the primer layer. In this disclosure, a primer containing a silicone compound may be referred to as a silane primer, and a primer containing a (meth)acrylic resin may be referred to as an acrylic primer.

[0054] The primer layer can be applied directly to the metal layer. From the perspective of adhesion between the polyurethane layer and the metal layer, it is preferable to apply the primer layer directly to the metal layer. When an optional layer, such as a decorative layer, is inserted between the metal layer and the primer layer, it is preferable to apply the optional layer partially to the metal layer, forming a portion in which the metal layer and the primer layer are in direct contact with each other. The primer layer can be applied by well-known coating methods, etc. When applying the primer layer to the metal layer, additional steps such as drying steps (e.g., drying at room temperature) and heating steps (e.g., oven, infrared heating) may be appropriately employed as needed.

[0055] The primer layer can improve the adhesion of the uncured polyurethane layer (polyurethane precursor layer) applied on the primer layer after the curing reaction.

[0056] Among the materials constituting the primer layer, silicone compounds are preferred. Because the adhesive layers used in known decorative laminates, such as heat-sensitive adhesive layers and primer layers containing (meth)acrylic resins, have poor weather resistance, in some cases it is necessary to color the polyurethane layer applied over these layers black to block light. Due to the excellent weather resistance of silicone compounds, when using a primer layer containing silicone compounds, the polyurethane layer is not limited in terms of coloring, and a transparent polyurethane layer can be used. Therefore, the decorative properties of the metal layer itself, such as its metallic luster, can be visually recognized.

[0057] Compounds having an alkoxysilyl group can be used as organosilicon compounds, wherein the alkoxysilyl group has a silicon atom and one to three alkoxy groups covalently bonded to the silicon atom. From the perspective of the adhesion between the polyurethane layer and the metal layer, compounds comprising a structure in which two or more alkoxy groups are covalently bonded to the silicon atom are preferred, and compounds comprising a structure in which three alkoxy groups are covalently bonded to the silicon atom are more preferred. Examples of alkoxy groups include methoxy, ethoxy, isopropoxy, n-butoxy, and tert-butoxy. Among these, methoxy and ethoxy are preferred from the perspective of the adhesion between the polyurethane layer and the metal layer. Organosilicon compounds may have epoxy, methacryl, acryloyl, amino, or styryl groups. Among these, from the perspective of the adhesion between the polyurethane layer and the metal layer, it is preferred that the organosilicon compound has an amino group. Organosilicon compounds can be used alone or in combination of two or more types thereof. Generally, reagents known as silane coupling agents can be used as organosilicon compounds.

[0058] Specific examples of organosilicon compounds include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-anilinepropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-isocyanate-propyltriethoxysilane.

[0059] (Meth)acrylic resins are not particularly restricted; for example, commercially available (meth)acrylic resins used as primers can be used. As primers containing (meth)acrylic resins, examples include KBS17A / B from Konishi Co., Ltd. (Osaka-shi, Osaka, Japan) and Hamatite (trade name) A-1100F from Sika Japan Ltd. (Minato-ku, Tokyo, Japan), both of which are commercially available as acrylic primers.

[0060] The thickness of the primer layer can be about 10 micrometers or less, less than about 10 micrometers, about 8 micrometers or less, or about 6 micrometers or less. From the perspective of adhesion between the metal layer and the polyurethane layer, resistance to opening, and the overall hardness of the decorative laminate, 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 primer layer thickness is not particularly limited, and it can be, for example, about 0.05 micrometers or more, about 0.5 micrometers or more, or about 1 micrometer or more.

[0061] In some embodiments, depending on the intended use, the primer layer may contain, as optional components, such as fillers, reinforcing materials, antioxidants, flame retardants, UV absorbers, light stabilizers, heat stabilizers, flame retardants, dispersants, plasticizers, flow improvers, tackifiers, leveling agents, catalysts, pigments, dyes, thickeners, and adhesive resins other than silicone compounds and (meth)acrylic resins. These optional components may be used alone or in combination of two or more of them.

[0062] The method for manufacturing a decorative laminate disclosed herein includes: directly applying a two-component curable polyurethane precursor layer (which may be simply referred to as the "precursor layer") containing a polyol and an isocyanate onto the aforementioned primer layer, and reacting the two-component curable polyurethane precursor layer to form a polyurethane layer. Here, "directly applying the two-component curable polyurethane precursor layer to the primer layer" can include not only applying the two-component curable polyurethane precursor layer directly to the entire surface of the primer layer, but also applying the two-component curable polyurethane precursor layer directly to a portion of the primer layer. The two-component curable polyurethane precursor layer can be applied by known coating methods, lamination methods, etc. When applying the two-component curable polyurethane precursor layer to the primer layer, or when reacting the two-component curable polyurethane precursor layer to form a polyurethane layer, additional steps such as a drying step (e.g., drying at room temperature) and a heating step (e.g., oven, infrared heating) may be appropriately employed as needed.

[0063] The two-component curable polyurethane precursor layer can have a single-layer structure or a laminated structure (e.g., a colored layer and a transparent surface layer). In the case of a laminated structure, at least the layer directly applied to the primer layer is a two-component curable polyurethane precursor layer. From the perspective of adhesion between the polyurethane layer and the metal layer, layers other than those directly applied to the primer layer are also preferably two-component curable polyurethane precursor layers, and curing is preferably performed after all precursor layers are laminated onto the primer layer.

[0064] In this disclosure, "two-component curable polyurethane precursor layer" refers to a polyurethane layer in an uncured state that is not fully cured. Whether the polyurethane layer is in an uncured or fully cured state can be evaluated, for example, using a Fourier transform infrared spectrometer (FT-IR Nicolet iS5, available from Yamato Scientific Co., Ltd. (Chuo-ku, Tokyo, Japan)). Specifically, when measuring the polyurethane layer with such a device, when it is observable that a curing point of 2270 cm⁻¹ is present... -1 When a reverse symmetric tensile peak is observed near the N=C=O point, curing is considered incomplete; conversely, when the wavelength region is almost flat and no peak is observed, curing is considered complete. Alternatively, in the method for manufacturing decorative laminates disclosed herein, the evaluation results of the following water resistance and heat resistance tests performed on the obtained decorative laminate can be used to indirectly evaluate whether the polyurethane precursor layer is in an uncured state when directly applied to the primer layer. That is, when the evaluation results of the water resistance and heat resistance tests are at a qualified level, it can be considered that the polyurethane precursor layer in an uncured state has been directly applied to the primer layer; and when the evaluation results are at a unqualified level, it can be considered that the polyurethane layer in a fully cured state has been directly applied to the primer layer.

[0065] The two-component curable polyurethane precursor layer can be, for example, an uncured polyurethane sheet or an uncured polyurethane coating. The uncured and cured states of the two-component curable polyurethane can be controlled by adjusting, for example, temperature conditions, curing reaction time, and the amount of catalyst blended. In some embodiments, the following method can be exemplified as a method for preparing an uncured polyurethane layer (a polyurethane layer with residual isocyanate groups after drying). After applying the two-component curable polyurethane resin composition to a substrate, etc., the polyurethane layer is dried to substantially eliminate solvent content without foaming. In this case, it is preferable that the transparent surface polyurethane layer has such softness that the polyurethane layer can be laminated with a PET film in a state with residual isocyanate groups without containing air, the polyurethane layer is not in a state of flow due to pressure during lamination, and when the polyurethane layer is touched with a fingertip and immediately removed, the polyurethane layer has fingerprints but does not adhere to the fingers. For colored polyurethane layers, it is preferable that the surface of the polyurethane layer is not sticky in the presence of residual isocyanate groups. Here, from the perspective of evaporating the solvent component without foaming, the drying temperature can be, for example, about 60°C or higher, about 70°C or higher, or about 80°C or higher, and about 150°C or lower, about 130°C or lower, or about 110°C or lower. The curing reaction time can vary depending on the temperature to be applied or the amount of catalyst blended, as described later, and the time can be, for example, about 1 minute or longer, about 2 minutes or longer, or about 3 minutes or longer, and about 1 hour or less, about 30 minutes or less, or about 10 minutes or less. For rapidly reacting acrylic polyols, there is no need to blend the catalyst to be added. In cases where polycaprolactone polyols, etc., have a slower reaction time than acrylic polyols, blending the catalyst is preferred. The catalyst can be blended in amounts of about 0.01% by mass or more, about 0.02% by mass or more, or about 0.04% by mass or more, and about 0.4% by mass or less, about 0.2% by mass or less, or about 0.1% by mass or less, relative to the solids content of the polyurethane layer (particularly the transparent polyurethane layer). The uncured polyurethane precursor layer can remain uncured for about one week, for example, at room temperature (about 20°C ± about 15°C) or lower, and for about several weeks at about 0°C. Therefore, even uncured polyurethane sheets stored for several days are suitable for use as the two-component curable polyurethane precursor layer of this disclosure.

[0066] The polyurethane precursor layer applied directly to the primer layer can be cured to form a polyurethane layer, for example, by further controlling the aforementioned temperature conditions and curing reaction time, or by controlling the storage temperature and storage time. Here, the storage temperature and storage time can be, for example, about 10 days or longer, about 2 weeks or longer, about 3 weeks or longer, or about 30 days or longer at room temperature.

[0067] The polyurethane layer disclosed herein is prepared using a two-component curable polyurethane resin composition containing a polyol and an isocyanate. Here, "isocyanate" in this disclosure includes not only isocyanates as monomers but also isocyanates referred to as polyisocyanates.

[0068] Examples of polyols include polyether polyols; polymeric polyols having carbon-carbon bonds in their main chain backbone, such as (meth)acrylic acid polyols, polybutadiene glycol, and hydrogenated polybutadiene polyols; and polyester polyols, such as polycaprolactone polyols and polycarbonate polyols. Polyester polyols are preferred because their elongation at break, particularly at high temperatures, can be improved; polycarbonate polyols and polycaprolactone polyols are more preferred; and polycaprolactone polyols are particularly preferred. Examples of polycarbonate polyols may include polycarbonate diol, and examples of polycaprolactone polyols may include polycaprolactone diol and polycaprolactone triol. From the perspective of adhesion between the polyurethane layer and the metal layer, it is preferred that, relative to the total amount of polyols, polycarbonate polyols, polycaprolactone polyols, or both thereof are included in 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. Polyols can be used alone, or in combination of two or more types. (Meth)acrylic polyols are preferred for dispersing pigments for coloring.

[0069] In some embodiments, the polyol comprises a polyester polyol having an average molecular weight of about 1,000 or less in an amount of about 0.4 equivalents or more relative to all polyols. When a polyester polyol with an average molecular weight of about 1,000 or less is included in an amount of about 0.4 equivalents or more, the elongation at break at high temperatures can be improved. Furthermore, polycarbonate polyols and polycaprolactone polyols are preferred from the perspective of elongation at break at high temperatures. Here, the weight-average molecular weight of the polyol refers to the number-average molecular weight based on polystyrene, measured by gel permeation chromatography (GPC).

[0070] Specific examples of polyester polyols include polycaprolactone diols such as TONE (trade name) 0201 (purchased from Dow Chemical Co., Midland, Mich., USA; average molecular weight 530), PLACEL (trade name) 205 (purchased from Daicel Corporation; average molecular weight 530), PLACEL (trade name) 205H (purchased from Daicel Corporation; average molecular weight 530), PLACEL (trade name) 208 (purchased from Daicel Corporation; average molecular weight 850), and PLACEL (trade name) 210 (purchased from Daicel Corporation; average molecular weight 1000); and polycaprolactone triols such as TONE (trade name) 0301 (purchased from Dow Chemical Co., Ltd.). Co., Ltd.; average molecular weight 300), TONE (trade name) 1303 (purchased from Dow Chemical Co., Ltd.; average molecular weight 425), TONE (trade name) 0305 (purchased from Dow Chemical Co., Ltd.; average molecular weight 540), PLACEL (trade name) 305 (purchased from Daicel Corporation; average molecular weight 550), and PLACEL (trade name) 308 (purchased from Daicel Corporation; average molecular weight 850); and polycarbonate diols such as NIPPOLLAN (trade name) 981 and NIPPOLLAN (trade name) 983 (purchased from Tosoh Corporation; average molecular weight 1000), T4671, T4691 and T5651 (purchased from Asahi Kasei Corporation, Minato-ku, Tokyo, Japan). Corporation (Minato-ku, Tokyo, Japan); Average molecular weight 1000).

[0071] When polycaprolactone diol and polycarbonate diol are combined in polyester polyols, these diols can be used in various quantitative ratios. For example, the equivalent ratio of polycaprolactone diol to polycarbonate diol can 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 ratios, the average molecular weight in this state can be about 1,000 or less, preferably about 850 or less, more preferably about 750 or less, and most preferably about 500 to about 600.

[0072] When polycaprolactone diol is used alone, its average molecular weight can be set to about 700 or less, and preferably in the range of about 500 to about 600.

[0073] Examples of isocyanates include at least one selected from the group consisting of isocyanates having a cyclohexane structure, isocyanates without carbon-carbon double bonds, and isocyanates having a branched structure. Examples of isocyanates having a branched structure include isocyanate trimers, biurets, and adducts.

[0074] In some embodiments, an isocyanate containing, for example, a trimer, biuret, isophorone diisocyanate (IPDI), or an adduct of 1,3-di(isocyanate methyl)cyclohexane (H6XDI), or a mixture of two or three of these, may be used, in an amount of at least about 0.5 equivalents relative to all isocyanates. Because such isocyanates improve elongation at break, particularly at high temperatures, they are more preferably trimers or adducts of isophorone diisocyanate or 1,3-di(isocyanate methyl)cyclohexane. Because trimers, adducts, or mixtures thereof of isophorone diisocyanate or 1,3-di(isocyanate methyl)cyclohexane improve elongation at break, particularly at high temperatures, they are preferably included in a ratio of about 50% or more, about 60% or more, about 70% or more, about 80% or more, or about 90% or more, relative to all isocyanates.

[0075] The trimer of isophorone diisocyanate may be purchased, for example, under the trade name "Desmodur Z4370" from Sumika Covestro Urethane Co., Ltd. (Amagasaki-shi, Hyogo, Japan), or under the trade name "VESTNAT T1890" from Evonik Japan Co., Ltd. (Shinjuku-ku, Tokyo, Japan). The adducts of isophorone diisocyanate are adducts of isophorone diisocyanate with trimethylolpropane, trimethylolethane, pentaerythritol, etc., and the adduct with trimethylolpropane is purchased, for example, under the trade name "TAKENATE D-140N" from Takeda Pharmaceutical Co., Ltd. (Chuo-ku, Tokyo, Japan). Trimers of 1,3-di(isocyanate methyl)cyclohexane, for example, are available under the trade name "D-127N" from Mitsui Chemicals, Inc. (Chuo-ku, Tokyo, Japan). Adducts of 1,3-di(isocyanate methyl)cyclohexane, for example, are available under the trade name "D-120N" from Mitsui Chemicals, Inc. (Chuo-ku, Tokyo, Japan).

[0076] The equivalence ratio of isocyanate to polyol in a polyurethane resin composition can be appropriately adjusted to obtain the desired properties (e.g., protective properties) of the polyurethane layer. For example, the equivalence ratio (isocyanate / polyol) can be in the range of about 0.7 or greater, about 0.8 or greater, about 0.9 or greater, or about 1.0 or greater, and about 2.0 or less, about 1.8 or less, about 1.6 or less, or about 1.5 or less. When the equivalence ratio of isocyanate to polyol is within this range, the adhesion between the polyurethane layer and the metal layer is excellent, and the elongation at break, especially at high temperatures, weather resistance, chemical resistance, and scratch resistance can also be improved.

[0077] Polyurethane resins can be prepared using known methods, relative to polyurethane resin compositions containing isocyanates and polyols. For example, polymerization can be carried out with a catalyst added to the polyurethane resin composition. Commonly used catalysts can be used as such catalysts, for example, dibutyltin dilaurate (DBTDL), zinc naphthenate, zinc octenate, triethylenediamine, etc. The amount of catalyst can be set from about 0.005% by mass to about 0.5% by mass relative to 100% by mass of the resin composition.

[0078] The polyurethane layer obtained by reacting a two-component curable polyurethane precursor layer can have a single-layer structure or a laminated structure. In the case of a laminated structure, for example, the polyurethane layer can be a laminate of a film formed from a polyurethane resin composition, or it can be a multilayer coating of the resin composition. The polyurethane layer can be colored or colorless. The polyurethane layer can be opaque, translucent, or transparent. The polyurethane layer can have an uneven shape, such as an embossed pattern on the entire surface or a portion of the surface.

[0079] The polyurethane layer can be formed, for example, by applying a polyurethane resin composition to a primer layer using known coating methods such as blade coating or bar coating. Alternatively, the polyurethane layer can be formed by coating a release liner with the resin composition to form a polyurethane precursor film, then pressing the film onto the primer layer and curing the film. Alternatively, the polyurethane layer can also be formed by pressing an uncured polyurethane precursor film, pre-formed into a film shape using extrusion, stretching, or the like, onto the primer layer, and then curing the film.

[0080] The thickness of the polyurethane layer can be appropriately adjusted according to the desired performance (e.g., protective performance). Such thicknesses can be, for example, about 1 micrometer or greater, about 3 micrometers or greater, or about 5 micrometers or greater, about 7 micrometers or greater, or about 10 micrometers or greater, about 50 micrometers or less, about 40 micrometers or less, about 30 micrometers or less, or about 20 micrometers or less.

[0081] The polyurethane layer of this disclosure may contain fillers, matting agents, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, flame retardants, hard coating materials, gloss improvers, dispersants, plasticizers, flow improvers, surfactants, leveling agents, silane coupling agents, catalysts, pigments, dyes, etc., as optional components, provided that the effects of this disclosure are not adversely affected. These optional components may be used alone or in combination of two or more types.

[0082] According to the method for manufacturing decorative laminates disclosed herein, a two-component curable polyurethane precursor layer is directly applied to a primer layer, and then the precursor layer is reacted to form a polyurethane layer. Therefore, the decorative laminate exhibits excellent adhesion and tamper resistance. Consequently, in the decorative laminates of this disclosure, when subjected to the following water resistance test, the polyurethane layer achieves a residual square count of 90 / 100 or greater, 95 / 100 or greater, or 97 / 100 or greater and 100 / 100 or less, or 99 / 100 or less, and when subjected to the following heat resistance test, the polyurethane layer exhibits an opening width and / or peel 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 greater, or greater than about 0 mm. Here, the construction of each layer of the decorative laminate of this disclosure (e.g., the material, thickness, etc. of each layer) can be adopted in the same manner as the construction described above in the method of manufacturing the decorative laminate of this disclosure.

[0083] Waterproofing test

[0084] The decorative laminate was immersed in water at 40°C for 240 hours. After removing the laminate, the moisture was wiped off, and the laminate was allowed to stand for 1 hour. Then, a total of 100 1mm square 10×10 grids were formed on the polyurethane layer of the laminate using a cutter. Sellotape (trade name) CT-24 (NICHIBAN Co., Ltd. (Bunkyo-ku, Tokyo, Japan)) was applied to these 100 grids. Immediately afterward, the Sellotape (trade name) was peeled off, and the number of remaining grids in the polyurethane layer that had not been peeled off was checked.

[0085] Heat resistance test

[0086] Using a DuPont drop hammer impact testing machine No. 517 (purchased from Yasuda Seiki Seisakusho, LTD., Nishinomiya-shi, Hyogo, Japan), a decorative laminate was placed on a grooved mold, with the groove covered and the metal layer of the laminate as the top surface, as shown in Figure 4. A 1 kg weight was dropped from a height of 50 cm into the top surface of the metal layer with a hemispherical punch having a half-inch diameter tip in contact with it, deforming the laminate into a convex shape (Figure 5(a)). Next, as shown in Figure 5(b), a cross-shaped cut was made in the polyurethane layer of the deformed laminate using a cutting blade. The laminate with the cut was subjected to the following thermal cycling, and the opening width and peel width of the polyurethane layer in the cut section were checked. Here, "height" in "50cm height" refers to the distance from the bottom of the weight to the top surface of the punch, as shown on the left side of Figure 4(a) or Figure 4(b). The following thermal cycles are typically performed sequentially:

[0087] (Heat cycle)

[0088] (1) Raise the temperature from 23°C to 80°C within 1 hour.

[0089] (2) Maintain the temperature at 80℃ for 18 hours.

[0090] (3) Let the temperature drop to -30℃ in 1 hour.

[0091] (4) Maintain the temperature at -30°C for 4 hours.

[0092] (5) Raise the temperature to 80℃ in 1 hour.

[0093] (6) Maintain the temperature at 80℃ for 18 hours.

[0094] Repeat steps (3) to (6) above 9 times.

[0095] (7) Let the temperature drop to -30℃ in 1 hour.

[0096] (8) Maintain the temperature at -30°C for 4 hours.

[0097] (9) Raise the temperature from -30℃ to 23℃ within 1 hour.

[0098] Unlike known products, the decorative laminate of this disclosure does not have an adhesive layer such as a thermosensitive polyurethane adhesive layer, which is a flexible layer applied between the polyurethane layer and the metal layer, and thus can improve the overall rigidity of the decorative laminate. In some embodiments, the decorative laminate of this disclosure is capable of achieving a pencil hardness of B or greater, HB or greater, or F or greater in the pencil hardness test described below. The upper limit of the pencil hardness is not particularly limited, and it can be, for example, 3H or less, 2H or less, or H or less.

[0099] The decorative laminate of this disclosure, due to its inclusion of a polyurethane layer, exhibits excellent corrosion resistance and impact resistance. Therefore, the decorative laminate of this disclosure meets the acceptable levels in the weather resistance and chemical resistance tests described below. Specifically, the decorative laminate manufactured using a two-component curable polyurethane resin composition containing at least one polyol selected from the group consisting of polycaprolactone polyols and polycarbonate polyols, and at least one isocyanate selected from the group consisting of isocyanates having a cyclohexane structure, isocyanates without carbon-carbon double bonds, and isocyanates with a branched structure, can further improve impact resistance. In some embodiments, the decorative laminate of this disclosure can exhibit impact resistance, i.e., when using a DuPont drop hammer impact tester No. 517 (purchased from Yasuda Seiki Seissakusho, LTD. (Nishinomiya-shi, Hyogo, Japan)), the laminate is placed on a mold with a groove, such that the groove of the mold is covered, and the metal layer of the laminate is the top surface; a 1 kg weight is dropped from a height of 50 cm into the punch with a hemispherical punch having a half-inch diameter tip in contact with the top surface of the metal layer.

[0100] In some embodiments, the decorative laminates of this disclosure optionally include additional layers besides those described above, to the extent that they do not adversely affect the effects of the invention. Examples of such additional layers include at least one selected from the group consisting of colored layers, decorative layers (e.g., patterned or embossed layers), gloss layers, adhesive layers, and release liner. The additional layers may be applied to the entire surface or a portion of the surface of the laminate. For example, when a colored layer, decorative layer, and gloss layer are applied between a polyurethane layer and a primer layer, these layers may be applied to a portion of the polyurethane layer and / or primer layer, provided that the adhesion between the polyurethane layer and the primer layer is not inhibited. Here, when the colored and decorative layers are formed using a two-component curable polyurethane resin composition in the same manner as the polyurethane layer described above, these layers can be considered as part of a polyurethane layer having the laminated structure described above, and in this case, these layers can be formed by applying the composition to the entire surface of the polyurethane layer and / or primer layer and following the method for manufacturing a decorative laminate as described above in this disclosure. The adhesive layer, as an additional layer, is intended to serve as a layer for bonding the decorative laminate of this disclosure to support members, etc., and the adhesive layer may be applied to the entire surface or a portion of the surface of the metal layer opposite to the surface on which the polyurethane layer is applied. The additional layer may have a three-dimensional shape, such as an embossed pattern on its surface.

[0101] The decorative laminate disclosed herein can be, for example, a sheet-like article, a roll-shaped body, or an article with a three-dimensional shape. Examples of articles with a three-dimensional shape include laminates processed into curved shapes, laminates pressed into predetermined shapes, etc. The decorative laminate of this disclosure exhibits excellent adhesion and other properties between the metal layer and the polyurethane layer, and is not prone to peeling or cracking even during three-dimensional molding. Therefore, the decorative laminate is suitable for three-dimensional molding.

[0102] Articles incorporating the decorative laminates of this disclosure may be referred to as decorative articles of this disclosure, having a three-dimensional shape formed by processing the decorative laminates of this disclosure. Such decorative articles can be produced by forming the decorative laminates of this disclosure using known forming methods, such as pressing or roll forming. Examples of pressing include compression forming, bending, deep drawing, etc. These methods may be used alone, or in combination of two or more types.

[0103] As a compression molding process, for example, the following method can be used: the metal layer side of the decorative laminate of this disclosure is placed in the female mold of a compression mold, and then a male mold is pressed from the polyurethane layer side of the decorative laminate to plastically deform the metal layer. Alternatively, the following method can be used: the polyurethane layer side of the decorative laminate of this disclosure is placed in the female mold of a compression mold, and then a male mold is pressed from the metal layer side of the decorative laminate to plastically deform the metal layer.

[0104] Roll forming can be performed using a roll forming machine, also known as a tube mill. For example, multiple rolls on the machine can be used to sequentially process the decorative laminate of this disclosure into curved shapes, such as tubular shapes.

[0105] Bending can be performed, for example, by fixing a portion of the decorative laminate disclosed herein, and then bending the unfixed portion at an arbitrary angle, starting from the boundary between the fixed and unfixed portions, by applying a mold to the unfixed portion or by manually tapping the unfixed portion.

[0106] Alternatively, resin or rubber materials can be injected into the processed decorative laminate with a three-dimensional shape using methods such as extrusion to make it integral.

[0107] 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, the decorative article including the support member and the decorative laminate adhered to the support member.

[0108] The materials used for supporting components are not particularly limited, and examples 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, ceramics, concrete, gypsum, calcium silicate, natural stone, and bitumen), rubber raw materials, fabrics (e.g., woven fabrics, knitted fabrics, and nonwoven fabrics), metal or metal alloy materials (e.g., iron, aluminum, and stainless steel), and wood raw materials including paper.

[0109] There are no particular restrictions on the shape or structure of the supporting components. The shape can be, for example, membrane-like, plate-like, or three-dimensional, and the structure can be a single-layer structure, a laminated structure, or a composite structure that combines multiple components with different shapes or materials.

[0110] Decorative articles incorporating the decorative laminates of this disclosure can be used in a variety of applications. Examples of such applications include signs; road signs; various interior or exterior articles, such as interior or exterior articles of vehicles such as automobiles, railways, airplanes, and ships (e.g., front components such as roof components, pillar components, door trim components, dashboard components and hoods, bumper components, fender components, side beam components, interior panel components, etc.), and interior or exterior articles of buildings (e.g., window glass, doors, window frames, roof components such as tiles, exterior wall components, wallpaper, etc.); electrical appliances, such as personal computers, smartphones, mobile phones, refrigerators, and air conditioners; stationery; furniture; tables; and various containers, such as cans. Among these, decorative articles incorporating the decorative laminates of this disclosure are suitable for use as interior or exterior articles of vehicles or buildings due to the excellent decorative properties of the decorative laminates of this disclosure, such as excellent metallic luster.

[0111] The method for applying the decorative laminate of this disclosure to the support member (adhesive) constituting the decorative article is not particularly limited, and known methods may be used appropriately. Examples of methods include manual application and injection molding methods (such as insert injection molding method, in-mold molding method, two-color injection molding method, core-back injection molding method and sandwich injection molding method).

[0112] Example

[0113] The following embodiments illustrate specific implementations of this disclosure, but the invention is not limited to these embodiments. Unless otherwise specified, all “parts” and “percentages” are by mass. Numerical values ​​substantially include errors arising from the measurement principle and measuring device. Numerical values ​​are generally indicated by rounded significant figures.

[0114] The products used in this embodiment are shown in Table 1 below.

[0115]

[0116] Experimental Example 1

[0117] In Experimental Example 1, the impact resistance, molding properties, and weather resistance of the test samples were evaluated.

[0118] Preparation of a two-component curable polyurethane resin composition BM for colored layers (blue metallic color)

[0119] A blue metallic paint was prepared by uniformly mixing 3 parts by weight of pearlescent agent, 0.5 parts by weight of black pigment, 0.2 parts by weight of purple pigment, 30 parts by weight of Desmophen (trade name) A565 (acrylic polyol), 30.1 parts by weight of toluene, 13.9 parts by weight of ethyl acetate, 6.9 parts by weight of butyl acetate, 6 parts by weight of xylene, 5.3 parts by weight of ethylbenzene, and 4.1 parts by weight of isobutyl acetate. 100 parts by weight of the resulting blue metallic paint was then uniformly mixed with 7 parts by weight of VESTNAT (trade name) T1890E to prepare a two-component curable polyurethane resin composition BM for use in colored layers.

[0120] Preparation of a two-component curable polyurethane resin composition GM for colored layers (gold metallic color)

[0121] A gold metallic paint was prepared by uniformly mixing 5 parts by weight of aluminum brightener, 0.5 parts by weight of yellow pigment, 0.1 parts by weight of black pigment, 0.1 parts by weight of white pigment, 30 parts by weight of Desmophen (trade name) A565 (acrylic polyol), 29.2 parts by weight of toluene, 13.4 parts by weight of ethyl acetate, 6.9 parts by weight of butyl acetate, 5.9 parts by weight of xylene, 4.9 parts by weight of ethylbenzene, and 4 parts by weight of isobutyl acetate. 100 parts by weight of the resulting gold metallic paint was then uniformly mixed with 7 parts by weight of VESTNAT (trade name) T1890E to prepare a two-component curable polyurethane resin composition GM for use in colored layers.

[0122] Preparation of a two-component curable polyurethane resin composition C for a surface layer (colorless)

[0123] A two-component curable polyurethane resin composition C for a surface layer was prepared by uniformly mixing 100 parts by weight of PLACEL (trade name) 205H, 2.0 parts by weight of TINUVIN (trade name) 292, 2.0 parts by weight of TINUVIN (trade name) 99-2, 25.0 parts by weight of butyl acetate, 0.15 parts by weight of catalyst, and 150 parts by weight of VESTNAT (trade name) T1890E. The solid content of composition C was 74.9%.

[0124] Preparation of a two-component curable polyurethane resin composition BB for a surface layer (blue-black).

[0125] A blue-black paint paste was prepared by uniformly mixing 35 parts by weight of copper-iron-manganese pigment, 17.5 parts by weight of Desmophen (trade name) A565 (acrylic polyol), 21.4 parts by weight of xylene, 15.2 parts by weight of ethylbenzene, 6.8 parts by weight of butyl acetate, and 4.1 parts by weight of isobutyl acetate. Next, a two-component curable polyurethane resin composition (BB) for the surface layer was prepared by uniformly mixing 100 parts by weight of PLACCEL (trade name) 205H, 2.0 parts by weight of TINUVIN (trade name) 292, 2.0 parts by weight of TINUVIN (trade name) 99-2, 25.0 parts by weight of butyl acetate, 0.15 parts by weight of catalyst, 150 parts by weight of VESTNAT (trade name) T1890E, and 8.0 parts by weight of the blue-black paint paste. The solids content of composition BB was 74.3%.

[0126] Preparation of a two-component curable polyurethane resin composition RB for the surface layer (red and black)

[0127] A reddish-black paint paste was prepared by uniformly mixing 11.6 parts by weight of carbon black pigment, 11.6 parts by weight of Desmophen (trade name) A565 (acrylic polyol), 30.9 parts by weight of xylene, 26.2 parts by weight of ethylbenzene, 13.8 parts by weight of butyl acetate, and 5.9 parts by weight of isobutyl acetate. Next, a two-component curable polyurethane resin composition RB for use as a surface layer was prepared by uniformly mixing 100 parts by weight of PLACCEL (trade name) 205H, 2.0 parts by weight of TINUVIN (trade name) 292, 2.0 parts by weight of TINUVIN (trade name) 99-2, 25.0 parts by weight of butyl acetate, 0.15 parts by weight of catalyst, 150 parts by weight of VESTNAT (trade name) T1890E, and 0.8 parts by weight of the reddish-black paint paste. The solids content of composition RB was 74.8%.

[0128] Example 1

[0129] After applying the two-component curable polyurethane resin composition C to PK-002 using a bar coater, the uncured composition was dried in a hot air oven at 80°C for 4 minutes, thereby preparing a colorless polyurethane precursor coating film with a thickness of approximately 0.05 mm. LUMIRROR (trade name) T60 was then laminated onto this coating film to prepare a film with a three-layer structure, and the film was allowed to stand at room temperature for 24 hours.

[0130] Silane coupling agent Z-6011 was diluted to 3% with alcohol and applied to a stainless steel plate (SUS430#8) as a metal substrate by wiping. The substrate was then baked at 200°C for 5 minutes, forming a primer layer approximately 1 micrometer thick. While still hot from baking, PK-002 was peeled off from the three-layer film, and the uncured polyurethane precursor coating was applied to the primer layer. This was then allowed to stand at room temperature for 24 hours. The resulting material was heated at 80°C for 1 hour, and then LUMIRROR (trade name) T60 was removed, yielding a test sample of the decorative laminate.

[0131] Examples 2 to 6

[0132] Except for changing the type of metal substrate, surface layer, and PET film to which the coating film applied to the surface layer is shown in Table 2, test samples of the decorative laminates of Examples 2 to 6 were obtained in the same manner as in Example 1.

[0133] Example 7

[0134] After applying a two-component curable polyurethane resin composition BM for the colored layer onto a biaxially stretched PET film (G2) using a bar coater, the uncured composition was dried in a hot air oven at 80°C for 20 minutes, thereby obtaining a polyurethane precursor colored coating film with a thickness of approximately 20 micrometers. Next, a two-component curable polyurethane resin composition C for the surface layer was coated onto the colored coating film using a bar coater, and then dried in a hot air oven at 80°C for 4 minutes, thereby preparing a colorless polyurethane precursor coating film with a thickness of approximately 0.05 mm. LUMIRROR (trade name) T60 was laminated onto this coating film to prepare a film with a four-layer structure, and the film was left to stand at room temperature for 24 hours.

[0135] Acrylic primer KBS17A / B was diluted with MEK and applied to a stainless steel plate (SUS430BA) as a metal substrate by wiping. It was then baked at 200°C for 5 minutes, forming a primer layer approximately 1 micrometer thick. While still hot from baking, G2 was peeled off from the four-layer film, and an uncured polyurethane precursor colored coating was applied to the primer layer. This was allowed to stand at room temperature for 24 hours. The resulting material was then heated at 80°C for 1 hour, and LUMIRROR (trade name) T60 was removed, yielding a test sample of the decorative laminate.

[0136] Example 8

[0137] Acrylic primer KBS17A / B was diluted with MEK and applied to a stainless steel plate (SUS430BA) as a metal substrate by wiping. It was then baked at 200°C for 5 minutes to form a primer layer approximately 1 micrometer thick. A two-component curable polyurethane resin composition GM for the colored layer was applied to the primer layer using a bar coater and placed in a hot air oven at 80°C for 20 minutes to dry the uncured composition, thereby obtaining a polyurethane precursor colored coating film approximately 20 micrometers thick. Next, a two-component curable polyurethane resin composition C for the surface layer was coated onto the colored coating film using a bar coater and placed in a hot air oven at 80°C for 4 minutes to dry the uncured composition, thereby preparing a colorless polyurethane precursor coating film approximately 0.05 mm thick. LUMIRROR (trade name) T60 was laminated onto this coating film, and the resulting material was allowed to stand at room temperature for 24 hours. After heating the obtained material at 80°C for 1 hour, LUMIRROR (trade name) T60 was removed, thus obtaining a test sample of the decorative laminate.

[0138] Comparative Example 1 and Comparative Example 2

[0139] Coated plates 1 and 2 were used as test samples for Comparative Examples 1 and 2. Since the surface layers of coated plates 1 and 2 are not polyurethane layers, the resin components constituting these surface layers are indicated in parentheses in Table 2.

[0140] Physical property evaluation test 1

[0141] The characteristics of each test sample were evaluated using the following tests. The results are shown in Table 2.

[0142] Appearance Test: Decorative

[0143] The decorative properties are evaluated by visually observing the appearance, such as gloss, of the test samples before molding and after the following three-dimensional molding performance test (i.e., after molding).

[0144] Impact resistance test: Impact resistance

[0145] Using a DuPont drop hammer impact testing machine No. 517 (purchased from Yasuda Seiki Seisakusho, LTD., Nishinomiya-shi, Hyogo, Japan), each test sample was placed on a grooved mold, with the groove covered and the metal layer of the laminate as the top surface. A 1 kg weight was dropped from a height of 50 cm into the top surface of the metal layer, with a hemispherical punch with a half-inch diameter tip in contact with the top surface of the metal layer. The deformed polyurethane layers (surface layer, colored layer) were visually inspected for any abnormalities such as cracking or peeling.

[0146] 3D molding performance testing: Molding performance (molding shape)

[0147] The test sample is stamped into a predetermined shape using a press and a stamping die so that it has the size and shape shown in Figure 3(c) after molding. Then, when the test sample is molded into the molded shape shown in Figure 3(c) using a press and a pressing die, the polyurethane layer (surface layer, colored layer) is visually inspected for any abnormalities such as cracking or peeling.

[0148] Weather resistance test: weather resistance

[0149] Test samples of the mold shape obtained in the above three-dimensional molding performance test were placed on an exposed platform facing south at 45° on land about 1 km from the coast of Numazu-shi, Shizuoka, Japan for 2 years. Then, abnormalities were visually inspected, such as obvious changes in color and gloss, cracking and peeling of polyurethane layers (surface layer, colored layer), and corrosion of the metal substrate.

[0150]

[0151] Experimental Example 2

[0152] In Experimental Example 2, the impact resistance, opening resistance, sealing and hardness of the test sample were evaluated based on whether there was a primer layer in the test sample and whether there was an adhesive layer between the primer layer and the polyurethane layer.

[0153] Preparation of polyester adhesive compositions for adhesive layers

[0154] A polyester adhesive composition for use in the adhesive layer was prepared by uniformly mixing 30 parts by weight of ELITEL (trade name) UE3230, 70 parts by weight of MEK and 2 parts by weight of Coronate (trade name) HL.

[0155] Preparation of polyurethane adhesive compositions for adhesive layers

[0156] A polyurethane adhesive composition for use in the adhesive layer was prepared by uniformly mixing 20 parts by weight of Desmocoll (trade name) 530, 80 parts by weight of MEK and 0.2 parts by weight of Desmodur (trade name) RFE.

[0157] Preparation of a two-component curable polyurethane resin composition B (black (masking)) for surface layer

[0158] A black paint paste was prepared by uniformly mixing 7.7 parts by weight of carbon black pigment, 1.9 parts by weight of titanium dioxide pigment, 28.3 parts by weight of Desmophen (trade name) A565 (acrylic polyol), 25.9 parts by weight of xylene, 21.2 parts by weight of ethylbenzene, 9.8 parts by weight of butyl acetate, and 5.2 parts by weight of isobutyl acetate. Next, a two-component curable polyurethane resin composition B for the surface layer was prepared by uniformly mixing 100 parts by weight of PLACCEL (trade name) 205H, 2.0 parts by weight of TINUVIN (trade name) 292, 2.0 parts by weight of TINUVIN (trade name) 99-2, 25.0 parts by weight of butyl acetate, 0.15 parts by weight of catalyst, 150 parts by weight of VESTNAT (trade name) T1890E, and 40.0 parts by weight of the black paint paste. The solids content of composition B was 74.1%.

[0159] Example 9

[0160] Test samples of the decorative laminate of Example 9 were obtained in the same manner as in Example 1.

[0161] Examples 10 and 11

[0162] Except for changing the metal substrate to the metal substrate shown in Table 3, test samples of the decorative laminates of Examples 10 and 11 were obtained in the same manner as in Example 1.

[0163] Comparative Example 3

[0164] After applying a two-component curable polyurethane resin composition C to PK-002 using a bar coater, the uncured composition was dried in a hot air oven at 80°C for 4 minutes, thereby preparing a colorless polyurethane precursor coating film with a thickness of approximately 0.05 mm. LUMIRROR (trade name) T60 was then laminated onto this coating film to prepare a three-layer film, and the film was allowed to stand at room temperature for 24 hours. Next, a polyester adhesive composition for the 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, thereby preparing a two-layer film including an adhesive layer with a thickness of approximately 20 micrometers. After peeling PK-002 from the three-layer film including the polyurethane precursor coating film, a two-layer film was applied so that the adhesive layer was in contact with the polyurethane precursor coating film, thereby preparing a four-layer film including PK-002 / adhesive layer / polyurethane precursor coating film / T60 (PET film).

[0165] Silane coupling agent Z-6011 was diluted to 3% with alcohol and applied to a stainless steel plate (SUS430#8) as a metal substrate by wiping. The substrate was then baked at 200°C for 5 minutes, forming a primer layer approximately 1 micrometer thick. While still hot from baking, PK-002 was peeled off from the four-layer film, and an adhesive layer was applied to the primer layer. The substrate was then allowed to stand at room temperature for 24 hours. The resulting material was heated at 80°C for 1 hour, and LUMIRROR (trade name) T60 was removed, yielding a test sample of the decorative laminate.

[0166] Comparative Example 4 and Comparative Example 5

[0167] Except for changing the metal substrate to the metal substrate shown in Table 3, the test samples of the decorative laminates of Comparative Examples 4 and 5 were obtained in the same manner as Comparative Example 3.

[0168] Example 12

[0169] Silane coupling agent Z-6011 was diluted to 3% with alcohol and applied to a stainless steel plate (SUS430BA) as a metal substrate by wiping. The substrate was then baked at 200°C for 5 minutes to form a primer layer approximately 1 micrometer thick. A two-component curable polyurethane resin composition C was applied to the primer layer using a bar coater and placed in a hot air oven at 80°C for 4 minutes to dry the uncured composition, thus preparing a colorless polyurethane precursor coating film approximately 0.05 mm thick. LUMIRROR (trade name) T60 was laminated onto this coating film, and the resulting material was allowed to stand at room temperature for 24 hours. After heating the resulting material at 80°C for 1 hour, LUMIRROR (trade name) T60 was removed, yielding a test sample of the decorative laminate.

[0170] Example 13

[0171] Test samples of the decorative laminate of Example 13 were obtained in the same manner as in Example 7.

[0172] Comparative Example 6

[0173] After applying a two-component curable polyurethane resin composition BM for the colored layer onto a biaxially stretched PET film (G2) using a bar coater, the uncured composition was dried in a hot air oven at 80°C for 20 minutes, thereby obtaining a polyurethane precursor colored coating film with a thickness of approximately 20 micrometers. Next, a two-component curable polyurethane resin composition C for the surface layer was coated onto the colored coating film using a bar coater, and then dried in a hot air oven at 80°C for 4 minutes, thereby preparing a colorless polyurethane precursor coating film with a thickness of approximately 0.05 mm. LUMIRROR (trade name) T60 was laminated onto this coating film to prepare a film with a four-layer structure, and the film was left to stand at room temperature for 24 hours.

[0174] Next, a polyurethane adhesive composition for the 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, thereby preparing a two-layer structure including an adhesive layer, the film having a thickness of approximately 20 micrometers. After peeling a biaxially stretched PET film (G2) from a four-layer structure including a colored layer, a two-layer structure film was applied so that the adhesive layer contacted the colored layer, thereby preparing a five-layer structure including PK-002 / adhesive layer / polyurethane precursor colored coating film / polyurethane precursor surface coating film / T60 (PET film), and the film was left to stand at room temperature for 24 hours.

[0175] Acrylic primer KBS17A / B was diluted with MEK and applied to a stainless steel plate (SUS430BA) as a metal substrate by wiping. It was then baked at 200°C for 5 minutes, forming a primer layer approximately 1 micrometer thick. While still hot from baking, PK-002, a five-layer structure, was peeled off, and an adhesive layer was applied to the primer layer. This was then allowed to stand at room temperature for 24 hours. The resulting material was heated at 80°C for 1 hour, and LUMIRROR (trade name) T60 was removed, yielding a test sample of the decorative laminate.

[0176] Comparative Example 7

[0177] Except that a polyester adhesive composition for the adhesive layer was used instead of a polyurethane adhesive composition for the adhesive layer, the test sample of the decorative laminate of Comparative Example 7 was obtained in the same manner as Comparative Example 6.

[0178] Example 14

[0179] Acrylic primer KBS17A / B was diluted with MEK and applied to a stainless steel plate (SUS430BA) as a metal substrate by wiping. The substrate was then baked at 200°C for 5 minutes to form a primer layer approximately 1 micrometer thick. A two-component curable polyurethane resin composition B was applied to the primer layer using a bar coater and then placed in a hot air oven at 80°C for 4 minutes to dry the uncured composition, thereby preparing a polyurethane precursor coating film with black opacity approximately 0.05 mm thick. LUMIRROR (trade name) T60 was laminated onto this coating film, and the resulting material was allowed to stand at room temperature for 24 hours. After heating the resulting material at 80°C for 1 hour, LUMIRROR (trade name) T60 was removed, thus obtaining a test sample of the decorative laminate.

[0180] Comparative Example 8

[0181] After applying the two-component curable polyurethane resin composition C for the surface layer to PK-002 using a bar coater, the uncured composition was dried in a hot air oven at 80°C for 4 minutes, thereby preparing a colorless polyurethane precursor coating film with a thickness of approximately 50 micrometers. LUMIRROR (trade name) T60 was then laminated onto this coating film to prepare a film with a three-layer structure, and the film was allowed to stand at room temperature for 24 hours.

[0182] A stainless steel sheet (SUS304#8) without a primer layer was heated to 200°C, and while still hot, PK-002 was peeled off from the three-layer film. An uncured polyurethane precursor coating was then applied to the surface of the primer layer and allowed to stand at room temperature for 24 hours. The resulting material was then heated at 80°C for 1 hour, and LUMIRROR (trade name) T60 was removed, thus obtaining a test sample of the decorative laminate.

[0183] Comparative Example 9

[0184] After applying the two-component curable polyurethane resin composition C to PK-002 using a bar coater, the uncured composition was dried in a hot air oven at 80°C for 4 minutes, thereby preparing a colorless polyurethane precursor coating film with a thickness of approximately 0.05 mm. LUMIRROR (trade name) T60 was then laminated onto this coating film to prepare a film with a three-layer structure, and the film was allowed to stand at room temperature for 24 hours.

[0185] 3M Adhesion Accelerator 86A was diluted 3 times with isopropanol and applied to a stainless steel plate (SUS304#8) as a metal substrate by wiping. The plate was then placed in a hot air oven at 200°C for 3 minutes, forming an adhesive layer approximately 1 micrometer thick. While still hot, PK-002 was peeled off from the three-layer film, and the uncured polyurethane precursor coating was applied to the adhesive layer. This was then allowed to stand at room temperature for 24 hours. The resulting material was heated at 80°C for 1 hour, and then LUMIRROR T60 was removed, yielding a test sample of the decorative laminate.

[0186] Physical property evaluation test 2

[0187] The characteristics of each test sample were evaluated by performing the appearance test and impact resistance test described in the above-mentioned physical property evaluation test 1, as well as the following tests. The results are indicated in Table 3.

[0188] Heat resistance test: resistance to opening

[0189] Using a DuPont drop hammer impact testing machine No. 517 (purchased from Yasuda Seiki Seisakusho, LTD., Nishinomiya-shi, Hyogo, Japan), the test sample was placed on a grooved mold, with the groove covered and the metal layer of the laminate as the top surface. A 1 kg weight was dropped from a height of 50 cm into the top surface of the metal layer with a hemispherical punch having a half-inch diameter tip in contact with it, deforming the test sample into a convex shape. The polyurethane layer of the convexly deformed test sample was transversely cut with a cutting blade, and the following thermal cycle was applied to the cut test sample. The opening width and peel width of the polyurethane layer at the cut portion were checked using calipers. Here, in this embodiment, a case where both the opening width and peel width are 0.5 mm or less is evaluated as "acceptable," and a case where either the opening width or peel width exceeds 0.5 mm is evaluated as "unacceptable."

[0190] (Heat cycle)

[0191] (1) Raise the temperature from 23°C to 80°C within 1 hour.

[0192] (2) Maintain the temperature at 80℃ for 18 hours.

[0193] (3) Let the temperature drop to -30℃ in 1 hour.

[0194] (4) Maintain the temperature at -30°C for 4 hours.

[0195] (5) Raise the temperature to 80℃ in 1 hour.

[0196] (6) Maintain the temperature at 80℃ for 18 hours.

[0197] Repeat steps (3) to (6) above 9 times.

[0198] (7) Let the temperature drop to -30℃ in 1 hour.

[0199] (8) Maintain the temperature at -30°C for 4 hours.

[0200] (9) Raise the temperature from -30℃ to 23℃ within 1 hour.

[0201] Waterproofing test: Sealing

[0202] The test sample was immersed in water at 40°C for 240 hours. After removal, the sample was wiped dry and allowed to stand for 1 hour. Then, using a cutter, a total of 100 1mm squares (10×10 squares) were formed on the polyurethane layer of the test sample. Sellotape (trade name) was pasted onto the 100 squares, and then immediately and forcefully peeled off the Sellotape (trade name), checking the number of remaining squares without peeling off the polyurethane layer. Here, when the number of remaining squares is 90 / 100 or more, the test sample is considered "pass," and when the number of remaining squares is 89 / 100 or less, the test sample is considered "fail."

[0203] Pencil hardness test: Hardness

[0204] A cylindrical pencil lead, smoothed with sandpaper, is applied to the polyurethane layer of the test sample at a 45° angle. The lead is moved 10 mm at a speed of 600 mm / min while a load of 750 g is applied to rub the polyurethane layer. Pencils with hardnesses from 6B to HB are used to test five times at different locations. The hardness of the test sample is determined by the hardness of the pencil used when the surface of the polyurethane layer is not scratched four or more times. Here, HB is considered "pass," and B or lower is considered "fail."

[0205]

[0206] Experimental Example 3

[0207] In Experimental Example 3, the chemical resistance, molding properties, and weather resistance of the test samples were evaluated.

[0208] Example 15

[0209] Test samples of the decorative laminate of Example 15 were obtained in the same manner as in Example 1.

[0210] Example 16

[0211] After applying the two-component curable polyurethane resin composition C to PK-002 using a bar coater, the uncured composition was dried in a hot air oven at 80°C for 4 minutes, thereby preparing a colorless polyurethane precursor coating film with a thickness of approximately 0.05 mm. LUMIRROR (trade name) T60 was then laminated onto this coating film to prepare a film with a three-layer structure, and the film was allowed to stand at room temperature for 24 hours.

[0212] A stainless steel sheet (SUS430#8) serving as the metal substrate was plasma-treated under a nitrogen atmosphere. Then, a silane coupling agent Z-6011 diluted to 3% alcohol was applied to the plasma-treated surface of the metal substrate by wiping, and the substrate was baked at 200°C for 5 minutes, thereby forming a primer layer with a thickness of approximately 1 micrometer. While still hot from baking, PK-002 was peeled off from the three-layer film, and the uncured polyurethane precursor coating film was applied to the primer layer and allowed to stand at room temperature for 24 hours. The resulting material was then heated at 80°C for 1 hour, and LUMIRROR (trade name) T60 was removed, yielding a test sample of the decorative laminate.

[0213] Example 17

[0214] Test samples of the decorative laminate of Example 17 were obtained in the same manner as in Example 14.

[0215] Comparative Example 10

[0216] As the test sample for Comparative Example 10, only stainless steel plate (SUS430#8) was used.

[0217] Physical property evaluation test 3

[0218] The characteristics of each test sample were evaluated using the following tests. The results are shown in Table 4.

[0219] Appearance Test: Decorative

[0220] The decorative properties are evaluated by visually observing the appearance, such as gloss, of the test samples before molding and after the following three-dimensional molding performance test (i.e., after molding).

[0221] Chemical resistance test: Chemical resistance

[0222] 1% by mass of hydrochloric acid 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 furnace at 40°C for 1 hour. Then, the surface with hydrochloric acid was washed with water, and traces such as discoloration were visually observed.

[0223] 3D molding performance test: Molding performance (hat shape)

[0224] Each test sample was cut into a circle with a diameter of approximately 135 mm, and then molded into a hat-like shape with a height of 45 mm and a diameter of 64 mm as shown in Figure 5 using a press and a pressing mold. During this process, the polyurethane layer or metal substrate was visually inspected for any abnormalities such as cracking.

[0225] Weather resistance test: weather resistance

[0226] The test samples in the hat shape obtained in the above three-dimensional molding performance test were placed on an exposure platform facing south at 45° on land about 1 km from the coast of Numazu-shi, Shizuoka, Japan for 2 years. Then, abnormalities were visually inspected, such as obvious changes in color and gloss, cracking and peeling of the polyurethane layer, and corrosion of the metal substrate.

[0227]

[0228] Various modifications and variations of the above-described embodiments and examples will be readily apparent to those skilled in the art without departing from the fundamental principles of the invention. Furthermore, it will be apparent to those skilled in the art that various modifications and variations of the invention can be made without departing from its spirit and scope.

[0229] List of reference numerals

[0230] 100, 200 decorative laminates

[0231] 101 and 201 metal layers

[0232] 103, 203 primer layers

[0233] 105 adhesive layer

[0234] 107, 207 polyurethane layers

[0235] 400 weight

[0236] 401 punch

[0237] 403 Test Sample (Decorative Laminate)

[0238] 405 mold

[0239] Items 1 through 10 below describe some implementations of this disclosure.

[0240] Project 1

[0241] A method for manufacturing a decorative laminate for three-dimensional molding, the method comprising:

[0242] Preparation of metal layer;

[0243] A primer layer is applied to the metal layer, the primer layer containing at least one selected from the group consisting of organosilicon compounds and (meth)acrylic resins;

[0244] A two-component curable polyurethane precursor layer containing polyols and isocyanates is directly applied to the primer layer; and

[0245] The two-component curable polyurethane precursor layer is reacted to form a polyurethane layer.

[0246] Project 2

[0247] According to the method described in Project 1, the polyurethane precursor layer is an uncured polyurethane sheet or an uncured polyurethane coating.

[0248] Project 3

[0249] According to the method of Project 1 or 2, the polyol is at least one selected from the group consisting of polycaprolactone polyol and polycarbonate diol, and the isocyanate is at least one selected from the group consisting of isocyanates having a cyclohexane structure, isocyanates without carbon-carbon double bonds, and isocyanates having a branched structure.

[0250] Project 4

[0251] The method according to any one of items 1 to 3, wherein the primer layer has a thickness of about 5 micrometers or less.

[0252] Project 5

[0253] A decorative laminate for three-dimensional molding, the laminate comprising, in sequence, a metal layer, a primer layer, and a polyurethane layer, wherein the primer layer contains at least one selected from the group consisting of organosilicon compounds and (meth)acrylic resins, and the polyurethane layer contains a curing reaction product of a two-component curable polyurethane resin composition comprising a polyol and an isocyanate.

[0254] The polyurethane layer is applied directly to the primer layer.

[0255] When the polyurethane layer of the laminate is subjected to the following water resistance test, the remaining square count of the polyurethane layer reaches 90 / 100 or more, and

[0256] When the polyurethane layer of the laminate is subjected to the following heat resistance test, the polyurethane layer exhibits an opening width or peel width of at most 0.5 mm or less:

[0257] Waterproofing test

[0258] The laminate was immersed in water at 40°C for 240 hours. After removing the laminate, the moisture was wiped off, and the laminate was allowed to stand for 1 hour. Then, a total of 100 squares (10×10) of 1 mm each were formed on the polyurethane layer of the laminate using a cutter. Sellotape (trade name) was applied to these 100 squares, and the Sellotape (trade name) was immediately peeled off. The number of remaining squares in the polyurethane layer that were not peeled off was then checked.

[0259] Heat resistance test

[0260] Using a DuPont No. 517 drop hammer impact testing machine, the laminate is placed on a grooved mold, with the groove covered and the metal layer of the laminate as the top surface. A 1 kg weight is dropped from a height of 50 cm into the top surface of the metal layer, with a hemispherical punch with a half-inch diameter tip in contact with the top surface of the metal layer, causing the laminate to deform into a convex shape. A cross-cut is made in the deformed polyurethane layer using a cutting blade, and after applying the following thermal cycles to the laminate, the opening width and peel width of the cut polyurethane layer are examined:

[0261] (Heat cycle)

[0262] (1) Raise the temperature from 23°C to 80°C within 1 hour.

[0263] (2) Maintain the temperature at 80℃ for 18 hours.

[0264] (3) Let the temperature drop to -30℃ in 1 hour.

[0265] (4) Maintain the temperature at -30°C for 4 hours.

[0266] (5) Raise the temperature to 80℃ in 1 hour.

[0267] (6) Maintain the temperature at 80℃ for 18 hours.

[0268] Repeat steps (3) to (6) 9 times.

[0269] (7) Let the temperature drop to -30℃ in 1 hour.

[0270] (8) Maintain the temperature at -30°C for 4 hours.

[0271] (9) Increase the temperature from -30°C to 23°C within 1 hour.

[0272] Project 6

[0273] According to the laminate of Project 5, the polyol is at least one selected from the group consisting of polycaprolactone polyol and polycarbonate polyol, and the isocyanate is at least one selected from the group consisting of isocyanates having a cyclohexane structure, isocyanates without carbon-carbon double bonds, and isocyanates having a branched structure.

[0274] Project 7

[0275] The laminate as described in Project 5 or 6, wherein the primer layer has a thickness of about 5 micrometers or less.

[0276] Project 8

[0277] According to any one of items 5 to 7, when the laminate is placed on a mold with a groove using a No. 517 DuPont drop hammer impact tester, such that the groove of the mold is covered, and the metal layer of the laminate is the top surface; when a 1 kg weight is dropped from a height of 50 cm into the top surface of the metal layer with a hemispherical punch having a half-inch diameter tip in contact with the top surface of the metal layer, the polyurethane layer, which deforms into a convex shape, does not crack or peel.

[0278] Project 9

[0279] A decorative article comprising the laminate described in any one of items 5 to 8, the decorative article having a three-dimensional shape.

[0280] Project 10

[0281] A method for manufacturing decorative articles, the method comprising pressing or rolling a laminate as described in any one of items 5 to 8.

Claims

1. A method for manufacturing a decorative laminate for three-dimensional molding, the method comprising: Preparation of metal layer; A primer layer is applied to the metal layer, the primer layer comprising at least one selected from the group consisting of organosilicon compounds and (meth)acrylic resins; A two-component curable polyurethane precursor layer containing polyols and isocyanates is directly applied to the primer layer; as well as The two-component curable polyurethane precursor layer is reacted 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.

3. The method according to claim 1 or 2, wherein the polyol is at least one selected from the group consisting of polycaprolactone polyol and polycarbonate polyol, and the isocyanate is at least one selected from the group consisting of isocyanates having a cyclohexane structure, isocyanates without carbon-carbon double bonds, and isocyanates 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, the laminate comprising, in sequence, a metal layer, a primer layer, and a polyurethane layer. The primer layer contains at least one selected from the group consisting of organosilicon compounds and (meth)acrylic resins, and the polyurethane layer contains a curing reaction product of a two-component curable polyurethane resin composition comprising a polyol and an isocyanate. The polyurethane layer is applied directly to the primer layer. When the polyurethane layer of the laminate is tested for water resistance, the remaining square count of the polyurethane layer reaches 90 / 100 or more, and When the polyurethane layer of the laminate is subjected to heat resistance testing, the polyurethane layer exhibits an opening width or peel width of at most 0.5 mm or less.

6. The laminate according to claim 5, wherein the polyol is at least one selected from the group consisting of polycaprolactone polyol and polycarbonate polyol, and the isocyanate is at least one selected from the group consisting of isocyanates having a cyclohexane structure, isocyanates without carbon-carbon double bonds, and isocyanates 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 the laminate is placed on a mold with a groove using a DuPont No. 517 drop hammer impact tester such that the groove of the mold is covered, and the metal layer of the laminate is the top surface, and a 1 kg weight is dropped from a height of 50 cm into the top surface of the metal layer with a hemispherical punch having a half-inch diameter tip in contact with the top surface of the metal layer, the polyurethane layer deformed into a convex shape does not crack or peel.

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

10. A method for manufacturing decorative articles, the method comprising pressing or rolling a laminate according to claim 5 or 6.

Images