Metallic texture decorative laminate, metallic texture article, and method for manufacturing decorative laminate

Abstract

The present application provides a metal texture decorative laminate, an intermediate laminate, a multi-layer laminate, a decorative laminate, and a metal texture article. The metal texture decorative laminate includes a lustrous resin layer containing a resin component (1), one or more than two pigments, and one or more than two lustrous materials; and a transparent resin layer containing a resin component (2). The resin component (1) contains one or more than two fluorine-based resins, and the resin component (2) contains one or more than two fluorine-based resins. The present application also provides a method for manufacturing the intermediate laminate and a method for manufacturing the decorative laminate.

Description

Technical Field

[0001] This invention relates to metallic decorative laminates, intermediate laminates, multilayer laminates, decorative laminates, metallic articles, methods for manufacturing the aforementioned intermediate laminates, and methods for manufacturing the aforementioned decorative laminates. Background Technology

[0002] To improve the appearance of resin molded articles, a process is performed to impart a metallic luster to the surface of the resin molded articles. As a method for imparting this metallic luster, metal plating is performed (Patent Document 1). Furthermore, as another application, a glossy coated resin article with electromagnetic wave transmittance has been developed (Patent Document 2).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2002-241948

[0006] Patent Document 2: Japanese Patent Application Publication No. 2010-030075 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] The present invention aims to provide a metallic decorative laminate, intermediate laminate, multilayer laminate, decorative laminate, and metallic article that presents an excellent metallic appearance design, reduces the environmental impact during manufacturing, and improves chemical resistance and weather resistance, and provides a method for manufacturing the intermediate laminate and the decorative laminate.

[0009] Methods for solving problems

[0010] In order to solve the above problems, the inventors conducted in-depth research and provided the following [1] to [7].

[0011] [1] A metallic decorative laminate comprising: a glossy resin layer containing a resin component (1), one or more pigments and one or more glossy materials; and a transparent resin layer containing a resin component (2), wherein the resin component (1) contains one or more fluorinated resins and the resin component (2) contains one or more fluorinated resins.

[0012] [2] An intermediate laminate comprising a substrate on the transparent resin layer side of the metallic decorative laminate described in [1].

[0013] [3] A multilayer laminate comprising a base layer on the glossy resin layer side of the intermediate laminate of [2].

[0014] [4] A decorative laminate comprising a base layer on the glossy resin layer side of the metallic decorative laminate described in [1].

[0015] [5] A metallic article having the metallic decorative laminate described in [1].

[0016] [6] A method for manufacturing the intermediate laminate described in [2] includes, in sequence: coating a coating liquid containing one or more fluorinated resins; coating a coating liquid containing one or more fluorinated resins, one or more pigments and one or more glossy materials; and heating.

[0017] [7] A method of manufacturing the decorative laminate of [4], comprising peeling a substrate from the multilayer laminate of [3].

[0018] Invention Effects

[0019] According to the present invention, it is possible to provide a metallic decorative laminate, intermediate laminate, multilayer laminate, decorative laminate, and metallic article that presents an excellent metallic appearance design, reduces the environmental impact during manufacturing, and improves chemical resistance and weather resistance. Furthermore, it is possible to provide a method for manufacturing the aforementioned intermediate laminate and a method for manufacturing the aforementioned decorative laminate. Attached Figure Description

[0020] Figure 1 This is a schematic diagram illustrating an example of a multilayer stack containing the metallic decorative laminate of this embodiment.

[0021] Figure 2 This is a schematic diagram of the glossy material in the glossy resin layer. Detailed Implementation

[0022] Patent Document 1 describes an invention relating to a metallized component for vehicles made of synthetic resin, which exhibits a metallic luster by plating a component made of synthetic resin. However, metal plating has problems such as complex processes, high manufacturing costs, and the generation of waste liquid, which puts a burden on the environment. In addition, it is difficult to achieve a uniform and aesthetically pleasing coating when the surface of the molded body has an uneven shape.

[0023] Patent document 2 described above describes an aluminum-textured bumper that allows millimeter waves to pass through. However, while it achieves a metallic appearance through thin aluminum sheets, it focuses on millimeter wave transmittance and does not adequately address chemical resistance and weather resistance.

[0024] In contrast, the metallic decorative laminate disclosed herein, by having a specific layer composition, can achieve a metallic decorative laminate that presents an excellent metallic appearance and has improved chemical resistance and weather resistance.

[0025] Furthermore, it is possible to provide intermediate laminates, multilayer laminates, decorative laminates, and metallic articles that are composed of the aforementioned metallic decorative laminates, and it is also possible to provide methods for manufacturing the aforementioned intermediate laminates and methods for manufacturing the aforementioned decorative laminates.

[0026] The following describes the metallic decorative laminate, intermediate laminate, multilayer laminate, decorative laminate, metallic article, and manufacturing method of the metallic decorative laminate of the present invention. It should be noted that the present invention is not limited to the examples described below.

[0027] It should be noted that in this disclosure, such as Figure 1 As shown, the thickness direction 100 refers to the stacking direction of the metallic decorative laminate or metallic article, and the width direction 110 is a direction different from the thickness direction, referring to the direction orthogonal to the length direction 120 of the metallic decorative laminate or metallic article. For example, in the case of manufacturing the intermediate laminate described later using roll-to-roll, the length direction 120 corresponds to the flow direction (MD: machine direction), and the width direction 110 corresponds to the transverse direction (TD) perpendicular to the MD.

[0028] The embodiments of this disclosure (hereinafter, sometimes referred to as "this embodiment") will be described below. It should be noted that in this disclosure, the numerical values ​​related to the description of numerical ranges, such as "above", "below", "~", etc., are numerical values ​​that can be arbitrarily combined.

[0029] Furthermore, the preferred limitation can be adopted arbitrarily. That is, one preferred limitation can be combined with one or more other preferred limitations. It can be said that the combination of preferred limitations is more preferred.

[0030] [Metallic Decorative Layers]

[0031] The metallic decorative laminate of this embodiment needs to be a metallic decorative laminate containing a glossy resin layer containing a resin component (1), one or more pigments and one or more glossy materials, and a transparent resin layer containing a resin component (2). The resin component (1) contains one or more fluorinated resins, and the resin component (2) contains one or more fluorinated resins.

[0032] The aforementioned metallic decorative laminate comprises a glossy resin layer and a transparent resin layer. The glossy resin layer contains resin component (1), pigment, and glossy material, wherein the resin component (1) contains a fluorinated resin. The transparent resin layer contains resin component (2), wherein the resin component (2) contains a fluorinated resin.

[0033] The metallic decorative laminate of this embodiment can be used, for example, to decorate resin parts and metal parts (hereinafter also referred to as "articles") such as automotive bumpers using film decoration methods such as embedding molding and overmolding of multilayer laminates containing metallic decorative laminates. Furthermore, multilayer laminates containing the aforementioned metallic decorative laminate can be used to decorate the surface of articles via adhesive layers or bonding layers, for example, as surface layers in automotive exterior parts such as automotive pillars, door trim strips, roof trim strips, entire door panels, and entire roof panels. In addition, the metallic decorative laminate of this embodiment exhibits an excellent metallic appearance design and excellent chemical resistance and weather resistance, making it preferably suitable for outdoor use. Furthermore, due to its excellent chemical resistance, it is preferably used for decorating four-wheeled vehicles, two-wheeled vehicles, pumps, and the like that use lubricating oil.

[0034] Furthermore, as will be described in detail later, the metallic decorative laminate of this embodiment is preferred because it is easy to manufacture and therefore has excellent mass production capabilities.

[0035] To improve the appearance and weather resistance, the thickness of the metallic decorative laminate in this embodiment is preferably 20 μm or more, more preferably 30 μm or more, further preferably 35 μm or more, and even more preferably 40 μm or more. To improve formability, it is preferably 100 μm or less, more preferably 80 μm or less, further preferably 70 μm or less, and even more preferably 65 μm or less. Although it is also believed that a thicker layer results in better chemical resistance, it is known that excessively thick layers can actually worsen the problem.

[0036] To achieve a balance between appearance, weather resistance and chemical resistance, the preferred thickness is 20 μm or more and 100 μm or less, more preferably 30 μm or more and 80 μm or less, even more preferably 35 μm or more and 70 μm or less, and even more preferably 40 μm or more and 65 μm or less.

[0037] In this disclosure, "design quality" refers to the ability to express a metallic appearance by applying the metallic decorative laminate of this disclosure to an article, thereby enabling the article to exhibit a metallic appearance, and to express the desired hue by means of the added pigments and glossy materials.

[0038] In this disclosure, "chemical resistance" refers to the property that the transparent resin layer contained in the metallic decorative laminate of this disclosure can be inhibited from dissolving, swelling, and reacting even if organic solvents or lubricating oils adhere to it. It refers to properties that include oil resistance and solvent resistance, which can be evaluated, for example, by the methods described in the examples.

[0039] In this disclosure, "weather resistance" refers to the property that the material is not easily deformed, discolored, or deteriorated when used outdoors, and can be evaluated, for example, by the methods described in the embodiments.

[0040] In this disclosure, "formability" refers to the ease of manufacturing when using the metallic decorative laminate of this disclosure to manufacture metallic articles. Formability is preferred because increasing the layer thickness can suppress cracking during molding, and it is also preferred because reducing the layer thickness allows for the decoration of small parts of the article. For example, it can be evaluated using the methods described in the embodiments.

[0041] The total light transmittance of the metallic decorative laminate of this embodiment can be adjusted as needed. As described below, the metallic decorative laminate of this embodiment achieves its metallic appearance design through the inclusion of glossy materials and pigments.

[0042] The total light transmittance of the metallic decorative laminate in this embodiment can be appropriately adjusted according to the content of glossy materials, the shape of glossy materials, the content of pigments, etc.

[0043] To ensure a metallic finish in bright outdoor light, such as midday sun, the total light transmittance of the metallic decorative layer in this embodiment is preferably low. This total light transmittance can be adjusted by the content of glossy materials and / or pigments. When a light source is placed on the article side of the metallic decorative layer, and color is displayed using light transmitted through the layer, a higher total light transmittance is preferable. Increasing the content of these materials results in a stronger metallic finish based on the glossy material, which lowers the total light transmittance and obscures the color of the metallic-looking article; this is therefore preferable. Furthermore, increasing the pigment content to adjust the hue also lowers the total light transmittance. To achieve this effect, the total light transmittance is preferably 3% or more, more preferably 5% or more, further preferably 6% or more, and even more preferably 8% or more. There is no particular limitation on the upper limit, but it is acceptable as long as the metallic texture of the metallic decorative laminate of this disclosure is achieved. Preferably, it is 40% or less, more preferably 30% or less, further preferably 20% or less, and even more preferably 15% or less. It can also be set such that the color of the item is substantially indistinguishable from the metallic decorative laminate side. More specifically, it is preferably 3% or more and 40% or less, more preferably 5% or more and 30% or less, further preferably 6% or more and 20% or less, and even more preferably 8% or more and 18% or less.

[0044] The total light transmittance described above can be measured, for example, using the method described in the embodiments.

[0045] The metallic decorative laminate of this embodiment may contain only the glossy resin layer and the transparent resin layer described later, or it may contain other resin layers described later.

[0046] When the metallic decorative laminate of this embodiment is disposed on an article to produce a metallic article as described later, it is preferable that the glossy resin layer is located on the article side, and it is preferable that the transparent resin layer is the outermost surface of the metallic article.

[0047] <Glossy Resin Layer>

[0048] The aforementioned glossy resin layer is a layer that imparts a metallic luster to a metallic decorative laminate, and it needs to contain a resin component (1) containing one or more fluorine-based resins, one or more pigments, and one or more glossy materials.

[0049] The aforementioned glossy resin layer may contain only the aforementioned fluorinated resin as the aforementioned resin component (1). The resin component (1) may further contain one or two or more thermoplastic resins, and may further contain other components described later. The aforementioned resin component (1) refers not only to the aforementioned fluorinated resin, but also to components other than the glossy material contained in the glossy resin layer.

[0050] The aforementioned glossy resin layer may contain only the aforementioned fluorinated resin, the aforementioned thermoplastic resin, pigment, and the aforementioned glossy material, or it may further contain other components described later.

[0051] As described above, metallic articles are preferably layered in the following order: article, glossy resin layer, and transparent resin layer. In particular, the transparent resin layer is preferably the outermost surface of the metallic article. Since the transparent resin layer comes into contact with the atmosphere, solvents, chemicals, etc., it is foreseeable that its chemical resistance and weather resistance will greatly contribute to improving the chemical resistance and weather resistance of the metallic article. However, repeated studies have shown that the composition of the glossy resin layer, which does not directly contact chemicals, is extremely important for improving the chemical resistance and weather resistance of the metallic article. Even when using the same transparent resin layer, the chemical resistance and weather resistance differ depending on the combination of the glossy resin layers. The aforementioned glossy resin layer, by containing fluorinated resin and glossy materials, can improve the chemical resistance and weather resistance of the metallic article. The glossy resin layer is a layer that does not directly contact external gases, etc., and therefore, those skilled in the art generally believe that it does not contribute to the chemical resistance and weather resistance of the metallic article. However, it has been found that by setting the layer configuration as in this embodiment, chemical resistance and weather resistance are improved. The reason is not yet clear, but it is believed that if the glossy resin layer contains fluorinated resin and glossy materials, the aggregation of fluorinated resin in the transparent resin layer is inhibited, and the fluorinated resin becomes uniformly dispersed in the transparent resin layer. Therefore, the chemical resistance and weather resistance characteristics of fluorinated resin are manifested on the surface of the layer.

[0052] Furthermore, because the aforementioned glossy resin layer contains pigments, it can exhibit metallic hues such as black, red, blue, white, dark blue, carmine, orange, and olive, which are difficult to achieve with glossy materials alone. It is also considered to include pigments in the aforementioned transparent resin layer to adjust the hue. However, as mentioned above, when the transparent resin layer becomes the outermost surface of a metallic-textured item, fading due to pigment oxidation or other factors can occur. Therefore, to suppress this fading, it is preferable to include pigments in the glossy resin layer.

[0053] Regarding the thickness of the aforementioned glossy resin layer, the thicker the layer, the greater the amount of glossy material, thus improving the appearance design. In addition, it exhibits the aforementioned effects on the transparent resin layer. Therefore, in order to improve the appearance design, chemical resistance, and weather resistance, it is preferable to be 5μm or more, more preferably 8μm or more, further preferably 10μm or more, and even more preferably 13μm or more. In order to improve chemical resistance and moldability, it is preferable to be 100μm or less, more preferably 60μm or less, further preferably 40μm or less, and even more preferably 35μm or less.

[0054] To achieve a balance between chemical resistance, weather resistance, appearance design and moldability, the preferred thickness is 5μm or more and 100μm or less, more preferably 8μm or more and 60μm or less, even more preferably 10μm or more and 40μm or less, and even more preferably 13μm or more and 35μm or less.

[0055] As described above, the glossy resin layer contains one or more fluorinated resins as resin components (1), and may further contain one or more thermoplastic resins. They may be mixtures (polymer alloys) or reactants, but in order to improve the dispersibility of the glossy material in the metallic decorative laminate, they are more preferably mixtures (polymer alloys).

[0056] Details of the fluorinated resins will be described later. Only one type of fluorinated resin can be used, or two or more types can be used in combination. If only one type is used, it is easy to manufacture a uniform metallic decorative laminate, so this is preferred. If two or more types are used, it is easy to adjust the melting point and other physical properties of the resin component (1), so this is also preferred.

[0057] Details of the aforementioned thermoplastic resin will be described later. The resin component (1) may use only one type of thermoplastic resin or a combination of two or more types. If only one type is used, it is easy to manufacture a uniform metallic decorative laminate, so this is preferred. If two or more types are used, the melting point and other physical properties of the resin component (1) can be easily adjusted by adjusting their content ratio, so this is also preferred.

[0058] The resin component (1) contained in the above-mentioned glossy resin layer may contain other components besides the above-mentioned fluorinated resin. Details of other components will be described later. In this disclosure, components other than glossy materials contained in the above-mentioned glossy resin layer are referred to as resin component (1).

[0059] When the total amount of resin component (1) contained in the above-mentioned glossy resin layer is set to 100% by mass, the total content of the above-mentioned fluorinated resin and the above-mentioned thermoplastic resin contained therein is preferably 80.00% by mass or more, more preferably 90.00% by mass or more, even more preferably 95.00% by mass or more, and even more preferably 97.00% by mass or more. There is no particular upper limit, but it is preferably substantially 100% by mass. "Substantially" means excluding unintentionally contained impurities, etc.

[0060] When the resin component (1) contained in the above-mentioned glossy resin layer contains the above-mentioned fluorinated resin and the above-mentioned thermoplastic resin, the ratio of the content of the above-mentioned fluorinated resin in the content of the above-mentioned thermoplastic resin (content of the above-mentioned fluorinated resin (mass%) / content of the above-mentioned thermoplastic resin (mass%)) is preferably 0.30 or more and 4.00 or less, more preferably 0.80 or more and 3.00 or less, even more preferably 1.10 or more and 2.00 or less, and even more preferably 1.30 or more and 1.80 or less. When using an acrylic resin described later as the thermoplastic resin, it is also preferably 0.30 or more and 4.00 or less, more preferably 0.80 or more and 3.00 or less, even more preferably 1.10 or more and 2.70 or less, and even more preferably 1.30 or more and 2.50 or less.

[0061] By increasing the content of the fluorinated resin to that of the thermoplastic resin (e.g., acrylic resin), the dispersibility of the fluorinated resin in the transparent resin layer is improved, as are its chemical resistance and weather resistance, which is therefore preferred.

[0062] In addition to the resin component (1), the glossy resin layer contains one or more pigments (described later) and one or more glossy materials (described later). Relative to a total of 100 parts by mass of the resin component (1), the glossy material in the glossy resin layer is preferably 0.01 parts by mass or more and 20.00 parts by mass or less. By setting the value to the lower limit or above, the chemical resistance, weather resistance, and appearance of the metallic decorative laminate are improved. Therefore, it is preferable that the value is set to the upper limit or below, thereby improving the formability. Therefore, it is preferable, more preferably 0.02 parts by mass or more and 15.00 parts by mass or less, further preferably 0.03 parts by mass or more and 10.00 parts by mass or less, even more preferably 0.05 parts by mass or more and 5.00 parts by mass or less, even more preferably 0.07 parts by mass or more and 3.00 parts by mass or less, and even more preferably 0.08 parts by mass or more and 2.00 parts by mass or less.

[0063] Relative to 100 parts by weight of the aforementioned resin component (1), the pigment in the aforementioned glossy resin layer is preferably 0.05 parts by weight or more and 20.00 parts by weight or less. By setting the value to the lower limit or above, the chemical resistance, weather resistance, and appearance design of the aforementioned metallic decorative laminate are improved. Therefore, it is preferable that the value is set to the upper limit or below, as the formability is improved. Therefore, it is preferable, more preferably 0.10 parts by weight or more and 15.00 parts by weight or less, further preferably 0.20 parts by weight or more and 13.00 parts by weight or less, even more preferably 0.30 parts by weight or more and 10.00 parts by weight or less, even more preferably 0.35 parts by weight or more and 7.00 parts by weight or less, and even more preferably 0.40 parts by weight or more and 5.00 parts by weight or less.

[0064] Relative to 100 parts by weight of the aforementioned resin component (1), the total amount of the aforementioned glossy material and the aforementioned pigment in the aforementioned glossy resin layer is preferably 0.05 parts by weight or more and 20.00 parts by weight or less. By setting the lower limit value or above, the chemical resistance, weather resistance, and appearance design of the aforementioned metallic decorative laminate are improved. Therefore, it is preferable that the formability is improved by setting the upper limit value or below. Therefore, it is preferable, more preferably 0.10 parts by weight or more and 15.00 parts by weight or less, further preferably 0.20 parts by weight or more and 13.00 parts by weight or less, even more preferably 0.30 parts by weight or more and 10.00 parts by weight or less, even more preferably 0.35 parts by weight or more and 7.00 parts by weight or less, and even more preferably 0.40 parts by weight or more and 5.00 parts by weight or less.

[0065] Fluoropolymer Resins

[0066] The aforementioned fluorinated resins are typically added to improve chemical resistance and weather resistance. In this embodiment, by including the aforementioned fluorinated resin in the resin component (1), the chemical resistance and weather resistance of the metallic articles using it are improved, even though the glossy resin layer does not come into direct contact with chemicals. Furthermore, when the resin component (1) contains a fluorinated resin, the dispersibility of the glossy material is improved, and the metallic articles using it have a uniform metallic luster.

[0067] As the aforementioned fluorinated resin, any fluorinated resin commonly used as a fluorinated resin can be used, with preferred examples including polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (CTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), perfluoroalkoxy fluoropolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), and ethylene-chlorotrifluoroethylene copolymer (ECTFE). In particular, polyvinylidene fluoride (PVDF), by being used as a component of the aforementioned resin, exhibits excellent film-forming properties, thereby becoming a glossy resin layer with excellent dispersibility for glossy materials, and is therefore preferred.

[0068] When using the thermoplastic resin (acrylic resin) described later, in order to facilitate the formation of polymer alloys, the mass-average molecular weight (Mw) of the fluorinated resin is preferably 800 or more and 5,000 or less, more preferably 1,000 or more and 3,000 or less, even more preferably 1,300 or more and 2,000 or less, and even more preferably 1,500 or more and 1,700 or less.

[0069] In order to facilitate the formation of polymer alloys with the acrylic resins described later, the polydispersity (Mw / Mn) of the fluorinated resin is preferably 0.5 or more and 5.0 or less, more preferably 0.8 or more and 2.5 or less, even more preferably 1.0 or more and 1.8 or less, and even more preferably 1.2 or more and 1.4 or less.

[0070] The content of the fluorinated resin in the resin component (1) of the above-mentioned glossy resin layer is preferably 30.00% by mass or more and 80.00% by mass or less, more preferably 35.00% by mass or more and 80.00% by mass or less, even more preferably 40.00% by mass or more and 75.00% by mass or less, even more preferably 50.00% by mass or more and 70.00% by mass or less, and even more preferably 55.00% by mass or more and 65.00% by mass or less.

[0071] <<Pigment>>

[0072] The pigments described above are included to achieve an appearance design of a hue that cannot be achieved by using only the glossy materials described later, by dispersing them in the resin composition described above, and do not include the glossy materials described later.

[0073] The pigments do not reflect external light (incident light), but instead absorb light of a specific wavelength to adjust the hue of the glossy resin layer.

[0074] The pigments contained in the aforementioned glossy resin layer are commonly used pigments in this technical field. There are no particular limitations as long as the aforementioned metallic decorative laminate exhibits the target metallic appearance design. Any pigment that absorbs visible light can be a dye or pigment, and can be an inorganic or organic compound, or a natural or synthetic pigment. Especially in outdoor applications requiring weather resistance, synthetic pigments are preferred, while organic pigments are preferred to improve color rendering. The aforementioned pigments preferably contain inorganic or organic pigments, and more specifically, examples include: inorganic pigments such as titanium dioxide, zinc white, iron oxide red, cinnabar, ultramarine, cobalt blue, titanium yellow, chrome yellow, and carbon black; and organic pigments (including dyes) such as isoindolinone, Hansa Yellow A, quinacridone, Permanent Red 4R, phthalocyanine blue, indanthrene blue RS, and aniline black.

[0075] <<Glossy Materials>>

[0076] The aforementioned glossy material is any material contained in order to reflect external light (incident light) by being dispersed in the aforementioned resin composition, to impart a metallic luster to the glossy resin layer, and to exhibit the appearance design of a metallic decorative laminate. It is not particularly limited and can be an inorganic pigment or an organic pigment, a natural material or a synthetic material. However, in order to improve the reflectivity of external light, an inorganic pigment is preferred.

[0077] The surface of the aforementioned glossy material may have a coating. The coating may be an organic coating using organic materials such as organosilicon, or an inorganic coating using inorganic materials such as silica gel or alumina.

[0078] As the aforementioned glossy material, it is preferable to contain at least one material selected from flake-like or sheet-like metal, flake-like or sheet-like alloy metal, flake-like or sheet-like metal oxide, flake-like or sheet-like mica, glass flakes, and film fragments. As long as the glossiness is achieved by inclusion in the resin composition, flake-like or sheet-like metal, flake-like or sheet-like mica, or film fragments are more preferred from the perspectives of ease of acquisition and improved appearance design. Flake-like or sheet-like metal or flake-like mica is even more preferred, and flake-like or sheet-like metal is still the most preferred.

[0079] The aforementioned flake-like or sheet-like metals are particles obtained by forming metal powder into sheet-like shapes. As for the aforementioned metals, any metal commonly used in flake-like or sheet-like metals is preferred, with aluminum, iron, copper, nickel, zinc, gold, silver, oxides of these metals, and alloys containing these metals being more preferred. Examples of flake-like or sheet-like metals include aluminum sheets, stainless steel sheets, copper sheets, and nickel sheets. To obtain a decorative laminate with an excellent metallic texture and superior aesthetic design, flake-like or sheet-like metals are preferably sheets of aluminum or its alloys, and more preferably aluminum sheets.

[0080] Examples of mica that can be scaly or flaky include white pearlescent pigments, interference pearlescent pigments, and colored pearlescent pigments.

[0081] The aforementioned white pearlescent pigment is formed by covering a scaly matrix such as mica, aluminum, or glass with a coating layer composed of colorless high-refractive-index materials such as titanium dioxide. The thickness of the coating layer is preferably between 0.1 μm and 0.15 μm.

[0082] The aforementioned interference pearlescent pigment is composed of a coating layer coated with a colorless high refractive index material such as titanium dioxide, and the thickness of the coating layer is preferably greater than 0.15 μm.

[0083] Preferably, the above-mentioned glossy material is in Figure 2 The glossy resin layer 30 is sufficiently and uniformly dispersed in the above-mentioned resin components, and is oriented in a manner in which the thickness direction 210 of the glossy material is substantially parallel to the thickness direction 100. Figure 2 The glossy material is schematically depicted as a disk shape, but is not limited to this. The longest length in the planar direction (particle size direction 220) of the glossy material 200 is defined as the particle size 221 of the glossy material, and the average thickness in the thickness direction perpendicular to the planar direction is defined as the thickness 211 of the glossy material. These are the average values ​​measured under an optical microscope from 20 randomly sampled glossy materials. The particle size 221 of the glossy material can be expressed as the volume average particle size (D) described in the examples. 50 To replace it, from the perspective of ease of obtaining and the appearance design that expresses a metallic texture, the particle size of the glossy material is 221 (D). 50 Preferably, the particle size is 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more. To increase transmitted light and improve chemical resistance and weather resistance, it is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, even more preferably 15 μm or less, and even more preferably 10 μm or less. Volume average particle size (D...) 50 It can be determined using conventional methods.

[0084] To achieve a balance between chemical resistance, weather resistance, appearance design and moldability, the preferred thickness is 3μm or more and 50μm or less, more preferably 3μm or more and 30μm or less, even more preferably 4μm or more and 20μm or less, even more preferably 4μm or more and 15μm or less, and even more preferably 5μm or more and 10μm or less.

[0085] In order to balance chemical resistance, weather resistance, appearance design and formability, the thickness 211 of the glossy material is preferably 0.05 μm or more and 1.00 μm or less, more preferably 0.10 μm or more and 0.80 μm or less, and even more preferably 0.10 μm or more and 0.50 μm or less.

[0086] The particle size of the glossy material is 221 (D) 50 The ratio of particle size to thickness 211 of the glossy material (=particle size / thickness) is preferably 3 or more and 200 or less, more preferably 5 or more and 150 or less, even more preferably 8 or more and 120 or less, and even more preferably 10 or more and 100 or less.

[0087] Fluoropolymers are prone to agglomeration. Agglomeration easily produces tiny particle-like shapes (hereinafter referred to as aggregates). These aggregates exhibit poor compatibility with other resin components, hindering the uniform distribution of the fluoropolymer. Even after the aggregates are crushed and stirred with, for example, a thermoplastic resin, re-agglomeration occurs in the resin composition, resulting in an unevenly dispersed state. When this resin composition is coated, there is a tendency for aggregates to exist unevenly on the coating surface. Such unevenness prevents the full expression of the properties of the fluoropolymer. To prevent aggregate growth, a method of adding a nucleating agent (described later) is known. Adding a nucleating agent inhibits particle size growth even when aggregates are formed. However, increasing the amount of nucleating agent reduces weather resistance and moldability. Glossy materials are added to improve appearance, but when used with fluoropolymers, their ability to inhibit aggregate growth has been confirmed. In addition, since fluorinated resins improve the dispersibility of glossy materials, the glossy resin layer becomes a uniform layer structure through the synergistic effect of using fluorinated resins and glossy materials simultaneously.

[0088] <<Thermoplastic Resins>>

[0089] The aforementioned glossy resin layer preferably further contains one or more thermoplastic resins.

[0090] The total content of thermoplastic resin in the resin component (1) of the above-mentioned glossy resin layer is preferably 20.00% by mass or more and less than 70.00% by mass, more preferably 25.00% by mass or more and less than 60.00% by mass, further preferably 30.00% by mass or more and less than 50.00% by mass, and even more preferably 35.00% by mass or more and less than 45.00% by mass.

[0091] Examples of thermoplastic resins include polyolefin resins, polyester resins, and polystyrene resins, but polyolefin resins are preferred for good moldability.

[0092] To improve impact resistance, the weight-average molecular weight (Mw) of the above-mentioned polyolefin resin is preferably 30,000 or more and 500,000 or less, more preferably 50,000 or more and 300,000 or less, even more preferably 70,000 or more and 200,000 or less, and even more preferably 90,000 or more and 100,000 or less.

[0093] To improve impact resistance, the polydispersity (Mw / Mn) of the above-mentioned polyolefin resin is preferably 1.5 or more and 5.0 or less, more preferably 1.6 or more and 4.0 or less, even more preferably 1.7 or more and 3.0 or less, and even more preferably 1.9 or more and 2.2 or less.

[0094] To improve impact resistance, the glass transition temperature (Tg) of the above-mentioned polyolefin resin is preferably 100°C or higher, more preferably 108°C or higher, even more preferably 115°C or higher, and even more preferably 117°C or higher.

[0095] There is no particular limit to the upper limit of Tg, but from the viewpoint of formability, it is preferably below 150°C, more preferably below 140°C, even more preferably below 130°C, and even more preferably below 125°C.

[0096] (Acrylic resin)

[0097] As the aforementioned polyolefin resin, acrylic resin is preferred. As an acrylic resin, any resin used as a polymer or copolymer of acrylic acid and its esters, or methacrylic acid derivatives such as methyl methacrylate, can be used. More specifically, polyethyl methacrylate (PEMA), polybutyl methacrylate (PBMA), polycyclohexyl methacrylate (PCHMA), and polyethylhexyl methacrylate (PEHMA) are preferred examples. In particular, polymethyl methacrylate (PMMA) resin, when used as a resin component, exhibits high transparency and high hardness, thus providing excellent damage resistance. Furthermore, it can be thermoplasticized into complex shapes, making it useful.

[0098] In order to facilitate the formation of polymer alloys with the aforementioned fluorinated resins, the mass-average molecular weight (Mw) of the aforementioned acrylic resins is preferably 30,000 or more and 500,000 or less, more preferably 50,000 or more and 300,000 or less, even more preferably 70,000 or more and 200,000 or less, and even more preferably 90,000 or more and 100,000 or less.

[0099] In order to facilitate the formation of polymer alloys with the above-mentioned fluorinated resins, the polydispersity (Mw / Mn) of the above-mentioned acrylic resins is preferably 1.5 or more and 5.0 or less, more preferably 1.6 or more and 4.0 or less, even more preferably 1.7 or more and 3.0 or less, and even more preferably 1.9 or more and 2.2 or less.

[0100] In order to make the resin composition of the above-mentioned fluorinated resin more uniform and to suppress the crystallinity of the fluorinated resin, the glass transition temperature (Tg) of the above-mentioned acrylic resin is preferably 100°C or more, more preferably 108°C or more, even more preferably 115°C or more, and even more preferably 117°C or more.

[0101] There is no particular limit to the upper limit of Tg, but from a processability point of view, it is preferably below 150°C, more preferably below 140°C, even more preferably below 130°C, and even more preferably below 125°C.

[0102] In order to achieve the above-mentioned Tg range, the above-mentioned acrylic resin preferably has an imide backbone in its structure.

[0103] <<Other Ingredients>>

[0104] Other components mentioned above may include nucleating agents, ultraviolet absorbers, antioxidants, pigments, antistatic agents, leveling agents, and defoamers, as needed.

[0105] (Nucleating agent)

[0106] As described above, the aggregation of the glossy resin layer can be controlled by using a nucleating agent, which is therefore preferred. Fluoropolymer resins are known to be crystalline resins, which can form crystals within the resin layer. If crystals are formed through aggregation within the resin layer, the crystallite diameter grows, and scattering caused by the crystals can sometimes cause the resin layer to become cloudy. Using the aforementioned nucleating agent can reduce the crystallite diameter, which is therefore preferred. Various nucleating agents can be selected depending on the resin composition used; if acrylic acid-modified polytetrafluoroethylene is used, the crystallite diameter of the fluorine resin can be controlled, which is therefore preferred.

[0107] Commonly used compounds can be used as UV absorbers, antioxidants, pigments, antistatic agents, leveling agents, and defoamers. Benzotriazole compounds are preferred as UV absorbers.

[0108] <Transparent resin layer>

[0109] The aforementioned transparent resin layer is a layer laminated on the side opposite to the article, compared to the glossy resin layer, and is preferably the outermost layer when making a metallic-textured article. The aforementioned transparent resin layer needs to contain resin component (2), which contains one or more fluorinated resins.

[0110] The difference between transparent resin layers and glossy resin layers depends on whether they contain glossy materials.

[0111] The resin component (2) may contain only the fluorinated resin, or may further contain one or more of the thermoplastic resins, or may contain only the fluorinated resin and the thermoplastic resin. The resin component (2) may further contain the other components mentioned above.

[0112] In the aforementioned metallic decorative laminate, external light passes through the transparent resin layer, a portion of which is reflected by the metallic resin layer and then passes through the transparent resin layer again, allowing the observer of the metallic object to perceive the metallic luster. Therefore, the transparent resin layer is required to have high transparency, with a total light transmittance preferably of 80% or more, more preferably 90% or more, further preferably 95% or more, and even more preferably 98% or more. There are no particular limitations on these upper limits, as long as the metallic decorative laminate of this disclosure exhibits its metallic appearance. The aforementioned total light transmittance can be measured, for example, using the method described in the embodiments.

[0113] The aforementioned transparent resin layer is preferably the outermost layer when the metallic-textured article is manufactured as described above. Therefore, in order to improve chemical resistance and weather resistance, the lower limit of its layer thickness is preferably larger, and in order to improve appearance design and moldability, the upper limit of its layer thickness is preferably smaller, preferably 5 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, and even more preferably 25 μm or more. In order to improve chemical resistance and moldability, it is preferably 100 μm or less, more preferably 60 μm or less, further preferably 40 μm or less, and even more preferably 35 μm or less.

[0114] To achieve a balance between chemical resistance, weather resistance, appearance design and moldability, the preferred thickness is 5μm or more and 100μm or less, more preferably 10μm or more and 60μm or less, further preferably 20μm or more and 40μm or less, and even more preferably 25μm or more and 35μm or less.

[0115] When the aforementioned glossy resin layer is used as the outermost surface of a metallic decorative laminate, various patterns can be applied to its surface through embossing or other processes as needed, or a matte finish can be achieved by creating fine textures. Alternatively, a sanding process can be used to create a matte appearance.

[0116] The fluorinated resin, thermoplastic resin and other components used in the above transparent resin layer can be the same as those used in the above resin component (1), and the content of each component is also the same as that of the resin component (1).

[0117] <Other Layers>

[0118] The aforementioned metallic decorative laminate may further include other layers.

[0119] Other layers mentioned above may include, as needed, a surface protective layer, a primer layer, and an adhesive layer.

[0120] As a surface protective layer and primer layer, a general-purpose film such as urethane resin, polyester resin, acrylic resin, urethane acrylate resin, vinyl chloride-vinyl acetate copolymer resin, etc. can be used as an adhesive layer. In order to obtain sufficient transparency and adhesive strength, a polyurethane adhesive layer is preferred.

[0121] [Intermediate layer]

[0122] In this embodiment, the intermediate laminate needs to further include the substrate described later on the transparent resin layer side of the above-described metallic decorative laminate.

[0123] The aforementioned intermediate laminates are manufactured during the production of the aforementioned metallic decorative laminates, etc. The manufacturing methods for each laminate are described below; by laminating a transparent resin layer and a glossy resin layer onto the substrate described later, metallic decorative laminates can be easily manufactured.

[0124] The intermediate laminate only needs to include the aforementioned metallic laminate and substrate, or it can include only the aforementioned metallic laminate and substrate, or it can further include the aforementioned other layers.

[0125] The thickness of the intermediate laminate can be adjusted appropriately, preferably 30 μm or more and 200 μm or less, more preferably 60 μm or more and 160 μm or less, even more preferably 80 μm or more and 140 μm or less, and even more preferably 100 μm or more and 120 μm or less.

[0126] <Substrate>

[0127] As described below, the substrate is used to coat a transparent resin layer during the manufacturing of a metallic decorative laminate. It is the outermost layer protecting the transparent resin layer side of the laminate during handling or storage. Since it is peeled off at any stage of the manufacturing process of the metallic article, it also functions as a release layer.

[0128] As the aforementioned substrate, any substrate used as a substrate in this technical field can be used, and appropriate selections can be made from polyethylene-based substrates, polyester-based substrates (including polyethylene terephthalate (PET) substrates), polycarbonate-based substrates, etc. PET is preferred from the perspective of ease of operation and availability during manufacturing.

[0129] The thickness of the substrate is acceptable as long as it does not hinder the manufacturing process; typically, a substrate thickness of 10μm or more but less than 150μm can be used.

[0130] [Multi-layered stacked body]

[0131] The aforementioned multilayer laminate requires a base layer to be included on the glossy resin layer side of the intermediate laminate. An adhesive layer may further be provided between the intermediate laminate and the base layer, preferably bonded together by the adhesive layer, and may also further include the aforementioned other layers.

[0132] The thickness of the aforementioned multilayer stack can be adjusted appropriately.

[0133] The above-mentioned multilayer laminates are preferably (1) to (4) below. Considering the ease of manufacturing each laminate and the metallic-textured article, (1) and (2) are more preferred, and (2) is even more preferred. It should be noted that " / " refers to the interlayer. The interlayer is sometimes unclear due to partial penetration, etc., and can also be referred to as the manufacturing configuration.

[0134] (1) Substrate / Transparent Resin Layer / Glossy Resin Layer / Base Layer

[0135] (2) Substrate / Transparent Resin Layer / Glossy Resin Layer / Adhesive Layer / Base Layer

[0136] (3) Substrate / Adhesive layer / Transparent resin layer / Glossy resin layer / Base layer

[0137] (4) Substrate / Adhesive layer / Transparent resin layer / Glossy resin layer / Adhesive layer / Base layer

[0138] <Basal layer>

[0139] As for the aforementioned base layer, the impact on appearance design can be considered. Depending on the application, a suitable base layer material can be selected from resins such as polyvinyl chloride, polyolefin, polystyrene, polyacrylic acid, polyurethane, polyamide, polycarbonate, and acrylonitrile-butadiene-styrene copolymer (ABS resin). Considerations include heat resistance when molding into glossy decorative molded products and compatibility with injection molding resins used in injection molding.

[0140] Furthermore, the thickness of the base layer can be set to, for example, 50 μm to 1000 μm, to be a typical thickness for decorative laminates. By setting the base layer thickness within the above range, defects such as wrinkles during film formation can be suppressed, and breakage of the metallic decorative laminate can be suppressed during the molding process of metallic articles, which is therefore preferable. However, if the base layer thickness exceeds 1000 μm, the moldability of the metallic article may decrease.

[0141] The aforementioned base layer preferably contains pigments. This allows for the suppression of the influence of the object's color on metallic-textured objects, and also enables the representation of a color gamut, thus improving the design aesthetics.

[0142] [Decorative Layered Form]

[0143] The aforementioned decorative laminate is a laminate after the aforementioned substrate (release layer) has been peeled from the aforementioned multilayer laminate, and a base layer needs to be included on the glossy resin layer side of the aforementioned metallic decorative laminate.

[0144] As will be described later, metallic items are made using decorative overlays.

[0145] The aforementioned base layer may contain pigments.

[0146] [Metallic items]

[0147] The metallic-textured item in this embodiment needs to have the aforementioned metallic-textured decorative laminate.

[0148] The metallic-textured articles of this embodiment are manufactured, for example, using the aforementioned metallic-textured decorative laminate through the manufacturing method described later, and can be shaped into a desired form according to the purpose. For example, they can be used for housings of smartphones and mobile phones, car bumpers, car logos, car door rearview mirror housings, front grilles, car door handles, center wheel covers, car logos, decorations, decorative parts, lamp reflectors, center consoles, mounting panels, etc., housings or decorative parts of personal computers or TVs, washing machines, refrigerators, etc., housings or decorative parts of pinball machines, marbles, game consoles, etc., or for general use in suitcases or luggage, etc., and can replace plating and metal materials to give them a metallic-textured decorative and aesthetic appearance.

[0149] In particular, the metallic decorative laminate of this embodiment not only gives the article a metallic appearance design, but also gives the article chemical resistance and weather resistance. In this disclosure, "article" refers to the precursor of a metallic article, which becomes a metallic article by being decorated using the above-described decorative laminate.

[0150] In addition to the above-described configuration, the metallic article of this embodiment may also have other configurations. For example, in order to keep the surfaces of the protective layer and the substrate layer clean and prevent dirt from adhering before using the metallic article of this embodiment, release paper, protective film, etc., may be provided on the surfaces of the protective layer and the substrate layer.

[0151] [Manufacturing methods for intermediate laminates, multi-layer laminates, decorative laminates, and metallic-textured items]

[0152] The metallic decorative laminate of this embodiment is common to intermediate laminates, multilayer laminates, decorative laminates, and metallic articles, and is formed during the manufacturing process of the aforementioned intermediate laminate.

[0153] The manufacturing method of the intermediate laminate described in this embodiment includes, in sequence: applying a coating liquid containing one or more of the above-mentioned fluorinated resins; applying a coating liquid containing one or more of the above-mentioned fluorinated resins, one or more of the above-mentioned pigments, and one or more of the above-mentioned glossy materials; and heating.

[0154] The descriptions of fluorinated resins, glossy materials, thermoplastic resins, other components, metallic decorative laminates, intermediate laminates, multilayer laminates, decorative laminates, and metallic items have already been provided, and therefore are omitted.

[0155] (Coating solution containing one or more of the above-mentioned fluorinated resins)

[0156] The coating liquid containing one or more of the above-mentioned fluorinated resins is a coating liquid used to form a transparent resin layer, and may further contain the above-mentioned thermoplastic resins and / or other components.

[0157] The above-mentioned coating liquid may further contain a solvent, which may be a homogeneous solvent or a slurry.

[0158] (solvent)

[0159] As the solvent mentioned above, any solvent commonly used in this field is acceptable. Polar solvents such as ester-based solvents, ether-based solvents, and ketone-based solvents can be selected; non-polar solvents such as hydrocarbon-based solvents and aromatic solvents can be selected; alcohol-based solvents such as methanol, ethanol, and isopropanol can be selected, with polar solvents such as ester-based solvents, ether-based solvents, and ketone-based solvents being preferred.

[0160] In the method for manufacturing the metallic decorative laminate of this embodiment, it is preferable to exhibit properties that are unsuitable for fluorinated resins and good for acrylic resins. If the fluorinated resin is not dissolved in the coating solution before the heating described later, it will not react with the acrylic resin before heating, and no agglomerates formed by the reactants of the fluorinated and acrylic resins will be generated in the coating solution; therefore, this is preferable. By preventing the formation of such agglomerates, uneven coating will not occur during application, thus enabling the production of a uniform, glossy resin layer. Butyl carbitol acetate is a preferred solvent exhibiting these properties.

[0161] When using the above-mentioned solvent, in order to shorten the heating treatment time described later and improve the coatability of the coating liquid to the substrate, the amount of solvent is preferably 80.0 parts by weight or more and 500.0 parts by weight or less, more preferably 100.0 parts by weight or more and 300.0 parts by weight or less, and even more preferably 150.0 parts by weight or more and 200.0 parts by weight or less, relative to a total of 100 parts by weight of the above-mentioned fluorinated resin and the above-mentioned acrylic resin.

[0162] (A coating liquid containing one or more of the above-mentioned fluorinated resins, one or more of the above-mentioned pigments, and one or more of the above-mentioned glossy materials)

[0163] The coating liquid containing one or more of the above-mentioned fluorinated resins, one or more of the above-mentioned pigments, and one or more of the above-mentioned glossy materials is a coating liquid used to form a glossy resin layer, and may further contain the above-mentioned thermoplastic resins and / or other components.

[0164] The above-mentioned coating liquid may further contain the above-mentioned solvent, which may be a homogeneous solvent or a slurry.

[0165] <Coating>

[0166] The above coating can be applied to the substrate or the resin layer formed on the substrate by known methods such as gravure coating machine, reverse coating machine, die coating machine, doctor blade coating machine, and roller coating machine.

[0167] <Heating>

[0168] The heating described above can begin before the coating process is completed or after the coating process is completely finished, preferably while the substrate still has the coating liquid on it. This heating also includes cases where the substrate is preheated before coating and then further heated.

[0169] By heating as described above, the solvent is removed by distillation when used in the coating solution. By heating the resin component to a Tg level above the resin component contained therein, it can be mixed with the fluorinated resin. As a result, the crystallite diameter of the fluorinated resin does not grow, the precipitation of the fluorinated resin from the resin component is suppressed, and the glossy material is uniformly dispersed, which is therefore preferable.

[0170] The heating temperature can be appropriately selected based on the heating time, the fluorinated resin, pigment, thermoplastic resin, other components, solvent and substrate used. In order to obtain a metallic decorative laminate with excellent appearance design and chemical resistance, weather resistance and formability, it is preferably 100°C or above, more preferably 150°C or above, even more preferably 170°C or above, preferably 250°C or below, more preferably 220°C or below, and even more preferably 200°C or below.

[0171] The heating method can be appropriately selected based on the shape, size, and other characteristics of the object being heated.

[0172] The heating time can be appropriately selected according to the size of the laminate being manufactured, the heating temperature, the fluorine resin, thermoplastic resin, solvent and substrate used. In order to obtain a metallic decorative laminate with excellent appearance design and excellent millimeter wave transmittance, it is preferred to be 30 seconds or more, more preferably 1 minute or more, more preferably 5 minutes or less, and more preferably 3 minutes or less.

[0173] <Removing Substrate>

[0174] The method for manufacturing the decorative laminate of this embodiment needs to include peeling a substrate from the multilayer laminate.

[0175] The metallic decorative laminate manufactured by the above-described method is formed on a substrate. Therefore, by peeling off the substrate (release layer), the decorative laminate is obtained.

[0176] There are no particular limitations on the method of stripping, as long as it is a method commonly used in the field.

[0177] <Methods for manufacturing metallic-looking items>

[0178] The metallic-textured article of this embodiment can be manufactured, for example, by the following method.

[0179] The molding process includes: setting the surface temperature of the decorative laminate to 150°C to 200°C, sealing it with a mold so that the base film side of the decorative laminate becomes the article side, and molding it on the surface of the article to obtain a metallic article.

[0180] (Molding process)

[0181] To thermoform the decorative laminate, the surface temperature of the decorative laminate is maintained at 150°C to 200°C. This prevents the decorative laminate from sagging or whitening during molding, thus ensuring good formability. By maintaining a surface temperature above 150°C, the decorative laminate softens sufficiently, preventing sagging and deformation caused by sagging, thus simplifying processing and molding. Furthermore, by maintaining a surface temperature below 200°C, the decorative laminate is prevented from becoming excessively soft and molten, thus avoiding difficulties in molding and the occurrence of whitening.

[0182] The shape of the mold that seals the decorative laminate can be set to any shape, allowing metallic objects to be molded into the desired form. For example, positive and negative molds with chrome-plated brass surfaces can be used. Furthermore, the mold temperature can be set to any temperature, taking into account the control of the surface temperature of the decorative laminate and the cooling conditions of the metallic object after the molding process.

[0183] As a method for sealing the decorative laminate within the mold, any method can be employed, such as linear forming using a female mold, curtain forming using a male mold, or plug-assisted forming using an auxiliary mold, taking into account factors such as ease of molding and cost. Alternatively, vacuum forming, where the metallic decorative laminate is sucked into the mold, or air-pressurized forming, where compressed air pressure seals the metallic decorative laminate within the mold, can be used. For example, by utilizing vacuum and / or compressed air to seal the metallic decorative laminate with the mold, the seal between the decorative laminate and the mold is improved, thus enabling the processing of more precise shapes.

[0184] (Clamping process)

[0185] The aforementioned method for manufacturing metallic articles may include a clamping step before the molding step to secure the decorative layer. This step allows for adjustment and fixation to prevent the decorative layer from loosening during molding. The clamp can be, for example, using multiple holding units capable of holding both sides of the decorative layer, such as holding both ends of the decorative layer. The holding of the decorative layer is not limited to its ends; any part of the decorative layer can be held. Typically, in the case of continuous production of metallic articles, both ends in the width direction of the decorative layer can be held. Furthermore, when mass-producing metallic articles by cutting the decorative layer into quadrilaterals of predetermined lengths, the ends of the four sides can be held by upper and lower frames.

[0186] (Heating process)

[0187] Furthermore, the manufacturing method of the aforementioned metallic-textured article may include a heating step after the clamping step, in which the decorative laminate is heated. For example, after clamping the room-temperature decorative laminate to prevent it from loosening, multiple heaters or the like can be used as heating units, positioned above and below the decorative laminate, to simultaneously and evenly heat both sides of the decorative laminate. This heating step allows the surface temperature of the decorative laminate to be controlled between 150°C and 200°C.

[0188] (Other processes)

[0189] In addition to the steps described above, the manufacturing method for metallic-textured articles may include other steps. For example, to maintain the surfaces of the protective layer and substrate layer in a clean state and prevent dirt adhesion before processing the metallic-textured article in the next step, a process of applying a protective film or similar material to the surfaces of the protective layer and substrate layer may be included. Furthermore, after inserting the metallic-textured article into an injection molding mold, resin embedding injection molding may be performed to decorate the surface of the injection-molded article.

[0190] The metallic decorative laminate, the intermediate laminate including the metallic decorative laminate, the multilayer laminate, the decorative laminate, the metallic article, and the manufacturing method of the intermediate laminate and the decorative laminate of this embodiment are preferably as described below [1] to

[13] .

[0191] [1] A metallic decorative laminate comprising: a glossy resin layer containing a resin component (1), one or more pigments and one or more glossy materials; and a transparent resin layer containing a resin component (2), wherein the resin component (1) contains one or more fluorinated resins and the resin component (2) contains one or more fluorinated resins.

[0192] [2] The metallic decorative laminate according to [1], wherein the resin component (1) further contains one or more thermoplastic resins.

[0193] [3] According to the metallic decorative laminate of [2], the glossy material in the glossy resin layer is 0.01 parts by mass or more and 20.00 parts by mass or less relative to 100 parts by mass of the resin component (1).

[0194] [4] The metallic decorative laminate according to any one of [1] to [3], wherein the above-mentioned glossy material contains at least one material selected from flake-like or sheet-like metal, flake-like or sheet-like alloy metal, flake-like or sheet-like metal oxide, flake-like or sheet-like mica, glass flakes and film pulverizers.

[0195] [5] The metallic decorative laminate according to any one of [1] to [4], wherein the pigment in the glossy resin layer is 0.05 parts by mass or more and 20.00 parts by mass or less relative to 100 parts by mass of the resin component (1).

[0196] [6] The metallic decorative laminate according to any one of [1] to [5], wherein the pigment contains an inorganic pigment or an organic pigment.

[0197] [7] The metallic decorative laminate according to any one of [1] to [7], wherein the resin component (2) further contains one or more thermoplastic resins.

[0198] [8] An intermediate laminate comprising a substrate on the transparent resin layer side of the metallic decorative laminate described in any one of [1] to [7].

[0199] [9] A multilayer laminate comprising a base layer on the glossy resin layer side of the intermediate laminate described in [8].

[0200]

[10] A decorative laminate comprising a base layer on the glossy resin layer side of the metallic decorative laminate described in any one of [1] to [7].

[0201]

[11] A metallic article having any one of the metallic decorative layers described in [1] to [7].

[0202]

[12] The method for manufacturing the intermediate laminate according to [8] includes, in sequence: coating with a coating liquid containing one or more fluorinated resins; coating with a coating liquid containing one or more fluorinated resins, one or more pigments and one or more glossy materials; and heating.

[0203]

[13] The method of manufacturing a decorative laminate according to

[10] includes peeling a substrate from the multilayer laminate of [9].

[0204] Example

[0205] The present invention will now be described in more detail using examples. However, the present invention is not limited to any of the examples described below.

[0206] (Evaluation Method)

[0207] 1. Evaluation of chemical resistance

[0208] The chemical resistance evaluation was conducted using a commercially available brake fluid (manufactured by ○○ Company, product name: ○○) with polyethylene glycol monoether as the main component, in vehicles such as four-wheeled or two-wheeled vehicles and vacuum pumps. A 25cm × 25cm decorative laminate obtained in the examples and comparative examples was prepared as a test sample. At 25°C, 1 mL of the above-mentioned brake fluid was added to the transparent resin layer side of the decorative laminate using a dropper, at 3 × 3 points (9 points in total). After standing for 5 hours, the brake fluid was washed with toluene, and the laminate was placed at 25°C for 1 hour. After confirming that the toluene was dry, the surface condition was visually observed and evaluated as A to D.

[0209] A: No changes were found in any of the 9 points compared to before the test.

[0210] B: Drip marks from brake fluid can be identified in areas smaller than 4 points.

[0211] C: Brake fluid drip marks can be identified in the area between 4 and 8 o'clock.

[0212] D: Brake fluid drip marks can be identified above 8 o'clock.

[0213] 2. Weather resistance evaluation

[0214] A xenon lamp weathering tester SX75 7.5kW (Suga tester) was used. The treatment conditions were: black panel temperature 63±2℃, humidity 50%RH, rainfall cycle (non-rainfall time / rainfall time) 102min / 18min, and illuminance 180W / m². 2 The temperature inside the tank is 25℃~35℃, and the concentration is 500MJ / m. 2 The color difference of the transparent resin layer side of the decorative laminates obtained in the Examples and Comparative Examples before and after treatment was measured using a colorimeter CM-3600A (manufactured by Konica Minolta), and evaluated as A to C below.

[0215] A: It is rated as having excellent weather resistance when △E* = 3.0 or less.

[0216] B: When △E* is greater than 3.0 and less than 5.0, it is evaluated as having weather resistance.

[0217] C: When △E* is greater than 5.0, it is evaluated as having no weather resistance.

[0218] 3. Heat resistance evaluation

[0219] The decorative laminates obtained in the examples and comparative examples were placed at 100°C for 500 hours. The color difference of the sample surface on the transparent resin layer side of the decorative laminate before and after the test was measured using a colorimeter CM-3600A (manufactured by Konica Minolta), and evaluated as A to C below.

[0220] A: When △b* = 1.0 or less and there are no adverse conditions such as peeling of decorative pieces, it is rated as having very good heat resistance.

[0221] B: When △b* is greater than 1.0 and less than 3.0 and there are few defects such as peeling of decorative pieces, it is evaluated as having heat resistance.

[0222] C: If △b* is greater than 5.0 and significant defects such as peeling of the decorative piece are confirmed, it is evaluated as having no heat resistance.

[0223] 4. Appearance Design Evaluation

[0224] The decorative laminates obtained in the Examples and Comparative Examples are evaluated as A or B by visually observing them from the transparent resin layer side.

[0225] A: It features a metallic-looking design.

[0226] B: The exterior design does not present a metallic texture, or it presents a matte finish.

[0227] 5. Total light transmittance

[0228] For the decorative laminates obtained in the examples or comparative examples, the total light transmittance was measured using a spectrophotometer (manufactured by Hitachi High Technology Co., Ltd., UH 4150) in accordance with JISK 7375:2008.

[0229] 6. Evaluation of the appearance design after molding

[0230] The metallic-textured items made using the decorative laminates obtained in the examples and comparative examples were evaluated by visual observation.

[0231] 7. Formability Evaluation

[0232] For metallic-textured articles made using the decorative laminates obtained in the examples and comparative examples, the presence of white turbidity in the stretched portion (200% stretch before stretching) of the laminate at the corner of the mold after the molding process is visually observed and evaluated as a measure of formability.

[0233] (Materials used)

[0234] (Fluoropolymer resin (manufactured by ARKEMA Corporation, kyanr 301))

[0235] Number average molecular weight (Mn): 1,200

[0236] Weight-average molecular weight (Mw): 1,600

[0237] Z-average molecular weight (Mz): 1,900

[0238] Polydispersity (Mw / Mn): 1.3

[0239] Peak area ratio: 14%

[0240] (Acrylic resin (manufactured by Asahi Kasei Corporation, SK 540))

[0241] Number average molecular weight (Mn): 46,000

[0242] Weight-average molecular weight (Mw): 93,000

[0243] Z-average molecular weight (Mz): 150,000

[0244] Polydispersity (Mw / Mn): 2.0

[0245] Peak area ratio: 86%

[0246] (Pigment 1)

[0247] White pigment: MHI White#148 (manufactured by Mikuni Shiki Co., Ltd.)

[0248] (Pigment 2)

[0249] Black pigment: MHI BLACK#C004 (manufactured by Mikuni Pigment Co., Ltd.)

[0250] (Pigment 3)

[0251] Blue pigment: MHI Blue#C362M (manufactured by Mikuni Shiki Co., Ltd.)

[0252] (Pigment 4)

[0253] Red pigment: MHI Red#CC361 (manufactured by Mikuni Shiki Co., Ltd.)

[0254] (Glossy Material 1)

[0255] Pearl pigment: TWINCLEPEARL SXC-SO (manufactured by Koken Kogyo Co., Ltd., Japan, volume average particle size (D) 50 ): 22μm

[0256] (Glossy Material 2)

[0257] Aluminum sheet: GX40A (manufactured by Asahi Kasei Corporation, volume average particle size (D) 50 ): 19μm

[0258] (Glossy Material 3)

[0259] Pearl pigment: TWINCLEPEARL (registered trademark) BXC-SO (manufactured by Koken Kogyo Co., Ltd., Japan, volume average particle size (D)50 ): 22μm

[0260] (Example 1)

[0261] <Manufacturing of intermediate layers containing metallic decorative layers>

[0262] (Film formation of transparent resin layer)

[0263] The transparent resin layer described later is coated onto the substrate (PET film (G2000 (manufactured by Toyobo Co., Ltd.))) using a coating solution. The coating amount is adjusted so that the thickness of the glossy resin layer after heating is 30 μm.

[0264] Immediately after coating, heat at 180°C for 2 minutes to form a transparent resin layer on the substrate. Then, cool to room temperature.

[0265] (Coating solution for transparent resin layer)

[0266] To 37.45 g of butyl carbitol acetate (manufactured by Sankyo Kasei Corporation), 8.75 g of acrylic resin (manufactured by Asahi Kasei Corporation, SK 540) was added, and the mixture was stirred at room temperature to form a homogeneous solution. Further addition of other components (0.57 g of ultraviolet absorber (manufactured by BASF Japan Corporation, Tinuvin 900) and 0.06 g of nucleating agent (manufactured by Mitsubishi Chemical Corporation, A-3000)) and 13.16 g of fluorinated resin (manufactured by ARKEMA Corporation, kyanr 301) was made, and the mixture was stirred further to form a transparent resin layer coating solution containing resin component (2).

[0267] Tables 1 and 2 record the contents of acrylic resin, fluorinated resin and other components in the resin components (2) used in the examples and comparative examples.

[0268] (Film formation of glossy resin layer)

[0269] The glossy resin layer, described later, is coated onto the transparent resin layer of the substrate with the aforementioned transparent resin layer using a coating solution. The coating amount is adjusted so that the film thickness of the glossy resin layer after heating is 30 μm.

[0270] Immediately after coating, heat at 180°C for 2 minutes to laminate a glossy resin layer. Then, cool to room temperature to create an intermediate laminate containing a metallic decorative laminate.

[0271] The substrate was peeled off from the obtained intermediate laminate, and the transparent resin layer side was evaluated for chemical resistance, weather resistance, heat resistance, appearance design, and total light transmittance. The results are recorded together with those of other examples and comparative examples in Tables 3 and 4.

[0272] (Coating for glossy resin layers)

[0273] To 37.45 g of butyl carbitol acetate (manufactured by Sankyo Kasei Corporation), 8.75 g of acrylic resin (manufactured by Asahi Kasei Corporation, SK 540) was added, and the mixture was stirred at room temperature to prepare a homogeneous solution. Further additions of other components (0.57 g of UV absorber (manufactured by BASF Japan Corporation, Tinuvin 900) and 0.06 g of nucleating agent (manufactured by Mitsubishi Chemical Corporation, A-3000), pigment 1 (used in a manner where the pigment component is 2.00 parts by weight relative to 1100 parts by weight of resin component 1), and 13.16 g of fluorinated resin (manufactured by Arkema Corporation, Kyanr 301) were added and stirred to prepare a solution containing resin component (1). To the obtained solution containing resin component (1), 1.13 g of glossy material 1 was added, and the mixture was stirred further to prepare a coating liquid for a glossy resin layer.

[0274] Tables 1 and 2 record the contents of acrylic resin, fluorinated resin and other components in the resin composition (1) used in the examples and comparative examples.

[0275] Tables 1 and 2 record the contents of acrylic resins, fluorinated resins, and other components in resin components (1) and (2), and also record the amount (parts by mass) of pigments and glossy materials used when resin component (1) is set to 100 parts by mass. In the tables, "-" indicates that no materials were used.

[0276] [Table 1]

[0277]

[0278] [Table 2]

[0279]

[0280] <Making Metallic Items>

[0281] (Film formation of adhesive layer and substrate layer)

[0282] On the glossy resin layer of the above intermediate laminate, a main agent consisting of a mixture of polyester diol, polycarbonate diol, carbodiimide, silane coupling agent with epoxy group and ethyl acetate, and a curing agent consisting of aliphatic isocyanate are mixed and used as a urethane adhesive for metallic decorative sheets.

[0283] As a polyester diol, TM-K51 (manufactured by Toyo Morton Co., Ltd.) was used; as a polycarbonate diol, DURANOL T5652 (manufactured by Asahi Kasei Corporation) was used; as a carbodiimide, CARBODILITE V-07 (manufactured by Nisshinbo Chemical Co., Ltd.) was used; as an epoxy-containing silane coupling agent, KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used; and as an aliphatic isocyanate, CAT-RT85 (manufactured by Toyo Morton Co., Ltd.) was used.

[0284] Using a standard of 10 μm for the dry film thickness of the aforementioned adhesive layer, a urethane adhesive is applied to the surface of a glossy resin layer using a bar coater. After drying the coating at 60°C for 1 minute, the coating is laminated with a PET film (average thickness 25 μm, Teflex FT3, Toyobo) as the base layer to manufacture a multilayer laminate.

[0285] The substrate is peeled off from the obtained multilayer laminate to manufacture a decorative laminate.

[0286] Using the obtained decorative laminate, a vacuum molding machine is used to clamp the base layer of the decorative laminate into a test mold, and the pre-forming temperature is set to 160°C and the vacuum pressure is set to 6 bar. The metallic decorative laminate is pre-formed in a manner that matches the mold used for injection molding. Unwanted parts protruding from the mold are trimmed and cut to obtain a metallic item.

[0287] The chemical resistance, weather resistance, heat resistance, appearance design, and total light transmittance of the decorative laminate and metallic articles obtained in Example 1 were evaluated, and the results are recorded in Tables 3 and 4.

[0288] Both the post-molding appearance design evaluation and the moldability evaluation showed no practical problems.

[0289] Examples 2 through 6 and Comparative Examples 1 through 5

[0290] Except for changing the film thickness, the amount of fluorinated resin, the amount of acrylic resin, the type of pigment, the amount of pigment, the type of glossy material, and the amount of glossy material as described in Tables 1 and 2 in Example 1, the decorative laminates and metallic articles of Examples 2 to 6 and Comparative Examples 1 to 5 were manufactured in the same manner as in Example 1. In Tables 1 and 2, the materials used are listed in the upper paragraph for “pigments” and “glossy materials”, and the amount used is listed in the lower paragraph relative to 100 parts by mass of resin component (1).

[0291] The chemical resistance, weather resistance, heat resistance, appearance design, and total light transmittance of the decorative laminates and metallic articles obtained in Examples 2 to 6 and Comparative Examples 1 to 5 were evaluated, and the results are recorded in Tables 3 and 4.

[0292] Both the post-molding appearance design evaluation and the moldability evaluation showed no practical problems.

[0293] [Table 3]

[0294]

[0295] [Table 4]

[0296]

[0297] As shown in Tables 3 and 4, the results of Examples 1 to 6 demonstrate that the metallic decorative laminate of this embodiment exhibits a metallic appearance and excellent properties in terms of chemical resistance, weather resistance, heat resistance, and total light transmittance. Furthermore, it reduces the environmental impact caused by wastewater generated from metal plating.

[0298] Furthermore, it can be confirmed that metallic items containing metallic decorative layers are functionally sound.

[0299] In contrast, in Comparative Examples 1 to 5, since the glossy resin layer does not contain glossy materials, it does not exhibit a metallic appearance design.

[0300] Industrial utilization potential

[0301] The metallic decorative laminate, intermediate laminate, multilayer laminate, decorative laminate, and metallic article of this embodiment present an excellent metallic appearance design, reduce the environmental impact during manufacturing, and have chemical resistance and weather resistance, resulting in excellent productivity. It can replace plating and metal materials to give metallic decorative and appearance design, and is suitable for use in automobiles, home appliances, information terminals, etc.

[0302] Explanation of reference numerals in the attached figures

[0303] 1: Metallic decorative layered body,

[0304] 2: Intermediate laminate,

[0305] 3: Decorative layered body,

[0306] 4: Multilayer stacked body

[0307] 10: Substrate (release layer),

[0308] 20: Transparent resin layer

[0309] 30: Glossy resin layer,

[0310] 31: The surface opposite to the item with a glossy resin layer.

[0311] 32: The surface of the item side with a glossy resin layer.

[0312] 40: Adhesive layer,

[0313] 50: Basal layer,

[0314] 100: In the thickness direction

[0315] 110: Width direction

[0316] 120: Length direction

[0317] 200: Glossy materials,

[0318] 210: Thickness direction of glossy materials,

[0319] 211: Thickness of glossy materials,

[0320] 220: Particle size orientation of glossy materials

[0321] 221: Particle size of glossy materials.

Claims

1. A metallic decorative laminate, comprising: A glossy resin layer containing resin component (1), one or more pigments, and one or more glossy materials, wherein the resin component (1) contains one or more fluorinated resins; and A transparent resin layer containing resin component (2), wherein the resin component (2) contains one or more fluorinated resins.

2. The metallic decorative laminate according to claim 1, wherein, The resin component (1) further contains one or more thermoplastic resins.

3. The metallic decorative laminate according to claim 2, wherein, The glossy material in the glossy resin layer is 0.01 parts by mass or more and 20.00 parts by mass or less relative to 100 parts by mass of the resin component (1).

4. The metallic decorative laminate according to claim 1, wherein, The bright material contains at least one material selected from flake-like or sheet-like metals, flake-like or sheet-like alloy metals, flake-like or sheet-like metal oxides, flake-like or sheet-like mica, glass flakes, and film fragments.

5. The metallic decorative laminate according to claim 1, wherein, The pigment in the glossy resin layer is 0.05 parts by mass or more and 20.00 parts by mass or less relative to 100 parts by mass of the resin component (1).

6. The metallic decorative laminate according to claim 1, wherein, The pigment contains inorganic or organic pigments.

7. The metallic decorative laminate according to claim 1, wherein, The resin component (2) further contains one or more thermoplastic resins.

8. An intermediate laminate comprising a substrate on the transparent resin layer side of the metallic decorative laminate of claim 1.

9. A multilayer laminate comprising a base layer on the glossy resin layer side of the intermediate laminate of claim 8.

10. A decorative laminate comprising a base layer on the glossy resin layer side of the metallic decorative laminate of claim 1.

11. A metallic article comprising the metallic decorative laminate as described in claim 1.

12. A method for manufacturing the intermediate laminate of claim 8, comprising, in sequence: Apply a coating solution containing one or more fluorinated resins; A coating liquid containing one or more fluorinated resins, one or more pigments, and one or more glossy materials; and Heat it up.

13. A method of manufacturing a decorative laminate of claim 10, comprising peeling a substrate from the multilayer laminate of claim 9.

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