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

Abstract

Provided is a metallic-toned decorative laminate comprising: a lustrous resin layer that contains one or more lustrous materials, one or more pigments, and a resin component (1) which contains one or more fluororesins; and a transparent resin layer that contains a resin component (2) which contains one or more fluororesins. Also provided are an intermediate laminate, a multilayer laminate, decorative laminate, a metallic-toned article, a method for producing the intermediate laminate, and a method for producing the decorative laminate.

Description

[Technical Field]

[0001] The present invention relates to a metallic-looking decorative laminate, an intermediate laminate, a multilayer laminate, a decorative laminate, a metallic-looking article, a method for manufacturing the intermediate laminate, and a method for manufacturing the decorative laminate. [Background technology]

[0002] To enhance the aesthetic appeal of resin molded products, a metallic luster has been imparted to the surface of these products. Metal plating has been used as a means of imparting this metallic luster (Patent Document 1). Furthermore, electromagnetic wave-transmitting glossy coated resin products (Patent Document 2) have been developed for other applications. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2002-241948 [Patent Document 2] Japanese Patent Publication No. 2010-030075 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The present invention aims to provide metallic decorative laminates, intermediate laminates, multilayer laminates, decorative laminates, and metallic articles that exhibit excellent metallic designs, reduce environmental impact during manufacturing, and have improved chemical resistance and weather resistance, as well as to provide a method for manufacturing the intermediate laminate and the decorative laminate. [Means for solving the problem]

[0005] The inventors have conducted diligent studies to solve the above problems and provide the following [1] to [7]. [1] A resin component (1) containing one or more types of fluororesins, a glossy resin layer containing one or more types of dyes and one or more types of glossy materials, A metallic decorative laminate comprising a transparent resin layer containing a resin component (2) containing one or more types of fluororesins. [2] An intermediate laminate comprising a substrate on the transparent resin layer side of the metallic decorative laminate described in [1]. [3] A multilayer laminate comprising a base layer on the glossy resin layer side of the intermediate laminate described in [2]. [4] A decorative laminate comprising a base layer on the glossy resin layer side of the metallic decorative laminate described in [1]. [5] A metallic article comprising a metallic decorative laminate as described in [1]. [6] A method for producing an intermediate laminate according to [2], comprising, in this order: applying a coating liquid containing one or more types of fluororesins; applying a coating liquid containing one or more types of fluororesins, one or more types of dyes and one or more types of glossy materials; and heating. A method for producing a decorative laminate according to [4], comprising peeling off a substrate from the multilayer laminate according to [3] [7] [3]. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide metallic decorative laminates, intermediate laminates, multilayer laminates, decorative laminates, and metallic articles that exhibit an excellent metallic design, reduce the environmental burden during manufacturing, and have improved chemical resistance and weather resistance, as well as to provide a method for manufacturing the intermediate laminate and a method for manufacturing the decorative laminate. [Brief explanation of the drawing]

[0007] [Figure 1] This is a schematic diagram showing an example of a multilayer laminate including a metallic decorative laminate according to this embodiment. [Figure 2] This is a schematic diagram of the lustrous material in a lustrous resin layer. [Modes for carrying out the invention]

[0008] Patent Document 1 describes an invention relating to a plated synthetic resin component for vehicles that exhibits a metallic luster when plated. However, metal plating has problems such as a complex process and high manufacturing costs, as well as the generation of wastewater which puts a burden on the environment. In addition, it was difficult to apply a uniform and beautiful plating film when the surface of the molded body had an uneven shape.

[0009] Patent Document 2 describes an aluminum-look bumper that transmits millimeter waves. However, although it achieves a metallic appearance through aluminum flakes, it focuses on millimeter wave transmission and has not adequately considered chemical resistance and weather resistance.

[0010] In contrast, the metallic decorative laminate of this disclosure, by having a specific layer structure, makes it possible to obtain a metallic decorative laminate that exhibits an excellent metallic design and has improved chemical resistance and weather resistance.

[0011] In addition, it is possible to provide intermediate laminates, multilayer laminates, decorative laminates, and metallic articles, which are composed of the metallic decorative laminate, as well as a method for manufacturing the intermediate laminate and a method for manufacturing the decorative laminate.

[0012] The following describes the metal-like decorative laminate, intermediate laminate, multilayer laminate, decorative laminate, metal-like article, and method for manufacturing the metal-like decorative laminate according to the present invention. However, the present invention is not limited to the following examples.

[0013] In this disclosure, the thickness direction 100 refers to the lamination direction of the metallic decorative laminate or metallic article, as shown in Figure 1, and the width direction 110 refers to a direction different from the thickness direction, and is perpendicular to the longitudinal direction 120 of the metallic decorative laminate or metallic article. For example, when the intermediate laminate described later is manufactured by roll-to-roll, the longitudinal direction 120 corresponds to the flow direction (MD: machine direction), and the width direction 110 corresponds to the TD (transverse direction) perpendicular to the MD.

[0014] Hereinafter, embodiments of the present disclosure (hereinafter may be referred to as "the present embodiments") will be described. In the present disclosure, numerical values related to descriptions of numerical ranges such as "above", "below", "~", etc. are numerical values that can be arbitrarily combined.

[0015] Also, the defined provisions that are considered preferable can be arbitrarily adopted. That is, one of the defined provisions that are considered preferable can be adopted in combination with one or more other defined provisions that are considered preferable. Combinations of preferable ones can be said to be more preferable.

[0016] 〔Metallic Decorative Laminate〕 The metallic decorative laminate of the present embodiment needs to be a metallic decorative laminate including a resin component (1) containing one or more fluorine-based resins, a phosphorescent resin layer containing one or more pigments and one or more phosphorescent materials, and a transparent resin layer containing a resin component (2) containing one or more fluorine-based resins..

[0017] The metallic decorative laminate includes a phosphorescent resin layer and a transparent resin layer. The phosphorescent resin layer contains a resin component (1), a pigment, and a phosphorescent material, and the resin component (1) contains a fluorine-based resin. The transparent resin layer contains a resin component (2), and the resin component (2) contains a fluorine-based resin.

[0018] The metallic decorative laminate of this embodiment can be used, for example, to decorate resin parts and metal parts (hereinafter also simply referred to as "articles") such as bumpers for automobiles by film decoration methods such as insert molding or overlay molding using a multilayer laminate including the metallic decorative laminate. Furthermore, the multilayer laminate including the metallic decorative laminate may be used to decorate the surface of an article via an adhesive layer or bonding layer, and can be used as a surface layer in the exterior of an automobile, such as pillars, door moldings, roof moldings, entire door surfaces, and entire roof surfaces. In addition, the metallic decorative laminate of this embodiment exhibits an excellent metallic design and has excellent chemical resistance and weather resistance, making it suitable for outdoor use. Moreover, due to its excellent chemical resistance, it is preferable to use it for decorating four-wheeled vehicles, two-wheeled vehicles, pumps, etc., where lubricating oil is used.

[0019] Furthermore, as will be described in more detail later, the metallic decorative laminate of this embodiment is preferable because it is easy to manufacture and therefore has excellent mass-producibility.

[0020] In this embodiment, the layer thickness of the metallic decorative laminate is preferably 20 μm or more, more preferably 30 μm or more, even more preferably 35 μm or more, and even more preferably 40 μm or more, while in order to improve moldability, it is preferably 100 μm or less, more preferably 80 μm or less, even more preferably 70 μm or less, and even more preferably 65 μm or less. Although it might seem that a thicker layer would be preferable for chemical resistance, it was found that if the layer thickness becomes too thick, it actually deteriorates.

[0021] To achieve a balance between aesthetic appeal, weather resistance, and chemical resistance, the particle size is preferably 20 μm to 100 μm, more preferably 30 μm to 80 μm, even more preferably 35 μm to 70 μm, and even more preferably 40 μm to 65 μm.

[0022] In this disclosure, "design appeal" means the property that, when the metallic decorative laminate of this disclosure is used in an article, the article exhibits a metallic design and can express the required color tone by adding pigments and lustrous materials.

[0023] In this disclosure, "chemical resistance" refers to the property that prevents dissolution, swelling, and reaction when organic solvents or lubricating oils come into contact with the transparent resin layer contained in the metallic decorative laminate of this disclosure, and includes oil resistance and solvent resistance, which can be evaluated, for example, by the method described in the examples.

[0024] In this disclosure, "weather resistance" means the property of being resistant to deformation, discoloration, deterioration, etc., when used outdoors, and can be evaluated, for example, by the method described in the examples.

[0025] In this disclosure, "formability" means the ease with which a metallic-looking laminate can be manufactured when producing a metallic-looking article using the metallic-looking laminate of this disclosure. Formability is preferable when the layer thickness is increased because it suppresses tearing during molding, and preferable when the layer thickness is decreased because it allows for decoration of fine details of the article. For example, it can be evaluated by the method described in the examples.

[0026] The total light transmittance of the metallic decorative laminate of this embodiment can be adjusted as needed. As described later, the metallic decorative laminate of this embodiment exhibits a metallic design due to the luminous materials and pigments it contains.

[0027] The total light transmittance of the metallic decorative laminate of this embodiment can be appropriately adjusted by the amount of lustrous material, the shape of the lustrous material, the amount of pigment, etc.

[0028] In this embodiment, a low total light transmittance is preferable for the metallic-looking laminate, as it allows the metallic design to be displayed when exposed to strong ambient light, such as sunlight during the day. The total light transmittance can be adjusted by the content of the luminous material and / or pigment. When a light source is placed on the article side of the metallic-looking laminate and the color is displayed by the light passing through the metallic-looking laminate, a high total light transmittance is preferable. When the content is increased to more strongly display the metallic design with the luminous material, the total light transmittance becomes lower, which is preferable because it blocks the color of the article to which the metallic look is applied. The total light transmittance can also be lowered by increasing the pigment content to adjust the color tone. In order to achieve such effects, the total light transmittance is preferably 3% or more, more preferably 5% or more, even more preferably 6% or more, and even more preferably 8% or more. There is no particular upper limit, as long as the metallic design of the metallic decorative laminate of this disclosure is achieved, it is preferably 40% or less, more preferably 30% or less, even more preferably 20% or less, and even more preferably 15% or less, and the color of the article may be substantially unrecognizable 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, even more preferably 6% or more and 20% or less, and even more preferably 8% or more and 18% or less.

[0029] The total light transmittance can be measured, for example, by the method described in the examples.

[0030] The metallic decorative laminate of this embodiment may contain only the glossy resin layer and the transparent resin layer described later, but may also contain other resin layers described later.

[0031] When the metallic decorative laminate of this embodiment is installed on an article to form a metallic article as described later, it is preferable that the glossy resin layer is located on the article side, and that the transparent resin layer is the outermost surface of the metallic article.

[0032] <Glitter resin layer> The aforementioned glossy resin layer is a layer that gives metallic luster to a metallic decorative laminate, and must contain a resin component (1) containing one or more types of fluororesin, one or more types of pigments, and one or more types of glossy materials.

[0033] The glossy resin layer may contain only the fluororesin as the resin component (1), but the resin component (1) may further contain one or more thermoplastic resins, and may also contain other components as described below. The resin component (1) means not only the fluororesin, but also the components excluding the glossy material contained in the glossy resin layer.

[0034] The glossy resin layer may contain only the fluororesin, the thermoplastic resin, the dye, and the glossy material, or it may also contain other components as described below.

[0035] As described above, it is preferable that the metallic-looking article is laminated in the order of article, glossy resin layer, and transparent resin layer. In particular, it is preferable that the transparent resin layer be the outermost surface of the metallic-looking article, and since the transparent resin layer comes into contact with the atmosphere, solvents, chemicals, etc., it is expected that its chemical resistance and weather resistance will play a major role in improving the chemical resistance and weather resistance of the metallic-looking article. However, after repeated studies, it was found that the configuration of the glossy resin layer, which does not come into direct contact with chemicals, etc., is extremely important for improving the chemical resistance and weather resistance of the metallic-looking article, and that even if the same transparent resin layer is used, the chemical resistance and weather resistance will differ depending on the glossy resin layer that is combined with it. The glossy resin layer contains a fluororesin and a glossy material, which improves the chemical resistance and weather resistance of the metallic-looking article. Since the glossy resin layer is a layer that does not come into direct contact with the outside air, etc., it is usually thought that it does not contribute to the chemical resistance and weather resistance of the metallic-looking article. However, it was found that the chemical resistance and weather resistance are improved by using the layer configuration as in this embodiment. The reason for this is not entirely clear, but it is thought that when the glossy resin layer contains fluororesin and glossy materials, the aggregation of the fluororesin in the transparent resin layer is suppressed, and the fluororesin becomes uniformly dispersed within the transparent resin layer, allowing the chemical resistance and weather resistance characteristics of the fluororesin to manifest on the layer surface.

[0036] In addition, because the glossy resin layer contains a pigment, it is possible to express metallic colors such as black, red, blue, white, navy blue, crimson, orange, and olive, which were difficult to express with glossy materials alone. It is also conceivable to adjust the color tone by incorporating the pigment into the transparent resin layer. However, as mentioned above, when the transparent resin layer becomes the outermost surface of a metallic-looking article, discoloration due to oxidation of the pigment occurs. For this reason, it is preferable to incorporate the pigment into the glossy resin layer in order to suppress this discoloration.

[0037] The thickness of the glossy resin layer is preferably 5 μm or more, more preferably 8 μm or more, even more preferably 10 μm or more, and even more preferably 13 μm or more, in order to improve the glossy appearance and the aforementioned effect on the transparent resin layer. In order to improve the glossy appearance, chemical resistance and weather resistance, the thickness is preferably 100 μm or less, more preferably 60 μm or less, even more preferably 40 μm or less, and even more preferably 35 μm or less.

[0038] To achieve a balance between chemical resistance, weather resistance, aesthetic appeal, and moldability, the particle size is preferably 5 μm to 100 μm, more preferably 8 μm to 60 μm, even more preferably 10 μm to 40 μm, and even more preferably 13 μm to 35 μm.

[0039] The glossy resin layer contains one or more fluororesins as resin component (1) as described above, and may further contain one or more thermoplastic resins. These may be a mixture (polymer alloy) or reactants, but a mixture (polymer alloy) is more preferable in order to improve the dispersibility of the glossy material of the metallic decorative laminate.

[0040] Details of the aforementioned fluororesins will be described later, but a single type of fluororesin may be used, or two or more types may be used in combination. Using only one type is preferable because it is easy to manufacture a uniform metallic decorative laminate, while using two or more types is preferable because it is easy to adjust the physical properties of the resin component (1), such as the melting point.

[0041] Details of the thermoplastic resin will be described later, but the resin component (1) may be a single type of thermoplastic resin or a combination of two or more types. Using only one type is preferable because it is easy to produce a uniform metallic decorative laminate, and using two or more types is preferable because the physical properties of the resin component (1), such as the melting point, can be easily adjusted by adjusting their content ratio.

[0042] The resin component (1) contained in the glossy resin layer may also contain other components besides the fluororesin. Details of the other components will be described later. In this disclosure, the resin component (1) refers to any component other than the glossy material contained in the glossy resin layer.

[0043] When the total amount of resin components (1) contained in the glossy resin layer is 100% by mass, the total content of the fluororesin and, if present, the thermoplastic resin 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. The upper limit is not particularly limited, but it is preferably substantially 100% by mass. Substantially means excluding impurities, etc., that are included unintentionally.

[0044] When the resin component (1) contained in the glossy resin layer contains the fluororesin and the thermoplastic resin, the ratio of the content of the fluororesin to the content of the thermoplastic resin (content of the fluororesin (mass%) / content of the 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 an acrylic resin described later is used as the thermoplastic resin, the ratio 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.

[0045] It is preferable to increase the content of the fluororesin compared to the content of the thermoplastic resin (e.g., acrylic resin) because this improves the dispersibility of the fluororesin in the transparent resin layer, thereby improving chemical resistance and weather resistance.

[0046] The glossy resin layer contains, in addition to the resin component (1), one or more of the following dyes and one or more of the following glossy materials, but it is preferable that the amount of the glossy material in the glossy resin layer is 0.01 parts by mass or more and 20.00 parts by mass or less per 100 parts by mass of the total amount of the resin component (1). It is preferable that the amount is above the lower limit because it improves the chemical resistance, weather resistance and design of the metallic decorative laminate, and it is preferable that it is below the upper limit because it improves the moldability, it is more preferable that it is 0.02 parts by mass or more and 15.00 parts by mass or less, it is even more preferable that it is 0.03 parts by mass or more and 10.00 parts by mass or less, it is even more preferable that it is 0.05 parts by mass or more and 5.00 parts by mass or less, it is even more preferable that it is 0.07 parts by mass or more and 3.00 parts by mass or less, and it is even more preferable that it is 0.08 parts by mass or more and 2.00 parts by mass or less.

[0047] Preferably, the amount of the dye in the glossy resin layer is 0.05 parts by mass or more and 20.00 parts by mass or less per 100 parts by mass of the resin component (1). It is preferable that the amount is above the lower limit because it improves the chemical resistance, weather resistance and design of the metallic decorative laminate, and it is preferable that it is below the upper limit because it improves the moldability, it is more preferable that it is 0.10 parts by mass or more and 15.00 parts by mass or less, it is even more preferable that it is 0.20 parts by mass or more and 13.00 parts by mass or less, it is even more preferable that it is 0.30 parts by mass or more and 10.00 parts by mass or less, it is even more preferable that it is 0.35 parts by mass or more and 7.00 parts by mass or less, and it is even more preferable that it is 0.40 parts by mass or more and 5.00 parts by mass or less.

[0048] Preferably, the total amount of the glossy material and the dye in the glossy resin layer is 0.05 parts by mass or more and 20.00 parts by mass or less per 100 parts by mass of the resin component (1). It is preferable that the amount be above the lower limit because it improves the chemical resistance, weather resistance and design of the metallic decorative laminate, and it is preferable that it be below the upper limit because it improves the moldability, it is more preferable that it be 0.10 parts by mass or more and 15.00 parts by mass or less, even more preferable that it be 0.20 parts by mass or more and 13.00 parts by mass or less, even more preferable that it be 0.30 parts by mass or more and 10.00 parts by mass or less, even more preferable that it be 0.35 parts by mass or more and 7.00 parts by mass or less, and even more preferable that it be 0.40 parts by mass or more and 5.00 parts by mass or less.

[0049] <<Fluorine-based resin>> The aforementioned fluororesin is generally added to improve chemical resistance and weather resistance. In this embodiment, by including the fluororesin 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 the fluororesin, the dispersibility of the glossy material is improved, and the metallic articles using it have a uniform metallic luster.

[0050] As the fluororesin, any resin commonly used as a fluororesin can be used, but polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (CTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), and ethylene-chlorotrifluoroethylene copolymer (ECTFE) are preferred. In particular, polyvinylidene fluoride (PVDF) is preferred when used as the resin component because it has excellent film-forming properties and further forms a glossy resin layer with excellent dispersibility of glossy materials.

[0051] When using the thermoplastic resin (acrylic resin) described later, the mass-average molecular weight (Mw) of the fluororesin is preferably 800 to 5,000, more preferably 1,000 to 3,000, even more preferably 1,300 to 2,000, and even more preferably 1,500 to 1,700, in order to facilitate the formation of a polymer alloy.

[0052] The polydispersity (Mw / Mn) of the fluororesin is preferably 0.5 to 5.0, more preferably 0.8 to 2.5, even more preferably 1.0 to 1.8, and still more preferably 1.2 to 1.4, in order to facilitate the formation of a polymer alloy with the acrylic resin described later.

[0053] The content of the fluororesin in the resin component (1) in the 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 most preferably 55.00% by mass or more and 65.00% by mass or less.

[0054] <<Dye>> The aforementioned pigment is included in the resin composition to express color tones that could not be expressed by the glossy materials described later alone, and is excluded from the glossy materials described later.

[0055] The aforementioned dye does not reflect ambient light (incident light), but rather absorbs light of a specific wavelength to adjust the hue of the lustrous resin layer.

[0056] The pigment contained in the glossy resin layer is one that is commonly used in the present art and is not particularly limited as long as the metallic decorative laminate exhibits the desired metallic design. It may be a dye or pigment, an inorganic compound or an organic compound, a natural pigment or a synthetic pigment, as long as it absorbs visible light. In particular, when used outdoors and weather resistance is required, a synthetic pigment is preferred, and an organic pigment is preferred to improve color development. The pigment preferably contains an inorganic pigment or an organic pigment, and is preferably an inorganic pigment or an organic pigment. More specifically, preferred examples include inorganic pigments such as titanium white (titanium dioxide), zinc oxide, iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, lead yellow, and carbon black; and organic pigments (including dyes) such as isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, induthlene blue RS, and aniline black.

[0057] <<Glitter material>> The aforementioned lustrous material is not particularly limited as long as it is included in the resin composition to reflect ambient light (incident light) and impart a metallic luster to the lustrous resin layer, thereby exhibiting the design characteristics of the metallic decorative laminate. It may be an inorganic pigment or an organic pigment, and may be a natural material or a synthetic material. However, an inorganic pigment is preferable in order to improve the reflection performance of ambient light.

[0058] The surface of the aforementioned glossy material may be coated. The coating may be made of an organic material such as silicone, or an inorganic material such as silica gel or alumina.

[0059] The glossy material preferably contains at least one material selected from flaky or flaky metals, flaky or flaky metal alloys, flaky or flaky metal oxides, flaky or flaky mica, glass flakes, and film pulverized materials. Any material that exhibits glossiness when included in the resin composition is acceptable, but flaky or flaky metals, flaky or flaky mica, or film pulverized materials are more preferred for ease of availability and improved design, and flaky or flaky metals or flaky or flaky mica are even more preferred, and flaky or flaky metals are even more preferred.

[0060] The aforementioned flaky or scale-like metal is a particle formed by flaking metal powder. While any metal commonly used for flaky or scale-like metals is preferable, aluminum, iron, copper, nickel, zinc, gold, silver, oxides of these metals, and alloys containing these metals are more preferable. Examples of flaky or scale-like metals include aluminum flakes, stainless steel flakes, copper flakes, and nickel flakes. To obtain a metallic decorative laminate with excellent metallic design, the flaky or scale-like metal is preferably aluminum or an alloy flake, with aluminum flakes being more preferable.

[0061] Examples of flaky or scale-like mica include white pearl pigments, interference pearl pigments, and colored pearl pigments.

[0062] The aforementioned white pearl pigment is made by covering a flaky matrix such as mica, aluminum, or glass with a coating layer made of a colorless, high refractive index material such as titanium dioxide, and the thickness of the coating layer is preferably 0.1 μm or more and 0.15 μm or less.

[0063] The interference pearl pigment has a coating layer made of a colorless, high refractive index material such as titanium dioxide, and the thickness of the coating layer is preferably greater than 0.15 μm.

[0064] Preferably, the lustrous material is sufficiently and uniformly dispersed in the resin component within the lustrous resin layer 30 in Figure 2, and oriented so that the thickness direction 210 of the lustrous material is substantially parallel to the thickness direction 100. Although Figure 2 schematically depicts the lustrous material as a disc, it is not limited to this. The longest length in the planar direction (particle diameter direction 220 of the lustrous material) of the lustrous material 200 is defined as the particle diameter 221 of the lustrous material, and the average thickness in the thickness direction perpendicular to the planar direction is defined as the thickness 211 of the lustrous material. These are average values ​​measured under an optical microscope after randomly sampling 20 pieces of the lustrous material. The particle diameter 221 of the lustrous material is the volume average particle diameter (D) as described in the examples. 50 ) can be used as a substitute. The particle size of the luminous material is 221 (D 50 For ease of availability and to achieve a metallic appearance, the particle size is preferably 3 μm or larger, more preferably 4 μm or larger, and even more preferably 5 μm or larger. To improve transmitted light, chemical resistance, and weather resistance, the particle size is preferably 50 μm or smaller, more preferably 30 μm or smaller, even more preferably 20 μm or smaller, even more preferably 15 μm or smaller, and most preferably 10 μm or smaller. 50 ) can be measured by standard methods.

[0065] To achieve a balance between chemical resistance, weather resistance, aesthetic appeal, and moldability, the particle size is preferably 3 μm to 50 μm, more preferably 3 μm to 30 μm, even more preferably 4 μm to 20 μm, even more preferably 4 μm to 15 μm, and most preferably 5 μm to 10 μm.

[0066] The thickness 211 of the glossy material is preferably 0.05 μm to 1.00 μm, more preferably 0.10 μm to 0.80 μm, and even more preferably 0.10 μm to 0.50 μm, in order to achieve a balance of chemical resistance, weather resistance, design, and moldability.

[0067] Particle size of luminous material 221(D 50 The ratio of the particle size to the thickness of the lustrous 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.

[0068] Fluorine-based resins have a tendency to aggregate. Aggregation makes it easier for them to take on the shape of fine parts (hereinafter referred to as aggregates), and when they form aggregates, their compatibility with other resin components is poor, and they tend to prevent the fluorine-based resin from being uniformly distributed. Even if the aggregates are crushed and then mixed with, for example, a thermoplastic resin, further aggregation occurs in the resin composition, resulting in a non-uniform dispersion of the resin composition. When this resin composition is applied, aggregates tend to be unevenly distributed on the applied surface. When it becomes this non-uniform state, the properties of the fluorine-based resin cannot be fully expressed. A method of adding nucleating agents, which will be described later, is known to prevent the growth of these aggregates. Adding nucleating agents has the effect of suppressing the growth of particle size even if aggregates are formed. However, increasing the amount of nucleating agent added can lead to a decrease in weather resistance and moldability. While glossy materials are added to improve aesthetics, when used with fluorine-based resins, they have been shown to suppress the growth of aggregates in the fluorine-based resin. Furthermore, since fluororesins improve the dispersibility of glossy materials, the synergistic effect of using fluororesins and glossy materials together results in a uniform layer structure for the glossy resin layer.

[0069] <<Thermoplastic resin>> The glossy resin layer preferably further contains one or more thermoplastic resins.

[0070] The total content of thermoplastic resin in the resin component (1) in the 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 60.00% by mass or less, even more preferably 30.00% by mass or more and 50.00% by mass or less, and even more preferably 35.00% by mass or more and 45.00% by mass or less.

[0071] Examples of the thermoplastic resin include polyolefin resins, polyester resins, and polystyrene resins, but polyolefin resins are preferred because they have good moldability.

[0072] The mass-average molecular weight (Mw) of the polyolefin resin is preferably 30,000 to 500,000, more preferably 50,000 to 300,000, even more preferably 70,000 to 200,000, and even more preferably 90,000 to 100,000 in order to improve impact resistance.

[0073] The polydispersity (Mw / Mn) of the polyolefin resin is preferably 1.5 to 5.0, more preferably 1.6 to 4.0, even more preferably 1.7 to 3.0, and even more preferably 1.9 to 2.2, in order to improve impact resistance.

[0074] The glass transition temperature (Tg) of the 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, in order to improve impact resistance.

[0075] The upper limit of Tg is not particularly limited, but from the viewpoint of moldability, it is preferably 150°C or lower, more preferably 140°C or lower, even more preferably 130°C or lower, and even more preferably 125°C or lower.

[0076] (Acrylic resin) As the polyolefin resin, acrylic resins are preferred. As the acrylic resin, any polymer or copolymer acrylic resin used as such can be used, including acrylic acid and its ester derivatives, as well as polymers and copolymers of methacrylic acid derivatives such as methyl methacrylate. More specifically, polyethyl methacrylate (PEMA), polybutyl methacrylate (PBMA), polycyclohexyl methacrylate (PCHMA), polyethylhexyl methacrylate (PEHMA), etc. are preferred, and polymethyl methacrylate resin (PMMA) is particularly useful when used as a resin component because it has high transparency, excellent scratch resistance due to its high hardness, and can be processed into complex shapes due to its thermoplastic properties.

[0077] The mass-average molecular weight (Mw) of the acrylic resin is preferably 30,000 to 500,000, more preferably 50,000 to 300,000, even more preferably 70,000 to 200,000, and even more preferably 90,000 to 100,000, in order to facilitate the formation of a polymer alloy with the fluororesin.

[0078] The polydispersity (Mw / Mn) of the acrylic resin is preferably 1.5 to 5.0, more preferably 1.6 to 4.0, even more preferably 1.7 to 3.0, and still more preferably 1.9 to 2.2, in order to facilitate the formation of a polymer alloy with the fluororesin.

[0079] The glass transition temperature (Tg) of the acrylic 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, in order to form a more uniform resin component with the fluororesin and to suppress the crystallinity of the fluororesin.

[0080] The upper limit of Tg is not particularly limited, but from the viewpoint of processability, it is preferably 150°C or lower, more preferably 140°C or lower, even more preferably 130°C or lower, and even more preferably 125°C or lower.

[0081] In order to achieve the aforementioned Tg range, the acrylic resin preferably has an imide skeleton in its structure.

[0082] <<Component B>> As other components, nucleating agents, ultraviolet absorbers, antioxidants, pigments, antistatic agents, leveling agents, and defoaming agents may be used as needed.

[0083] (Nuclear agent) As mentioned above, using a nucleating agent is preferable because it allows for control of the aggregation of the glossy resin layer. Fluorine-based resins are crystalline resins and are known to crystallize within the resin layer. Aggregation within the resin layer can lead to crystal formation, and as the crystallite size grows, the resin layer may become cloudy due to scattering by the crystals. Using the aforementioned nucleating agent is preferable because it allows for a reduction in the crystallite size. Various nucleating agents can be selected depending on the resin components used, but acrylic-modified polytetrafluoroethylene is preferable because it allows for control of the crystallite size of the fluorine-based resin.

[0084] Commonly used compounds can be used as UV absorbers, antioxidants, pigments, antistatic agents, leveling agents, and defoaming agents. Benzotriazole compounds are preferred as UV absorbers.

[0085] <Transparent resin layer> The transparent resin layer is laminated on the side opposite to the article from the glossy resin layer, and is preferably the outermost layer when the article is made metallic. The transparent resin layer must contain a resin component (2) containing one or more types of fluororesin.

[0086] The difference between a transparent resin layer and a glossy resin layer lies in whether or not they contain glossy materials.

[0087] The resin component (2) may contain only the fluororesin, or it may further contain one or more of the thermoplastic resins, or it may contain only the fluororesin and the thermoplastic resins. The resin component (2) may further contain the other components.

[0088] In the aforementioned metallic decorative laminate, ambient light passes through the transparent resin layer, a portion of which is reflected by the metallic resin layer and passes through the transparent resin layer again, allowing the viewer of the metallic article to perceive its metallic luster. For this reason, the transparent resin layer is required to be transparent, and its total light transmittance is preferably 80% or more, more preferably 90% or more, even more preferably 95% or more, and even more preferably 98% or more. There is no particular upper limit, as long as the metallic design of the metallic decorative laminate of this disclosure is expressed. The total light transmittance can be measured, for example, by the method described in the examples.

[0089] The transparent resin layer is preferably the outermost layer when the material is made into a metallic-looking article as described above. For this reason, in order to improve chemical resistance and weather resistance, it is preferable that the lower limit of the layer thickness be large, and in order to improve design and moldability, it is preferable that the upper limit of the layer thickness be small, preferably 5 μm or more, more preferably 10 μm or more, even more preferably 20 μm or more, and even more preferably 25 μm or more, and in order to improve chemical resistance and moldability, it is preferably 100 μm or less, more preferably 60 μm or less, even more preferably 40 μm or less, and even more preferably 35 μm or less.

[0090] To achieve a balance between chemical resistance, weather resistance, aesthetic appeal, and moldability, the particle size is preferably 5 μm to 100 μm, more preferably 10 μm to 60 μm, even more preferably 20 μm to 40 μm, and even more preferably 25 μm to 35 μm.

[0091] When the aforementioned glossy resin layer is used as the outermost surface of a metallic decorative laminate, the surface may be given various patterns by embossing or other processes as needed, or a matte finish may be given by creating fine irregularities. Alternatively, a hairline finish may be applied to give a hairline-like design.

[0092] The fluororesin, thermoplastic resin, and other components used in the transparent resin layer can be the same as those used in resin component (1), and the content of each component is also the same as in resin component (1).

[0093] <Other layering> The aforementioned metallic decorative laminate may further include other layers.

[0094] The aforementioned other layers may include, as necessary, a surface protection layer, a primer layer, an adhesive layer, and the like.

[0095] For the surface protection layer and primer layer, general-purpose films such as urethane resin, polyester resin, acrylic resin, acrylic urethane resin, and vinyl chloride-vinyl acetate copolymer resin can be used, and for the adhesive layer, a polyurethane-based adhesive layer is preferred in order to obtain sufficient transparency and adhesive strength.

[0096] [Intermediate laminate] The intermediate laminate of this embodiment requires that the transparent resin layer side of the metallic decorative laminate further include the substrate described later.

[0097] The aforementioned intermediate laminate is manufactured when producing the metallic decorative laminate, etc. The manufacturing methods for each laminate will be described later, but a metallic decorative laminate can be easily produced by laminating a transparent resin layer and a glossy resin layer on the substrate described later.

[0098] The intermediate laminate may include the metallic laminate and the substrate, but may also include only the metallic laminate and the substrate, or may further include the other layers.

[0099] The thickness of the intermediate laminate can be adjusted as appropriate, but is preferably 30 μm to 200 μm, more preferably 60 μm to 160 μm, even more preferably 80 μm to 140 μm, and even more preferably 100 μm to 120 μm.

[0100] <Base material> The aforementioned substrate is used to apply a coating solution that forms a transparent resin layer to the metallic decorative laminate when manufacturing it, as described later. It is a layer that protects the outermost surface of the transparent resin layer when transporting or storing the multilayer laminate described later. It also serves as a release layer because it is peeled off at one of the stages of the manufacturing process of the metallic article.

[0101] The aforementioned substrate can be any substrate used in the relevant technical field, and can be appropriately selected from polyethylene-based substrates, polyester-based substrates (including polyethylene terephthalate (PET) substrates), polycarbonate-based substrates, etc. PET is more preferred due to requirements such as ease of handling during manufacturing and availability.

[0102] The thickness of the substrate can be as long as it does not interfere with the manufacturing process, but generally, a thickness of 10 μm to 150 μm can be used.

[0103] [Multilayer laminate] The multilayer laminate must include a base layer on the side of the intermediate laminate that is the glossy resin layer. There may be an adhesive layer between the intermediate laminate and the base layer, and it is preferable that the intermediate laminate and the base layer are bonded together by the adhesive layer, and the other layers may be included further.

[0104] The layer thickness of the aforementioned multilayer laminate can be adjusted as appropriate.

[0105] The multilayer laminate is preferably one of the following (1) to (4), with (1) and (2) being more preferred, and (2) being even more preferred, as these facilitate the manufacture of each laminate and the metallic-looking article. Note that " / " indicates the space between layers. The spaces between each layer may not be clearly defined due to partial penetration, etc., and can be said to be the manufacturing configuration during production. (1) Substrate / Transparent resin layer / Glossy resin layer / Base layer (2) Substrate / Transparent resin layer / Glossy resin layer / Adhesive layer / Base layer (3) Substrate / Adhesive layer / Transparent resin layer / Glossy resin layer / Base layer (4) Substrate / Adhesive layer / Transparent resin layer / Glossy resin layer / Adhesive layer / Base layer

[0106] <Base layer> As for the base layer, considering the impact on the design, a material for the base layer can be appropriately selected from resins such as polyvinyl chloride, polyolefin, polystyrene, polyacrylic, polyurethane, polyamide, polycarbonate, and acrylonitrile-butadiene-styrene copolymer (ABS resin), depending on the application, taking into consideration the heat resistance to the temperature at which it is molded into a glossy decorative molded product, compatibility with injection molding resins in insert injection molding, etc.

[0107] Furthermore, the thickness of the base layer can be set to a typical thickness for decorative laminates, for example, 50 μm to 1000 μm. A base layer thickness within this range is preferable because it suppresses the occurrence of defects such as wrinkles during film formation and suppresses the fracture of the metallic decorative laminate during the molding process of the metallic-looking article. However, if the base layer thickness exceeds 1000 μm, the moldability of the metallic-looking article may decrease.

[0108] It is also preferable that the base layer contains pigment. This suppresses the influence of the article's color on the metallic-looking article and allows for the expression of a wider color gamut, thereby improving the design.

[0109] [Decorated laminate] The decorative laminate is obtained by peeling the substrate (release layer) from the multilayer laminate, and the metallic decorative laminate must include a base layer on the glossy resin layer side.

[0110] As will be described later, metallic-looking articles are manufactured using decorative laminates.

[0111] The base layer may contain a pigment.

[0112] [Metal-like articles] The metallic-looking article of this embodiment is required to include the metallic-looking decorative laminate.

[0113] The metallic articles of this embodiment are manufactured using the metallic decorative laminate by, for example, the manufacturing method described later, and are molded into a desired shape according to their purpose. For example, they can be used in the casings and decorative parts of home appliances such as personal computers, TVs, washing machines, and refrigerators, as well as in the casings and decorative parts of pachinko machines, pachislot machines, and game machines, or in general use in carry bags and suitcases, and can provide metallic decorative and design features in place of plating or metal materials.

[0114] In particular, the metallic decorative laminate of this embodiment not only imparts a metallic design to an article, but also imparts chemical resistance and weather resistance to the article. In this disclosure, "article" refers to a precursor of a metallic article, which becomes a metallic article by being decorated with the decorative laminate.

[0115] The metallic-looking article of this embodiment may have other configurations in addition to the above-described configuration. For example, in order to keep the surface of the protective layer and base layer clean and prevent dirt from adhering until the metallic-looking article of this embodiment is used, release paper, protective film, etc., may be provided on the surface of the protective layer and base layer.

[0116] [Method for manufacturing intermediate laminates, multilayer laminates, decorative laminates, and metallic-looking articles] The metallic decorative laminate of this embodiment is a common feature of the intermediate laminate, multilayer laminate, decorative laminate, and metallic article, and is formed during the manufacturing process of the intermediate laminate.

[0117] The method for manufacturing the intermediate laminate of this embodiment requires, in this order, to apply a coating liquid containing one or more types of fluororesins, to apply a coating liquid containing one or more types of fluororesins, one or more types of dyes, and one or more types of glossy materials, and to heat.

[0118] Fluorine-based resins, glossy materials, thermoplastic resins, other components, metallic-look decorative laminates, intermediate laminates, multilayer laminates, decorative laminates, and metallic-look articles have already been explained and will be omitted here.

[0119] (A coating liquid containing one or more of the aforementioned fluororesins) The coating liquid containing one or more of the aforementioned fluororesins is a coating liquid for forming a transparent resin layer, and may further contain the aforementioned thermoplastic resin and / or other components.

[0120] The coating liquid may further contain a solvent, and may be a homogeneous solvent or a slurry.

[0121] (solvent) The aforementioned solvent can be any solvent that is generally used in the field in question. Possible solvents include polar solvents such as ester solvents, ether solvents, and ketone solvents; nonpolar solvents such as hydrocarbon solvents and aromatic solvents; and alcoholic solvents such as methanol, ethanol, and isopropyl alcohol. However, polar solvents such as ester solvents, ether solvents, and ketone solvents are preferred.

[0122] In the manufacturing method of the metallic decorative laminate of this embodiment, it is preferable that the solvent exhibits poor solvent properties with respect to fluororesins and good solvent properties with respect to acrylic resins. If the fluororesin is not dissolved in the coating solution before heating, as described later, it will not react with the acrylic resin before heating, and clumps of reaction products of the fluororesin and acrylic resins will not form in the coating solution, which is preferable. Because such clumps do not form, uneven coating does not occur during application, and a uniform glossy resin layer can be produced. Butyl carbitol acetate is a preferred example of a solvent having such properties.

[0123] When using the aforementioned solvent, in order to shorten the heating process time described later and improve the applicability of the coating liquid to the substrate, the total amount of the fluororesin and the acrylic resin is preferably 80.0 parts by mass or more and 500.0 parts by mass or less, more preferably 100.0 parts by mass or more and 300.0 parts by mass or less, and even more preferably 150.0 parts by mass or more and 200.0 parts by mass or less, per 100 parts by mass.

[0124] (A coating liquid containing one or more of the aforementioned fluororesins, one or more of the aforementioned dyes, and one or more of the aforementioned glossy materials) The coating liquid containing one or more types of fluororesins, one or more types of dyes, and one or more types of glossy materials is a coating liquid for forming a glossy resin layer, and may further contain the thermoplastic resin and / or other components.

[0125] The coating liquid may further contain the solvent, and may be a homogeneous solvent or a slurry.

[0126] <To apply> The coating can be performed by known means such as a gravure coater, reverse coater, die coater, knife coater, or roll coater on the substrate or a resin layer formed on the substrate.

[0127] <To heat> The aforementioned heating may be started before the coating is completed or after the coating is completely finished, but it is preferable to heat while the coating liquid is on the substrate. The aforementioned heating also includes cases where the substrate is heated beforehand, the coating is applied, and then further heating is performed.

[0128] By heating as described above, the solvent is removed if the solvent is used in the coating liquid. By heating the resin component to a temperature above the Tg of the resin component it contains, it can be mixed with the fluororesin. This is preferable because it prevents the crystallite size of the fluororesin from growing, suppresses the precipitation of the fluororesin from the resin component, and allows for uniform dispersion of the glossy material.

[0129] The heating temperature can be appropriately selected depending on the heating time, the fluororesin, dye, thermoplastic resin, other components, solvent, and substrate used, but in order to obtain a metallic decorative laminate that has excellent design and achieves chemical resistance, weather resistance, and moldability, a temperature of 100°C or higher is preferable, 150°C or higher is more preferable, 170°C or higher is even preferable, 250°C or lower is preferable, 220°C or lower is more preferable, and 200°C or lower is even preferable.

[0130] The heating method can be appropriately selected based on the shape, size, and other factors of the object to be heated, using a heating method appropriate for the field.

[0131] The heating time can be appropriately selected depending on the size of the laminate to be manufactured, the heating temperature, the fluororesin, thermoplastic resin, solvent, and substrate used, but in order to obtain a metallic decorative laminate with excellent design and millimeter-wave transmittance, 30 seconds or more is preferable, 1 minute or more is more preferable, 5 minutes or less is preferable, and 3 minutes or less is even more preferable.

[0132] <Removing the substrate> The method for manufacturing the decorative laminate of this embodiment requires peeling the substrate from the multilayer laminate.

[0133] The metallic decorative laminate produced by the aforementioned method for manufacturing a metallic decorative laminate is formed on a substrate. Therefore, the decorative laminate is obtained by peeling off the substrate (release layer).

[0134] The method of removal is not particularly limited, as long as it is a method commonly used in the field.

[0135] <Method for manufacturing metallic articles> The metallic articles of this embodiment can be manufactured, for example, by the following method.

[0136] The process includes a molding step in which the surface temperature of the decorative laminate is set to 150°C to 200°C, and the decorative laminate is brought into close contact with a mold so that the base film side of the laminate faces the article side, and then molded onto the surface of the article to obtain a metallic-looking article.

[0137] (molding process) To thermoform the decorative laminate, the surface temperature of the decorative laminate is 150°C to 200°C. This prevents drawdown and whitening during molding, thus ensuring good moldability. A surface temperature of 150°C or higher allows the decorative laminate to soften sufficiently, preventing sagging and deformation due to drawdown, which can make processing and molding difficult. Conversely, a surface temperature of 200°C or lower prevents the decorative laminate from becoming too soft and difficult to mold, or from becoming prone to whitening.

[0138] The shape of the mold used to press the decorative laminate can be any shape necessary to form the metallic-looking article into the desired shape. For example, molds such as male and female molds with a brass surface chrome-plated can be used. The mold temperature can also be set to any temperature, taking into consideration the control of the surface temperature of the decorative laminate and the cooling conditions of the metallic-looking article after the molding process.

[0139] Methods for adhering the decorative laminate to the mold include straight molding using a female mold, drape molding using a male mold, and plug-assisted molding using a plug (auxiliary mold). Any method can be adopted considering ease of molding and cost. In addition, vacuum forming, which sucks the metallic decorative laminate into the mold, and compressed air forming, which uses compressed air pressure to adhering the metallic decorative laminate to the mold, can be employed. For example, by adhering the metallic decorative laminate to the mold using vacuum and / or compressed air, the adhesion between the decorative laminate and the mold is improved, allowing for processing into more precise shapes.

[0140] (Clamping process) The manufacturing method for the metallic-looking article may include a clamping step of clamping the decorative laminate before the molding step. This step allows the decorative laminate to be adjusted and fixed so that it does not sag during molding. Clamping can be performed, for example, by using multiple gripping means capable of gripping both sides of the decorative laminate, such as gripping both ends of the decorative laminate. Gripping of the decorative laminate is not limited to both ends, but any part of the decorative laminate can be gripped. Typically, when continuously producing metallic-looking articles, both ends in the width direction of the decorative laminate can be gripped. Also, when batch producing metallic-looking articles using rectangular pieces of decorative laminate cut to a predetermined length, the ends of all four sides can be gripped with upper and lower frames.

[0141] (Heating process) Furthermore, the method for manufacturing the metallic-looking article may include a heating step in which the decorative laminate is heated after the clamping step. For example, after clamping the decorative laminate at room temperature to prevent loosening, multiple heaters or the like can be used as heating means, with these heaters positioned above and below the decorative laminate to simultaneously and uniformly heat both sides of the decorative laminate. This heating step allows the surface temperature of the decorative laminate to be controlled to 150°C to 200°C.

[0142] (Other processes) The manufacturing method for metallic articles may include other steps in addition to the steps described above. For example, a bonding step may be included in which a protective film or the like is attached to the surface of the protective layer or base layer to maintain the surface of the protective layer or base layer in a clean state and prevent contamination until the metallic article is processed in the next step. Furthermore, after inserting the metallic article into an injection molding die, insert injection molding is performed by injecting resin, and the surface of the injection molded product can be decorated.

[0143] The following [1] to

[13] are preferred for the metallic decorative laminate, the intermediate laminate including the metallic decorative laminate, the multilayer laminate, the decorative laminate, the metallic article, and the method for manufacturing the intermediate laminate and the decorative laminate of this embodiment. [1] A resin component (1) containing one or more types of fluororesins, a glossy resin layer containing one or more types of dyes and one or more types of glossy materials, A metallic decorative laminate comprising a transparent resin layer containing a resin component (2) containing one or more types of fluororesins. [2] The metallic decorative laminate according to [1], wherein the resin component (1) further contains one or more thermoplastic resins. [3] The metallic decorative laminate according to [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 per 100 parts by mass of the resin component (1). [4] The metallic decorative laminate according to any one of [1] to [3], wherein the glossy material contains at least one material selected from flaky or flake metals, flaky or flake metal alloys, flaky or flake metal oxides, flaky or flake mica, glass flakes, and film pulverized material. [5] The metallic decorative laminate according to any one of [1] to [4], wherein the amount of the dye in the glossy resin layer is 0.05 parts by mass or more and 20.00 parts by mass or less per 100 parts by mass of the resin component (1). [6] The metallic decorative laminate according to any one of [1] to [5], wherein the dye contains an inorganic pigment or an organic pigment. [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. [8] An intermediate laminate comprising a base material on the transparent resin layer side of a metallic decorative laminate according to any one of [1] to [7]. [9] [8] A multilayer laminate comprising a base layer on the glossy resin layer side of the intermediate laminate described above.

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

[11] A metallic article comprising a metallic decorative laminate as described in any one of [1] to [7].

[12] Apply a coating solution containing one or more types of fluororesins. Apply a coating solution containing one or more types of fluororesins, one or more types of pigments, and one or more types of glossy materials. A method for producing an intermediate laminate according to [8], comprising heating in this order. A method for producing a decorative laminate according to

[10] , comprising peeling off a substrate from the multilayer laminate described in

[13] [9]. [Examples]

[0144] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited in any way to the following examples.

[0145] (Evaluation method) 1. Chemical resistance evaluation Chemical resistance evaluation was performed using commercially available brake fluid (manufactured by XX company, product name: XX) with polyethylene glycol monoether as the main component, assuming use in four-wheeled or two-wheeled vehicles, vacuum pumps, etc. 25cm x 25cm decorative laminates obtained in the examples and comparative examples were prepared as test samples. At 25°C, 1 mL of the brake fluid was dropped onto the transparent resin layer side of the decorative laminate at 9 points in a 3x3 arrangement using a dropper. After standing for 5 hours, the brake fluid was washed off with toluene, and after leaving it at 25°C for 1 hour to confirm that the toluene had dried, the surface condition was visually observed and evaluated as follows (A-D). A: No change was observed in any of the 9 points compared to before the exam. B: In areas with less than 4 points, traces of dripped brake fluid can be seen. C: In the area with a score between 4 and 8 points, traces of dripped brake fluid can be seen. D: Drip marks from brake fluid can be seen in areas with 8 or more points.

[0146] 2. Weather resistance evaluation A xenon weather meter SX75 7.5kW (manufactured by Suga Test Instruments) was used. The treatment conditions were: black panel temperature 63±2℃, humidity 50%RH, rainfall cycle (non-rainfall time / rainfall time) 102 min / 18 min, and illuminance 180 W / m 2 , tank temperature 25~35℃, 500MJ / m 2 The color difference of the transparent resin layer side of the decorated 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 follows (A to C). A: A value of △E* = 3.0 or less was considered to indicate very good weather resistance. B: Weather resistance was evaluated as such if △E* was greater than 3.0 and less than or equal to 5.0. If C:△E* is greater than 5.0, it was evaluated as having no weather resistance.

[0147] 3. Heat resistance evaluation The decorated laminates obtained in the examples and comparative examples were left in an environment of 100°C for 500 hours. The color difference of the sample surface on the transparent resin layer side of the decorated laminate before and after the test was measured using a color difference meter CM-3600A (manufactured by Konica Minolta) and evaluated as follows (A to C). A: △b* = 1.0 or less, and if there are no defects such as peeling of the decorative sheet, it was evaluated as having very good heat resistance. B:Heat resistance was evaluated as being present if △b* was greater than 1.0 and less than or equal to 3.0, and there were only minor defects such as peeling of the decorative sheet. If C:△b* is greater than 5.0, or if major defects such as peeling of the decorative sheet are observed, the material is evaluated as lacking heat resistance.

[0148] 4. Design evaluation The decorative laminates obtained in the examples and comparative examples were visually observed from the transparent resin layer side and evaluated as either A or B below. A: It has a metallic design. B: It does not have a metallic design, or it has a matte finish.

[0149] 5.Total light transmittance Total light transmittance was measured for the decorated laminates obtained in the examples or comparative examples using a spectrophotometer (Hitachi High-Tech Science Corporation, UH4150) in accordance with JIS K7375:2008.

[0150] 6. Post-molding design evaluation Metallic articles prepared using the decorative laminates obtained in the examples and comparative examples were visually observed and evaluated.

[0151] 7. Evaluation of moldability For metallic-looking articles prepared using the decorative laminates obtained in the examples and comparative examples, the moldability was evaluated by visually observing whether or not the stretched portion of the laminate (stretched to 200% of its original length) at the corner of the mold after the molding process was cloudy.

[0152] (Materials used) (Fluorine-based resin (manufactured by Arkema Corporation, kyanr301)) Number average molecular weight (Mn) 1,200 Weight average molecular weight (Mw) 1,600 Z average molecular weight (Mz) 1,900 Polydispersity (Mw / Mn) 1.3 Peak area ratio 14% (Acrylic resin (manufactured by Asahi Kasei Corporation, SK540)) Number average molecular weight (Mn) 46,000 Weight average molecular weight (Mw) 93,000 Z average molecular weight (Mz) 150,000 Polydispersity (Mw / Mn) 2.0 Peak area ratio 86% (Pigment 1) White pigment MHI White #148 (manufactured by Mikuni Pigment Co., Ltd.) (Pigment 2) Black pigment MHI Black #C004 (manufactured by Mikuni Pigment Co., Ltd.) (Pigment 3) Blue pigment MHI Blue #C362M (manufactured by Mikuni Pigment Co., Ltd.) (Pigment 4) Red pigment MHI Red #CC361 (manufactured by Mikuni Pigment Co., Ltd.) (Luminescent material 1) Pearl pigment TWINCLEPEARL SXC-SO (manufactured by Nippon Kogaku Kogyo Co., Ltd., volume average particle diameter (D 50 ): 22μm) (Luminescent material 2) Aluminum flake GX40A (manufactured by Asahi Kasei Corporation, volume average particle diameter (D 50 ): 19μm) (Luminescent material 3) Pearl pigment TWINCLEPEARL (registered trademark) BXC-SO (manufactured by Nippon Kogaku Kogyo Co., Ltd., volume average particle diameter (D 50 ): 22μm)

[0153] (Example 1) <Manufacturing of intermediate laminates including metallic decorative laminates> (Formation of a transparent resin layer) The transparent resin coating solution described below was applied to the substrate (PET film (G2000 (manufactured by Toyobo Co., Ltd.))). The amount applied was adjusted so that the thickness of the glossy resin layer after heating was 30 μm. Immediately after application, the substrate was heated at 180°C for 2 minutes to form a transparent resin film. It was then cooled to room temperature.

[0154] ((Coating liquid for transparent resin layer)) 37.45 g of butyl carbitol acetate (manufactured by Sankyo Kasei Sangyo Co., Ltd.) was mixed with 8.75 g of acrylic resin (manufactured by Asahi Kasei Corporation, SK540), and stirred at room temperature to obtain a homogeneous solution. Further addition of other components (0.57 g of ultraviolet absorber (manufactured by BASF Japan Ltd., Tinuvin900) and 0.06 g of nucleating agent (manufactured by Mitsubishi Chemical Corporation, A-3000)) and 13.16 g of fluororesin (manufactured by Arkema K.K., kyanr301) was added, and the mixture was stirred further to obtain a coating solution for a transparent resin layer containing resin component (2).

[0155] Tables 1 and 2 show the respective content of acrylic resin, fluororesin, and other components in resin component (2) used in the examples and comparative examples.

[0156] (Formation of a glossy resin layer) The coating solution for the glossy resin layer, described below, was applied to the transparent resin layer of the substrate on which the transparent resin layer had been formed as described above. The amount applied was adjusted so that the thickness of the glossy resin layer after heating was 30 μm.

[0157] Immediately after application, the material was heated at 180°C for 2 minutes to laminate a glossy resin layer. Afterward, it was cooled to room temperature to produce an intermediate laminate containing a metallic-looking decorative laminate.

[0158] The substrate was peeled off from the obtained intermediate laminate, and chemical resistance evaluation, weather resistance evaluation, heat resistance evaluation, design evaluation, and total light transmittance measurement were performed on the transparent resin layer side. The results are shown in Tables 3 and 4, along with those of other examples and comparative examples.

[0159] (Coating liquid for glitter resin layer) 37.45 g of butyl carbitol acetate (manufactured by Sankyo Kasei Sangyo Co., Ltd.) was mixed with 8.75 g of acrylic resin (manufactured by Asahi Kasei Corporation, SK540), and stirred at room temperature to obtain a homogeneous solution. Further, other components (0.57 g of ultraviolet absorber (manufactured by BASF Japan Ltd., Tinuvin900) and 0.06 g of nucleating agent (manufactured by Mitsubishi Chemical Corporation, A-3000)), dye 1 (used in an amount of 2.00 parts by mass of dye component per 100 parts by mass of resin component 1), and 13.16 g of fluororesin (manufactured by Arkema K.K., kyanr301) were added and stirred to obtain a solution containing resin component (1). 1.13 g of glossy material 1 was added to the obtained solution containing resin component (1), and further stirred to obtain a coating liquid for a glossy resin layer.

[0160] Tables 1 and 2 show the respective content of acrylic resin, fluororesin, and other components in resin component (1) used in the examples and comparative examples.

[0161] Tables 1 and 2 show the respective content of acrylic resin, fluororesin, and other components in resin components (1) and (2), and the amount (parts by mass) of dyes and glossy materials used when resin component (1) is set at 100 parts by mass. In the tables, "-" means that it was not used.

[0162] [Table 1]

[0163] [Table 2]

[0164] <Manufacturing of metallic-looking products> (Formation of adhesive layer and base layer) A urethane-based adhesive for metallic decorative sheets was used, which consisted of a main component comprising a mixture of polyester diol, polycarbonate diol, carbodiimide, a silane coupling agent having an epoxy group, and ethyl acetate, and a curing agent comprising an aliphatic isocyanate, on the glossy resin layer of the aforementioned intermediate laminate.

[0165] TM-K51 (manufactured by Toyo Morton Co., Ltd.) was used as the polyester diol, Duranol T5652 (manufactured by Asahi Kasei Corporation) as the polycarbonate diol, Carbodilite V-07 (manufactured by Nisshinbo Chemical Co., Ltd.) as the carbodiimide, KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as the silane coupling agent with an epoxy group, and CAT-RT85 (manufactured by Toyo Morton Co., Ltd.) as the aliphatic isocyanate.

[0166] A urethane-based adhesive was applied to the surface of the glossy resin layer using a bar coater so that the dry film thickness of the adhesive layer was approximately 10 μm. After drying the coated material at 60°C for 1 minute, the coated material was laminated with a PET film (average thickness 25 μm, Teflex FT3, manufactured by Toyobo) as a base layer to produce a multilayer laminate.

[0167] The substrate was peeled off from the resulting multilayer laminate to produce a decorative laminate.

[0168] Using the obtained decorative laminate, a compression molding machine was used to clamp the base layer of the decorative laminate into a test mold so that it would become an article. Then, with a pre-forming temperature of 160°C and a compressed air pressure of 6 bar, the metallic decorative laminate was preformed to fit a mold for injection molding, and any excess material that protruded from the mold was trimmed to obtain a metallic article.

[0169] Chemical resistance, weather resistance, heat resistance, aesthetic appeal, and total light transmittance were measured for the decorative laminate and metallic-looking articles obtained in Example 1, and the results are shown in Tables 3 and 4.

[0170] Both the post-molding design evaluation and the moldability evaluation were satisfactory for practical purposes. (Examples 2) to (Examples 6) and (Comparative Example 1) to (Comparative Example 5) 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, except that the film thickness, amount of fluororesin used, amount of acrylic resin used, type of dye, amount of dye used, type of glossy material, and amount of glossy material used were changed as shown in Tables 1 and 2. In Tables 1 and 2, the "dye" and "glossy material" are listed in the upper row for the material used and in the lower row for the amount used (parts by mass) per 100 parts by mass of resin component (1).

[0171] Chemical resistance, weather resistance, heat resistance, aesthetic appeal, and total light transmittance were measured for the decorative laminates and metallic articles obtained in Examples 2 to 6 and Comparative Examples 1 to 5, and the results are shown in Tables 3 and 4.

[0172] Both the post-molding design evaluation and the moldability evaluation were satisfactory for practical purposes.

[0173] [Table 3]

[0174] [Table 4]

[0175] The results from Examples 1 to 6 shown in Tables 3 and 4 indicate that the metallic decorative laminate of this embodiment exhibits a metallic design and possesses excellent properties in terms of chemical resistance, weather resistance, heat resistance, and total light transmittance. Furthermore, environmental burden due to the generation of waste liquids, similar to that of metal plating, was suppressed.

[0176] Furthermore, it was confirmed that all metallic-looking articles, including the metallic-looking decorative laminates, pose no practical problems.

[0177] In contrast, in Comparative Examples 1-5, the glossy resin layer did not contain any glossy material, and therefore did not exhibit a metallic appearance. [Industrial applicability]

[0178] The metallic decorative laminates, intermediate laminates, multilayer laminates, decorative laminates, and metallic articles of this embodiment exhibit excellent metallic designs, reduce environmental impact during manufacturing, possess chemical resistance and weather resistance, and offer superior productivity. They can provide metallic decorative and aesthetic appeal in place of plating or metal materials, and are suitable for use in automobiles, home appliances, information terminals, and the like. [Explanation of Symbols]

[0179] 1: Metallic decorative laminate 2: Intermediate laminate 3: Decorated laminate 4: Multilayer laminate 10: Substrate (release layer) 20: Transparent resin layer 30: Glitter resin layer 31: Surface of the article opposite to the glossy resin layer 32: Surface of the article side of the glossy resin layer 40: Adhesive layer 50: Base layer 100: Thickness direction 110: Width direction 120: Longitudinal direction 200: Glitter material 210: Thickness direction of the bright material 211: Thickness of bright material 220: Particle diameter direction of luminous materials 221: Particle size of luminous materials

Claims

1. A resin component (1) containing one or more types of fluororesins, a glossy resin layer containing one or more types of dyes and one or more types of glossy materials, and A metallic decorative laminate comprising a transparent resin layer containing a resin component (2) containing one or more types of fluororesins, wherein the thickness of the glossy resin layer is 5 μm or more, the dye contains an organic pigment, and the transparent resin layer, the glossy resin layer and the adhesive layer are included in this order.

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 amount of the glossy material in the glossy resin layer is 0.01 parts by mass or more and 20.00 parts by mass or less, based on 100 parts by mass of the resin component (1).

4. The metallic decorative laminate according to claim 1, wherein the glossy material contains at least one material selected from flaky or flake metals, flaky or flake metal alloys, flaky or flake metal oxides, flaky or flake mica, glass flakes, and film pulverized material.

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

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

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

8. A multilayer laminate comprising a base layer on the glossy resin layer side of the intermediate laminate according to claim 7.

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

10. A metallic-looking article comprising a metallic-looking decorative laminate as described in claim 1.

11. Apply a coating solution containing one or more types of fluororesins. Apply a coating solution containing one or more types of fluororesins, one or more types of pigments, and one or more types of glossy materials. A method for producing an intermediate laminate according to claim 7, comprising heating in this order, wherein the dye contains an organic pigment.

12. A method for manufacturing a decorative laminate according to claim 9, comprising peeling off a substrate from the multilayer laminate according to claim 8.

Images