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

Abstract

To provide a metallic decorative laminate, an intermediate laminate, a multilayer laminate, a decorative laminate and a metallic article which exhibit excellent metallic designs, reduce environmental loads during manufacture, and have improved chemical resistance and weather resistance, and a method for manufacturing the intermediate laminate and a method for manufacturing the decorative laminate.SOLUTION: A metallic decorative laminate includes a brilliant resin layer containing one or more kinds of fluorine-based resins and one or more kinds of brilliant materials, and a transparent resin layer containing one or more kinds of fluorine-based resins, in which a content of the fluorine-based resin to a resin component (1) in the brilliant resin layer exceeds 30 mass%, and a content of the fluorine-based resin to a resin component (2) in the transparent resin layer exceeds 30 mass%.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a metal-like decorative laminate, an intermediate laminate, a multilayer laminate, a decorative laminate, a metal-like article, a method for manufacturing the intermediate laminate, and a method for manufacturing the decorative laminate.

Background Art

[0002] In order to enhance the designability of a resin molded body, imparting a metallic luster to the surface of the resin molded body has been carried out. As a means for imparting this metallic luster, metal plating has been performed (Patent Document 1). Further, as another application, an electromagnetic wave-transmissive glossy painted resin product (Patent Document 2) has been developed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a metal-like decorative laminate, an intermediate laminate, a multilayer laminate, a decorative laminate, and a metal-like article that exhibit an excellent metal-like design, reduce the environmental load during production, and have improved chemical resistance and weather resistance, and also to provide a method for manufacturing the intermediate laminate and a method for manufacturing the decorative laminate.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above problems, the present inventors provide the following [1] to [7]. [1] A metallic decorative laminate including a resin component (1) containing one or more fluororesins and a phosphorescent resin layer containing one or more phosphorescent materials, and a transparent resin layer containing a resin component (2) containing one or more fluororesins, wherein the content of the fluororesin in the resin component (1) in the phosphorescent resin layer is more than 30% by mass, and the content of the fluororesin in the resin component (2) in the transparent resin layer is more than 30% by mass. [2] An intermediate laminate including a substrate on the transparent resin layer side of the metallic decorative laminate according to [1]. [3] A multilayer laminate including a base layer on the phosphorescent resin layer side of the intermediate laminate according to [2]. [4] A decorative laminate including a base layer on the phosphorescent resin layer side of the metallic decorative laminate according to [1]. [5] A metallic article including the metallic decorative laminate according to [1]. [6] A method for manufacturing the intermediate laminate according to claim 6, including applying a coating liquid containing one or more fluororesins, applying a coating liquid containing one or more fluororesins and one or more phosphorescent materials, and heating, in this order. [7] A method for manufacturing the decorative laminate according to [4], including peeling a substrate from the multilayer laminate.

Advantages of the Invention

[0006] According to the present invention, there are provided a metallic decorative laminate, an intermediate laminate, a multilayer laminate, a decorative laminate, and a metallic article that exhibit an excellent metallic design, reduce the environmental load during manufacturing, and have improved chemical resistance and weather resistance, and also a method for manufacturing the intermediate laminate and a method for manufacturing the decorative laminate.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Mode for Carrying Out the Invention

[0008] Patent Document 1 describes an invention related to a plated member made of synthetic resin for a vehicle that exhibits a metallic luster by plating a member made of synthetic resin. However, electroplating has problems such as a complicated process and high manufacturing cost, generation of waste liquid and environmental load. Further, when the surface of the molded body has an uneven shape, it has been difficult to apply a uniform and beautiful plating film.

[0009] Patent Document 2 describes an aluminum bumper that transmits millimeter waves. However, although this expresses a metallic design by aluminum flakes, it focuses on millimeter wave transmissibility and has not been sufficiently studied for chemical resistance and weather resistance.

[0010] On the other hand, the metallic decorative laminate of the present disclosure has a specific layer structure, so that it is 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 an intermediate laminate, a multilayer laminate, a decorative laminate, and a metallic article that include the metallic decorative laminate as a component, and also to provide a method for manufacturing the intermediate laminate and a method for manufacturing the decorative laminate.

[0012] Hereinafter, the metal-like decorative laminate, intermediate laminate, multilayer laminate, decorative laminate, metal-like article, metal-like article, and method for manufacturing a metal-like decorative laminate according to the present invention will be described. Note that the present invention is not limited to the following examples.

[0013] In the present disclosure, the thickness direction 100 means the lamination direction of the metal-like decorative laminate or the metal-like article as illustrated in FIG. 1, and the width direction 110 means a direction different from the thickness direction and perpendicular to the longitudinal direction 120 of the metal-like decorative laminate or the metal-like article. For example, when manufacturing the intermediate laminate described later in a roll-to-roll manner, 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 sometimes referred to as "the present embodiments") will be described. In the present disclosure, the numerical values related to "above", "below", "~", etc. in the description of numerical ranges are numerical values that can be arbitrarily combined.

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

[0016] 〔Metal-like decorative laminate〕 The metal-like decorative laminate of the present embodiment includes a glitter resin layer containing one or more fluororesins and one or more glitter materials, and a transparent resin layer containing one or more fluororesins. The content of the fluororesin in the resin component (1) in the glitter resin layer is more than 30% by mass, and the content of the fluororesin in the resin component (2) in the transparent resin layer is more than 30% by mass. It is required to be a metal-like decorative laminate.

[0017] The metallic decorative laminate of the present embodiment can be used, for example, for decorating resin parts and metal parts such as automotive bumpers (hereinafter also simply referred to as "articles") by film decoration methods such as insert molding and overlay molding using a multilayer laminate including the metallic decorative laminate. Further, the multilayer laminate including the metallic decorative laminate may be used to decorate the surface of an article via an adhesive layer or an adhesive layer. For example, it can be used as a surface layer in automotive exterior parts such as automotive pillars, door moldings, roof moldings, entire doors, and entire roofs. Further, the metallic decorative laminate of the present embodiment exhibits an excellent metallic design and is excellent in chemical resistance and weather resistance, so it is preferable for outdoor use. Furthermore, since it is excellent in chemical resistance, it is preferably used for decorating four-wheeled vehicles, two-wheeled vehicles, pumps, etc. that use lubricating oil.

[0018] Furthermore, although details will be described later, the metallic decorative laminate of the present embodiment is preferable because its production is easy and it is excellent in mass productivity.

[0019] The layer thickness of the metallic decorative laminate of the present embodiment is preferably 20 μm or more, more preferably 30 μm or more, still more preferably 35 μm or more, and even more preferably 40 μm or more in order to improve design properties and weather resistance. In order to improve moldability, it is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 70 μm or less, and even more preferably 65 μm or less. Although it might seem that chemical resistance is preferably better with a thicker layer thickness, it has been found that if the layer thickness becomes too thick, it will rather deteriorate.

[0020] In order to balance design properties, weather resistance, and chemical resistance, it is preferably 20 μm or more and 100 μm or less, more preferably 30 μm or more and 80 μm or less, still more preferably 35 μm or more and 70 μm or less, and even more preferably 40 μm or more and 65 μm or less.

[0021] In the present disclosure, "design property" means the property that an article exhibits a metallic design by using the metallic decorative laminate of the present disclosure for the article.

[0022] In the present disclosure, "chemical resistance" means a property in which even if an organic solvent, lubricating oil, or the like adheres to the transparent resin layer contained in the metal-like decorative laminate of the present disclosure, dissolution, swelling, and reaction are suppressed, and it means a property including oil resistance and solvent resistance, and can be evaluated, for example, by the method described in the examples.

[0023] In the present disclosure, "weather resistance" means a property in which deformation, discoloration, deterioration, etc. are unlikely to occur when used outdoors, and can be evaluated, for example, by the method described in the examples.

[0024] In the present disclosure, "moldability" means a property that is easy to manufacture when manufacturing a metal-like article using the metal-like decorative laminate of the present disclosure. The moldability can suppress breakage during molding by increasing the layer thickness, and can decorate fine parts of the article by reducing the layer thickness. It can be evaluated, for example, by the method described in the examples.

[0025] The total light transmittance of the metal-like decorative laminate of the present embodiment can be adjusted as necessary. As will be described later, the metal-like decorative laminate of the present embodiment exhibits a metal-like design due to the contained brightening material, but it is also preferable from the viewpoint of expressing design properties to adjust the color tone by adding pigments or the like described later as necessary.

[0026] The total light transmittance of the metal-like decorative laminate of the present embodiment can be appropriately adjusted by the content of the brightening material, the shape of the brightening material, and the content of pigments or the like. When the pigment is not contained or even if it is contained but the content is small, the total light transmittance can be increased.

[0027] The total light transmittance of the metallic decorative laminate of the present embodiment is preferable because it can exhibit a metallic design when external light such as sunlight is strong on a sunny day. The total light transmittance can be adjusted by the content of the luminescent material. When the content is increased to more strongly exhibit the metallic design by the luminescent material, the total light transmittance decreases, which is preferable for shielding the color of the article to which the metallic tone is imparted. In order to exhibit such an effect, the total light transmittance is preferably 3% or more, more preferably 5% or more, still more preferably 6% or more, even more preferably 8% or more, and the upper limit is not particularly limited, but it is sufficient to exhibit the metallic design of the metallic decorative laminate of the present disclosure, and it is preferably 40% or less, more preferably 30% or less, still more preferably 20% or less, even more preferably 15% or less, and the color of the article may be substantially unrecognizable from the side of the metallic decorative laminate.

[0028] The total light transmittance can be measured, for example, by the method described in the examples. The metallic decorative laminate of the present embodiment may include only the luminescent resin layer and the transparent resin layer described later, or may include other resin layers described later.

[0029] When the metallic decorative laminate of the present embodiment is installed on an article to form a metallic article described later, the luminescent resin layer is preferably located on the article side, and the transparent resin layer is preferably the outermost surface of the metallic article.

[0030] <Luminescent resin layer> The luminescent resin layer is a layer that imparts a metallic luster to the metallic decorative laminate, contains a resin component (1) containing one or more fluorine-based resins and one or more luminescent materials, and the content of the fluorine-based resin in the resin component (1) in the luminescent resin layer is required to be more than 30% by mass.

[0031] The bright 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 further contain other components described later. The bright resin layer may contain only the fluororesin, the thermoplastic resin, and the brightening material, and may further contain other components described later.

[0032] As described above, it is preferable that the metallic-looking article is laminated in the order of the article, the bright resin layer, and the transparent resin layer. In particular, it is preferable that the transparent resin layer is on the outermost surface of the metallic-looking article. Since the transparent resin layer comes into contact with the atmosphere, solvents, chemicals, etc., its chemical resistance and weather resistance are expected to play a major role in improving the chemical resistance and weather resistance of the metallic-looking article. However, as a result of repeated studies, it was found that the composition of the bright resin layer that does not directly contact chemicals, etc. is extremely important for improving the chemical resistance and weather resistance of the metallic-looking article. Even when the same transparent resin layer is used, the chemical resistance and weather resistance differ depending on the bright resin layer to be combined. The bright resin layer can improve the chemical resistance and weather resistance of the metallic-looking article by containing a fluororesin and a brightening material. The fluororesin and the brightening material are not usually considered to have an effect of improving chemical resistance and weather resistance. Furthermore, since the bright resin layer is a layer that does not directly contact the outside air, etc., a person skilled in the art usually considers 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 adopting the configuration as in this embodiment. The reason for this is not clear, but it is considered that when the bright resin layer contains a fluororesin and a brightening material, the aggregation of the fluororesin in the transparent resin layer is suppressed, and the fluororesin is uniformly dispersed in the transparent resin layer, so that the chemical resistance and weather resistance characteristics of the fluororesin are expressed on the layer surface.

[0033] The layer thickness of the fluorescent resin layer is preferably 5 μm or more, more preferably 8 μm or more, still more preferably 10 μm or more, and even more preferably 13 μm or more in order to improve the design property because the amount of the fluorescent material increases as the layer thickness increases and to improve the design property, chemical resistance, and weather resistance because the effects on the transparent resin layer are achieved by the invention. In order to improve the chemical resistance and moldability, it is preferably 100 μm or less, more preferably 60 μm or less, still more preferably 40 μm or less, and even more preferably 35 μm or less.

[0034] In order to balance the chemical resistance, weather resistance, design property, and moldability, it is preferably 5 μm or more and 100 μm or less, more preferably 8 μm or more and 60 μm or less, still more preferably 10 μm or more and 40 μm or less, and even more preferably 13 μm or more and 35 μm or less.

[0035] As described above, the fluorescent resin layer contains one or more fluorine-based resins as the resin component (1), and may further contain one or more thermoplastic resins. These may be a mixture (polymer alloy) or a reaction product, but a mixture (polymer alloy) is more preferable for improving the dispersibility of the fluorescent material in the metallic decorative laminate.

[0036] Details of the fluorine-based resin will be described later. Only one type of single fluorine-based resin may be used, or two or more types may be used in combination. Using only one type is preferable because a uniform metallic decorative laminate can be easily manufactured, and using two or more types is preferable because physical property values such as the melting point of the resin component (1) can be easily adjusted.

[0037] Details of the thermoplastic resin will be described later. Only one type of single thermoplastic resin may be used, or two or more types may be used in combination. Using only one type is preferable because a uniform metallic decorative laminate can be easily manufactured, and using two or more types is preferable because physical property values such as the melting point of the resin component (1) can be easily adjusted.

[0038] The resin component (1) contained in the fluorescent resin layer may contain other components other than the fluororesin. Details of the other components will be described later. In the present disclosure, components other than the fluorescent material contained in the fluorescent resin layer are defined as the resin component (1).

[0039] When the total of the resin component (1) contained in the fluorescent resin layer is 100% by mass, the total content of the fluororesin and the thermoplastic resin when contained is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 97% by mass or more. The upper limit is not particularly limited and is preferably substantially 100% by mass. "Substantially" means excluding impurities and the like that are inadvertently included.

[0040] When the resin component (1) contained in the fluorescent resin layer contains the fluororesin and the thermoplastic resin, the ratio of the content of the fluororesin in the content of the thermoplastic resin (content of the fluororesin (% by mass) / content of the thermoplastic resin (% by mass)) is preferably 0.30 or more and 4.00 or less, more preferably 0.80 or more and 3.00 or less, still more preferably 1.10 or more and 2.00 or less, and even more preferably 1.30 or more and 1.80 or less. Even when an acrylic resin described later is used as the thermoplastic resin, it is preferably 0.30 or more and 4.00 or less, more preferably 0.80 or more and 3.00 or less, still more preferably 1.10 or more and 2.70 or less, and even more preferably 1.30 or more and 2.50 or less.

[0041] It is preferable to increase the content of the fluororesin compared to the content of the thermoplastic resin (acrylic resin) because the dispersibility of the fluororesin in the transparent resin layer is improved, and the chemical resistance and weather resistance are improved.

[0042] The brightening resin layer contains one or more brightening materials described below in addition to the resin component (1), and the brightening material in the brightening resin layer is preferably 0.05 parts by mass or more and 20.00 parts by mass or less based on 100 parts by mass in total of the resin component (1). Setting it to be not less than the lower limit value is preferable because the chemical resistance, weather resistance, and design property of the metallic decorative laminate are improved. Setting it to be not more than the upper limit value is preferable because the moldability is improved. More preferably, it is 0.50 parts by mass or more and 15.00 parts by mass or less, still more preferably 1.00 parts by mass or more and 13.00 parts by mass or less, even more preferably 3.00 parts by mass or more and 10.00 parts by mass or less, particularly preferably 4.00 parts by mass or more and 7.00 parts by mass or less, and most preferably 4.50 parts by mass or more and 5.50 parts by mass or less.

[0043] <<Fluororesin>> Generally, the fluororesin is added for the purpose of improving chemical resistance, weather resistance, etc. In the present embodiment, since the resin component (1) contains the fluororesin, the chemical resistance and weather resistance of the metallic article using this are improved even though the brightening resin layer does not directly contact chemicals or the like. Furthermore, when the resin component (1) contains a fluororesin, the dispersibility of the brightening material is improved, and the metallic article using this will have a uniform metallic luster.

[0044] As the fluororesin, any generally used as a fluororesin can be used. Examples thereof preferably include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (CTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene - hexafluoropropylene copolymer (FEP), ethylene - tetrafluoroethylene copolymer (ETFE), ethylene - chlorotrifluoroethylene copolymer (ECTFE), etc. In particular, polyvinylidene fluoride (PVDF) is preferable because when used as the resin component, it has excellent film - forming property and further forms a brightening resin layer with excellent dispersibility of the brightening material.

[0045] When using the thermoplastic resin (acrylic resin) described later, the weight average molecular weight (Mw) of the fluororesin is preferably 800 or more and 5,000 or less, more preferably 1,000 or more and 3,000 or less, still more preferably 1,300 or more and 2,000 or less, and even more preferably 1,500 or more and 1,700 or less in order to facilitate the formation of the polymer alloy.

[0046]

[0047]

[0048] <<Luminescent material>>

[0049] The luminescent material is not particularly limited as long as it is contained in order to reflect external light (incident light) by being dispersed in the resin composition, impart a metallic luster to the luminescent resin layer, and exhibit the design property 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.

[0050] The surface of the luminescent material may be coated. The coating may be a coating with an organic substance such as silicone or a coating with an inorganic substance such as silica gel or alumina.​​As the brightening material, it is preferable to contain at least one material selected from scaly or flaky metals, scaly or flaky alloy metals, scaly or flaky metal oxides, scaly or flaky mica, glass flakes, and film pulverized bodies. As long as the resin composition contains a material that can exhibit brightness, any material can be used. However, from the viewpoints of easy availability and improved design, scaly or flaky metals, scaly or flaky mica, or film pulverized bodies are more preferable, scaly or flaky metals or scaly or flaky mica are even more preferable, and scaly or flaky metals are even more preferable.

[0051] The scaly or flaky metal is particles obtained by making metal powder into a flaky shape. As the metal, any metal that is usually used for scaly or flaky metals can be preferably used, but aluminum, iron, copper, nickel, zinc, gold, silver, oxides of these metals, and alloys containing these metals are more preferably mentioned. Examples of scaly or flaky metals include aluminum flakes, stainless steel flakes, copper flakes, nickel flakes, etc. In order to obtain a metallic decorative laminate with excellent metallic design, the scaly or flaky metal is preferably flakes of aluminum or its alloy, and aluminum flakes are more preferable.

[0052] Examples of scaly or flaky mica include white pearl pigments, interference pearl pigments, colored pearl pigments, etc. The white pearl pigment is obtained by covering a scaly matrix such as mica, aluminum, or glass with a coating layer made of a colorless high refractive index material such as titanium dioxide. The layer thickness of the coating layer is preferably about 0.1 μm or more and 0.15 μm or less. The interference pearl pigment has a structure in which the coating layer is coated with a colorless high refractive index material such as titanium dioxide. The layer thickness of the coating layer is preferably more than 0.15 μm.

[0053] The luminescent material is preferably uniformly dispersed in the resin component within the luminescent resin layer 30 in FIG. 2 and oriented such that the thickness direction 210 of the luminescent material is substantially parallel to the thickness direction 100. Although FIG. 2 schematically depicts the luminescent material as a disk shape, it is not limited thereto. The longest length in the planar direction (particle diameter direction 220 of the luminescent material) of the luminescent material 200 is defined as the particle diameter 221 of the luminescent material, and the average thickness in the thickness direction of the luminescent material perpendicular to the planar direction is defined as the thickness 211 of the luminescent material. These are average values measured under an optical microscope by randomly sampling 20 luminescent materials. The particle diameter 221 of the luminescent material can be substituted by the volume average particle diameter (D 50 ) described in the examples. The particle diameter 221 (D 50 ) of the luminescent material is preferably 3 μm or more, more preferably 4 μm or more, still more preferably 5 μm or more, in order to facilitate acquisition and exhibit a metallic design. In order to improve the transmitted light amount and chemical resistance and weather resistance, it is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less, even more preferably 15 μm or less, and most preferably 10 μm or less.

[0054] To balance chemical resistance, weather resistance, design, and moldability, it is preferably 3 μm or more and 50 μm or less, more preferably 3 μm or more and 30 μm or less, still more preferably 4 μm or more and 20 μm or less, even more preferably 4 μm or more and 15 μm or less, and most preferably 5 μm or more and 10 μm or less.

[0055] The thickness 211 of the luminescent 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, still more preferably 0.10 μm or more and 0.50 μm or less, in order to achieve both chemical resistance, weather resistance, design, and moldability.

[0056] The particle diameter 221 (D 50)The ratio of the particle size of the phosphorescent material to its thickness 211 (= 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 still more preferably 10 or more and 100 or less.

[0057] Fluorine-based resins have a tendency to aggregate. By aggregating, they tend to take on a fine particulate shape (hereinafter referred to as aggregates), and by becoming such aggregates, their compatibility with other resin components is poor, and there is a tendency to prevent the uniform presence of the fluorine-based resin. Even if the aggregates are pulverized and then stirred with, for example, a thermoplastic resin, re-aggregation occurs in the resin composition, and the resin composition becomes a non-uniform dispersion state. When the resin component is applied, the aggregates tend to be unevenly present on the coating surface. When it becomes such a non-uniform state, the characteristics of the fluorine-based resin cannot be fully exhibited. A method of adding a nucleating agent described later is known to prevent the growth of these aggregates. When a nucleating agent is added, there is an effect of suppressing the growth of the particle size even if aggregates are generated. However, if the addition amount of the nucleating agent is increased, it causes a decrease in weather resistance and a decrease in moldability. The phosphorescent material is added to improve the designability, and when used together with a fluorine-based resin, an effect of suppressing the growth of aggregates of the fluorine-based resin was confirmed. In addition, since the fluorine-based resin improves the dispersibility of the phosphorescent material, due to the synergistic effect of using both the fluorine-based resin and the phosphorescent material, the phosphorescent resin layer has a uniform layer structure.

[0058] <<Thermoplastic resin>> The phosphorescent resin layer preferably further contains one or more thermoplastic resins.

[0059] The total content of the thermoplastic resin in the resin component (1) in the phosphorescent resin layer is preferably 20% by mass or more and less than 70% by mass, more preferably 25% by mass or more and 60% by mass or less, even more preferably 30% by mass or more and 50% by mass or less, and still more preferably 35% by mass or more and 45% by mass or less.

[0060] Examples of the thermoplastic resin include polyolefin resins, polyester resins, polystyrene resins, etc. Among them, polyolefin resins are preferred because they have good moldability.

[0061] The mass average molecular weight (Mw) of the polyolefin resin is preferably 30,000 or more and 500,000 or less, more preferably 50,000 or more and 300,000 or less, still more preferably 70,000 or more and 200,000 or less, and even more preferably 90,000 or more and 100,000 or less in order to improve impact resistance.

[0062] The polydispersity (Mw / Mn) of the polyolefin resin is preferably 1.5 or more and 5.0 or less, more preferably 1.6 or more and 4.0 or less, still more preferably 1.7 or more and 3.0 or less, and even more preferably 1.9 or more and 2.2 or less in order to improve impact resistance.

[0063] The glass transition temperature (Tg) of the polyolefin resin is preferably 100°C or more, more preferably 108°C or more, still more preferably 115°C or more, and even more preferably 117°C or more in order to improve impact resistance.

[0064] The upper limit value of Tg is not particularly limited, but from the viewpoint of moldability, it is preferably 150°C or less, more preferably 140°C or less, still more preferably 130°C or less, and even more preferably 125°C or less.

[0065] (Acrylic resin) As the polyolefin resin, an acrylic resin is preferable. As the acrylic resin, any derivative such as acrylic acid and its esters, and polymers and copolymers of methacrylic acid derivatives such as methyl methacrylate can be used as long as they are used as acrylic resins. More specifically, polyethyl methacrylate (PEMA), polybutyl methacrylate (PBMA), polycyclohexyl methacrylate (PCHMA), polyethylhexyl methacrylate (PEHMA), etc. are preferably mentioned. In particular, methyl polymethacrylate resin (PMMA) is useful when used as a resin component because it has high transparency, excellent scratch resistance due to high hardness, and is thermoplastic and can be processed into complex shapes.

[0066] The mass average molecular weight (Mw) of the acrylic resin is preferably 30,000 or more and 500,000 or less, more preferably 50,000 or more and 300,000 or less, still more preferably 70,000 or more and 200,000 or less, and even more preferably 90,000 or more and 100,000 or less in order to facilitate the formation of a polymer alloy with the fluororesin.

[0067] The polydispersity (Mw / Mn) of the acrylic resin is preferably 1.5 or more and 5.0 or less, more preferably 1.6 or more and 4.0 or less, still more preferably 1.7 or more and 3.0 or less, and even more preferably 1.9 or more and 2.2 or less in order to facilitate the formation of a polymer alloy with the fluororesin.

[0068] The glass transition point (Tg) of the acrylic resin is preferably 100°C or more, more preferably 108°C or more, still more preferably 115°C or more, and even more preferably 117°C or more when forming a resin component with the fluororesin, so as to be more uniform and suppress the crystallinity of the fluororesin.

[0069] The upper limit value 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, still more preferably 130 °C or lower, and even more preferably 125 °C or lower.

[0070] In order to achieve the above-mentioned Tg range, the acrylic resin preferably has an imide skeleton in its structure.

[0071] <<Other Components>> As the other components, a nucleating agent, an ultraviolet absorber, an antioxidant, a pigment, an antistatic agent, a leveling agent, a defoaming agent, etc. can be used as necessary.

[0072] (Nucleating Agent) As described above, it is preferable to use a nucleating agent because it can control the aggregation of the bright resin layer. The fluororesin is a crystalline resin and is known to form crystals in the resin layer. When crystals are generated and the crystallite size grows due to aggregation in the resin layer, the resin layer may become cloudy due to scattering by the crystals. When the nucleating agent is used, it is preferable because the crystallite size can be reduced. The nucleating agent can be variously selected depending on the resin component to be used, but it is preferable to use acrylic-modified polytetrafluoroethylene because it can control the crystallite size of the fluororesin.

[0073] As the ultraviolet absorber, antioxidant, pigment, antistatic agent, leveling agent, and defoaming agent, general-purpose compounds can be used. As the ultraviolet absorber, benzotriazole-based compounds are preferable.

[0074] <Transparent Resin Layer> The transparent resin layer is a layer laminated on the surface opposite to the article with respect to the bright resin layer, and is preferably the outermost layer when the article has a metallic appearance. The transparent resin layer contains a resin component (2) containing one or more fluororesins, and the content of the fluororesin in the resin component (2) in the transparent resin layer needs to be more than 30% by mass.

[0075] The resin component (2) may contain only the fluororesin, or may further contain one or more thermoplastic resins, or may contain only the fluororesin and the thermoplastic resin. The resin component (2) may further contain other components described below.

[0076] For the metal-decorated laminate, external light passes through the transparent resin layer, a part of which is reflected by the metal-like resin layer and then passes through the transparent resin layer again, so that the viewer of the metal-like article can recognize the metallic luster. Therefore, the transparent resin layer is required to have transparency, and its total light transmittance is preferably 80% or more, more preferably 90% or more, still more preferably 95% or more, even more preferably 98% or more, and the upper limit is not particularly limited as long as the metallic design of the metal-decorated laminate of the present disclosure can be exhibited. The total light transmittance can be measured, for example, by the method described in the examples.

[0077] The transparent resin layer is preferably the outermost layer when the article has a metallic appearance as described above. Therefore, in order to improve chemical resistance and weather resistance, it is preferable that the lower limit of the layer thickness is larger, and in order to improve design and moldability, it is preferable that the upper limit of the layer thickness is smaller. It is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more, 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, still more preferably 40 μm or less, even more preferably 35 μm or less.

[0078] In order to balance chemical resistance, weather resistance, design, and moldability, it is preferably 5 μm or more and 100 μm or less, more preferably 10 μm or more and 60 μm or less, still more preferably 20 μm or more and 40 μm or less, even more preferably 25 μm or more and 35 μm or less.

[0079] When using the luminous resin layer as the outermost surface of the metallic decorative laminate, if necessary, various patterns may be applied to the surface by embossing or the like, and a matte feeling may be imparted by providing fine irregularities. Also, a hairline design may be imparted by hairline processing.

[0080] The fluororesin, thermoplastic resin, and other components used in the transparent resin layer can be the same as those used in the resin component (1), and the content of each component is also the same as that of the resin component (1).

[0081] <Other layer structure> The metallic decorative laminate may further include other layers. As the other layers, a surface protection layer, a primer layer, an adhesive layer, etc. may be included as necessary.

[0082] As the surface protection layer and the primer layer, general-purpose films such as urethane resin, polyester resin, acrylic resin, acrylic urethane resin, vinyl chloride-vinyl acetate copolymer resin can be used. As the adhesive layer, a polyurethane-based adhesive layer is preferable in order to obtain sufficient transparency and adhesive strength.

[0083] 〔Intermediate laminate〕 The intermediate laminate of this embodiment needs to further include a base material described later on the transparent resin layer side of the metallic decorative laminate.

[0084] The intermediate laminate is manufactured when manufacturing the metallic decorative laminate or the like. Although the manufacturing method of each laminate will be described later, a metallic decorative laminate can be easily manufactured by laminating a transparent resin layer and a luminous resin layer on the base material described later. The intermediate laminate may include the metallic laminate and the base material, but may include only the metallic laminate and the base material, or may further include the other layers described above. The layer thickness of the intermediate laminate may be adjusted as appropriate, but is preferably 30 μm or more and 200 μm or less, more preferably 60 μm or more and 160 μm or less, still more preferably 80 μm or more and 140 μm or less, and even more preferably 100 μm or more and 120 μm or less.

[0085] <Base material> The base material is used for applying a coating liquid for forming a transparent resin layer thereon when manufacturing a metal-like decorative laminate as described later, and is a layer for protecting the outermost surface on the transparent resin layer side when transporting or storing the multilayer laminate described later. It also serves as a release layer for peeling at any stage of the manufacturing process of the metal-like article.

[0086] As the base material, any material that can be used as a base material in the technical field can be used, and it can be appropriately selected from polyethylene-based base materials, polyester-based base materials (including polyethylene terephthalate (PET) base materials), polycarbonate-based base materials, etc. PET is more preferable due to requirements such as handling properties during manufacturing and ease of availability.

[0087] The thickness of the base material may be within a range that does not interfere with the manufacturing process, but generally, those with a thickness of 10 μm or more and 150 μm or less can be used.

[0088] 〔Multilayer laminate〕 The multilayer laminate needs to include a base layer on the side of the intermediate laminate where the bright resin layer is located. An adhesive layer may further be provided between the intermediate laminate and the base layer, and it is preferable that the intermediate laminate and the base layer are adhered by an adhesive layer, and the multilayer laminate may further include the other layers described above. The layer thickness of the multilayer laminate may be adjusted as appropriate.

[0089] <Base layer> As the base layer, considering the influence on the design and taking into account the heat resistance to the temperature during molding into a shiny decorative molded article, compatibility with injection molding resins in insert injection molding, etc., from resins such as polyvinyl chloride-based, polyolefin-based, polystyrene-based, polyacrylic-based, polyurethane-based, polyamide-based, polycarbonate-based, acrylonitrile-butadiene-styrene copolymer-based (ABS resin), etc., the material for the base layer can be appropriately selected.

[0090] Also, the layer thickness of the base layer can be, for example, 50 μm to 1000 μm so as to be a general thickness as a decorative laminate. When the layer thickness of the base layer is within the above range, it is preferable because it can suppress the occurrence of defects such as wrinkles during film formation and can also suppress the breakage of the metallic decorative laminate during the molding process of metallic articles. Further, if the layer thickness of the base layer exceeds 1000 μm, the moldability of metallic articles may decrease. It is also preferable that the base layer contains a pigment. Thereby, the influence of the color of the article on the metallic article can be suppressed, and it is also possible to express a color gamut that is difficult to express only with the shiny material, so that the design can be improved.

[0091] 〔Decorative laminate〕 The decorative laminate is obtained by peeling the base material (release layer) from the multilayer laminate, and it is necessary to include a base layer on the shiny resin layer side of the metallic decorative laminate. As will be described later, metallic articles are manufactured using the decorative laminate. The base layer may contain a pigment.

[0092] 〔Metallic article〕 The metallic article of this embodiment needs to include the metallic decorative laminate.

[0093] The metal-like article of the present embodiment is manufactured using the metal-like decorative laminate by, for example, the manufacturing method described below, and is formed into a desired shape according to the purpose. For example, it is used for smartphones, mobile phone casings, automobile bumpers, emblems, door mirror housings, front grills, door handles, center wheel caps, emblems, ornaments, garnishes, lamp reflectors, center consoles, installation panels, etc., casings and decorative parts of personal computers, TVs, and home appliances, casings and decorative parts of pachinko machines, pachislot machines, game machines, etc., or generally used for carry-on bags, suitcases, etc., and can impart metal-like decorativeness and designability instead of plating or metal materials.

[0094] In particular, the metal-like decorative laminate of the present embodiment not only imparts a metal-like design to the article, but also imparts chemical resistance and weather resistance to the article. In the present disclosure, an "article" is a precursor of the metal-like article, which becomes a metal-like article by being decorated with the decorative laminate.

[0095] In addition to the above configuration, the metal-like article of the present embodiment may include other configurations. For example, until the metal-like article of the present embodiment is used, a release paper, a protective film, etc. can be provided on the surface of the protective layer or the base material layer to keep the surface of the protective layer or the base material layer clean and prevent dirt from adhering.

[0096] 〔Manufacturing methods of intermediate laminate, multilayer laminate, decorative laminate, and metal-like article〕 The metal-like decorative laminate of the present embodiment is common to the intermediate laminate, the multilayer laminate, the decorative laminate, and the metal-like article, and is formed in the process of manufacturing the intermediate laminate.

[0097] The manufacturing method of the intermediate laminate of the present embodiment requires applying a coating liquid containing one or more of the fluorine-based resins, applying a coating liquid containing one or more of the fluorine-based resins and one or more of the brightening materials, and heating, in this order.

[0098] Since fluororesins, brightening materials, thermoplastic resins, other components, metallic decorative laminates, intermediate laminates, multilayer laminates, decorative laminates, and metallic articles have already been described, they will be omitted.

[0099] (Coating liquid containing one or more of the above fluororesins) The coating liquid containing one or more of the above fluororesins is a coating liquid for forming a transparent resin layer, and may further contain the thermoplastic resin and / or other components. The coating liquid may further contain a solvent, which may be a uniform solvent or a slurry.

[0100] (Solvent) As the solvent, any solvent generally used as a solvent in the art may be used. Examples of the solvent include polar solvents such as ester solvents, ether solvents, and ketone solvents; nonpolar solvents such as hydrocarbon solvents and aromatic solvents; and alcohol solvents such as methanol, ethanol, and isopropyl alcohol. However, polar solvents such as ester solvents, ether solvents, and ketone solvents are preferred.

[0101] In the method for producing a metallic decorative laminate of the present embodiment, it is preferable that the solvent exhibits the property of a poor solvent with respect to the fluororesin and the property of a good solvent with respect to the acrylic resin. If the fluororesin is not dissolved in the coating liquid before heating described later, it is preferable because the acrylic resin does not react with the fluororesin before heating, and no lumps are generated due to the reaction products of the fluororesin and the acrylic resin in the coating liquid. Since no such lumps are generated, coating unevenness or the like does not occur during coating, and a uniform brightening resin layer can be produced. As a solvent having such characteristics, butyl carbitol acetate can be preferably mentioned.

[0102] When using the solvent, in order to shorten the processing time of the subsequent heating and improve the coatability of the coating liquid on the substrate, the total 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 still more preferably 150.0 parts by mass or more and 200.0 parts by mass or less with respect to 100 parts by mass.

[0103] (Coating liquid containing one or more of the fluororesins and one or more of the luminescent materials) The coating liquid containing one or more of the fluororesins and one or more of the luminescent materials is a coating liquid for forming a luminescent resin layer, and may further contain the thermoplastic resin and / or other components. The coating liquid may further contain the solvent, and may be a uniform solvent, a slurry, or the like.

[0104] <Coating> The coating can be performed by known means such as a gravure coater, a reverse coater, a die coater, a knife coater, a roll coater, etc. on the substrate or on the resin layer formed on the substrate.

[0105] <Heating> The heating may be started before the coating is completed or may be performed after the coating is completely completed, but it is preferable to heat in a state where the coating liquid is on the substrate. The heating includes the case where the substrate is pre-heated and then coated and further heated. By the heating, when the solvent is used in the coating liquid, the solvent is distilled off. By heating the resin component to a temperature equal to or higher than the Tg of the resin component contained therein, it can be mixed with the fluororesin. As a result, the crystallite diameter of the fluororesin does not grow, precipitation of the fluororesin from the resin component is suppressed, and the luminescent material is also uniformly dispersed, which is preferable.

[0106] The heating temperature can be selected appropriately depending on the heating time, the fluorine-based resin, thermoplastic resin, other components, solvent, and substrate used, etc., but in order to obtain a metallic decorative laminate that has excellent design and achieves chemical resistance, weather resistance, and moldability, the heating temperature is preferably 100°C or higher, more preferably 150°C or higher, even more preferably 170°C or higher, preferably 250°C or lower, more preferably 220°C or lower, and even more preferably 200°C or lower. The heating method can be appropriately selected from heating methods used in the relevant field depending on the shape, size, etc. of the object to be heated.

[0107] The heating time can be selected appropriately depending on the size of the laminate to be produced, the heating temperature, the fluorine-based resin, thermoplastic resin, solvent, and substrate to be used, etc., but in order to obtain a metallic decorative laminate with excellent design and excellent millimeter wave transmittance, the heating time is preferably 30 seconds or more, more preferably 1 minute or more, and preferably 5 minutes or less, and more preferably 3 minutes or less.

[0108] <Removing the substrate> The method for producing the decorative laminate of this embodiment must include peeling the substrate from the multi-layer laminate. The metallic decorative laminate produced by the method for producing the metallic decorative laminate is formed on a substrate, and therefore the decorative laminate can be obtained by peeling off the substrate (release layer). The peeling method is not particularly limited as long as it is a method commonly used in the relevant field.

[0109] <Metallic Product Manufacturing Method> The metallic article of this embodiment can be produced, for example, by the following method. The method includes a molding step in which the surface temperature of the decorative laminate is set to 150°C to 200°C, the decorative laminate is brought into close contact with a mold so that the base film side faces the article, and the decorative laminate is molded onto the surface of the article to obtain a metallic article.

[0110] (molding process) When the surface temperature of the decorative laminate is 150°C to 200°C for thermoforming, the decorative laminate does not draw down during molding, and whitening and other phenomena do not occur, resulting in satisfactory moldability. A surface temperature of 150°C or higher sufficiently softens the decorative laminate, preventing it from sagging and deforming due to drawdown, which would make processing and molding difficult. Furthermore, a surface temperature of 200°C or lower prevents the decorative laminate from entering a molten state and becoming too soft, making molding difficult, or from easily causing whitening and other phenomena.

[0111] The shape of the mold to which the decorative laminate is adhered can be any shape so that the metallic article can be molded into the desired shape. For example, a male mold or a female mold with a chrome-plated brass surface can be used. The temperature of the mold can be set to any temperature taking into consideration control of the surface temperature of the decorative laminate and control of the cooling conditions of the metallic article after the molding process.

[0112] As a method for adhering the decorative laminate to a mold, any method can be used taking into consideration ease of molding, cost, etc., such as straight molding using a female mold, drape molding using a male mold, or plug-assist molding using a plug (auxiliary mold). Also, a vacuum forming method in which the metallic decorative laminate is sucked into a mold, or a pressure forming method in which the metallic decorative laminate is adhered to a mold using compressed air pressure can be used. For example, by adhering the metallic decorative laminate to a mold using vacuum and / or compressed air, the adhesion between the decorative laminate and the mold is improved, allowing it to be processed into a more precise shape.

[0113] (Clamping process) The method for manufacturing the metal-like article can 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 loosen during molding. Clamping can be performed, for example, by using multiple gripping means capable of gripping both sides of the decorative laminate, for example, by gripping both ends of the decorative laminate. Grip of the decorative laminate is not limited to both ends of the decorative laminate, and any part of the decorative laminate can be gripped. Typically, when metal-like articles are continuously produced, both ends of the decorative laminate in the width direction can be gripped. Furthermore, when metal-like articles are batch-produced using rectangular pieces of the decorative laminate cut to a predetermined length, the ends of the four sides can be gripped by upper and lower frames.

[0114] (Heating process) The method for producing the metallic article can also include a heating step of heating the decorative laminate 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, and these heaters can be arranged above and below the decorative laminate to uniformly heat both sides of the decorative laminate simultaneously. This heating step can control the surface temperature of the decorative laminate to 150°C to 200°C.

[0115] (Other processes) The method for producing a metal-like article may include other steps in addition to the steps described above. For example, it may include a step of attaching a protective film or the like to the surface of the protective layer or the base layer in order to keep the surface of the protective layer or the base layer clean and prevent contamination until the metal-like article is processed in the next step. Furthermore, after inserting the metal-like article into an injection molding die, insert injection molding is performed in which a resin is injected, and the surface of the injection-molded product can be decorated.

[0116] The metallic decorative laminate of this embodiment, the intermediate laminate, multilayer laminate, decorative laminate, metallic article, and the manufacturing method of the intermediate laminate and the decorative laminate are preferably the following [1] to

[13] . [1] A photoluminescent resin layer containing a resin component (1) containing one or more fluorine-based resins and one or more photoluminescent materials; and a transparent resin layer containing a resin component (2) containing one or more fluorine-based resins, the content of the fluorine-based resin in the resin component (1) in the glittering resin layer is more than 30% by mass, The metallic decorative laminate has a fluorine-based resin content of 30% by mass or more in the resin component (2) in the transparent resin layer. [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 [1] or [2], wherein the amount of the glittering material in the glittering 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). [4] The metallic decorative laminate according to any one of [1] to [3], wherein the lustrous material contains at least one material selected from the group consisting of scaly or flaky metals, scaly or flaky alloy metals, scaly or flaky metal oxides, scaly or flaky mica, glass flakes, and pulverized film. [5] The metallic decorative laminate according to any one of [1] to [4], wherein the resin component (2) further contains one or more thermoplastic resins. [6] An intermediate laminate comprising a substrate on the transparent resin layer side of the metallic decorative laminate according to any one of [1] to [5]. [7] A multilayer laminate comprising a base layer on the photoluminescent resin layer side of the intermediate laminate according to [6]. [8] The multilayer laminate according to [7], wherein the base layer contains a pigment. [9] A decorative laminate comprising a base layer on the glittering resin layer side of the metallic decorative laminate according to any one of [1] to [5].

[10] The decorative laminate according to [9], wherein the base layer contains a pigment.

[11] A metallic article comprising the metallic decorative laminate according to any one of [1] to [5].

[12] Applying a coating liquid containing one or more fluororesins

[12] Applying a coating liquid containing one or more fluororesins and one or more luminescent materials Heating, in this order, the manufacturing method of the intermediate laminate according to [6].

[13] A method for manufacturing a decorated laminate according to [9] or

[10] , including peeling a base material from a multilayer laminate.

Examples

[0117] Hereinafter, the present invention will be described more specifically using examples. However, the present invention is not limited to the following examples at all.

[0118] (Evaluation method) 1. Chemical resistance evaluation The chemical resistance evaluation was carried out using a commercially available brake fluid (manufactured by ○○, product name: ○○) mainly composed of polyethylene glycol monoether, assuming use in four-wheel vehicles or two-wheel vehicles, vacuum pumps, etc. Decorated laminates 25 cm × 25 cm 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 decorated laminate at 9 points in a 3×3 pattern using a dropper. After standing for 5 hours, the brake fluid was washed with toluene, left at 25°C for 1 hour, and after confirming that the toluene had dried, the surface state was visually observed and evaluated as follows: A~D. A: No change is observed at all 9 points compared to before the test. B: Dripping marks of the brake fluid can be confirmed in parts with less than 4 points. C: Dripping marks of the brake fluid can be confirmed in parts with 4 or more and less than 8 points. D: Dripping marks of the brake fluid can be confirmed in parts with 8 or more points.

[0119] 2. Weather resistance evaluation A xenon weather meter SX75 7.5kW (manufactured by Suga Test Instruments) was used. The treatment conditions were a black panel temperature of 63±2°C, humidity of 50%RH, rainfall cycle (non-rainfall time / rainfall time) of 102 min / 18 min, and illuminance of 180 W / m 2 , tank temperature 25~35℃, 500MJ / m 2 The color difference between the sample surface on the transparent resin layer side of the decorative laminate obtained in the Examples and Comparative Examples before and after treatment was measured using a color difference meter CM-3600A (manufactured by Konica Minolta), and was evaluated as A to C below. A: When ΔE*=3.0 or less, the weather resistance was evaluated as very good. B: When ΔE* was greater than 3.0 and not greater than 5.0, the sample was evaluated as having weather resistance. C: When ΔE* was greater than 5.0, it was evaluated as not having weather resistance.

[0120] 3. Heat resistance evaluation The decorative laminates obtained in the examples and comparative examples were left in an environment of 100°C for 500 hours, and 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 color difference meter CM-3600A (manufactured by Konica Minolta), and evaluated as A to C as follows. A: When Δb*=1.0 or less and there is no defect such as peeling of the decorative sheet, the heat resistance was evaluated as very good. B: When Δb* was greater than 1.0 and not greater than 3.0, and there was only slight trouble such as peeling of the decorative sheet, the product was evaluated as having heat resistance. C: When Δb* was greater than 5.0 and a major defect such as peeling of the decorative sheet was observed, the sample was evaluated as having no heat resistance.

[0121] 4.Design evaluation The decorative laminates obtained in the examples and comparative examples were visually observed from the transparent resin layer side and rated as A or B below. A: It has a metallic design. B: It does not have a metallic design or has a matte finish.

[0122] 5. Measurement of crystalline state by X-ray diffraction (XRD) By XRD measurement, X-rays were irradiated from the transparent resin layer side of the decorated laminate obtained in the examples or comparative examples, and the diffraction intensity was measured. The decorated laminates (3 cm × 3 cm) obtained in the examples and comparative examples were prepared as test samples for inspection. These samples were sealed with a Kapton film for XRD and measured under the following conditions using a powder X-ray diffractometer D2 PHASER manufactured by BRUKER Corporation. The Intensity of the X-ray diffraction spectrum was Tube voltage: 30 kV Tube current: 10 mA X-ray wavelength: Cu-Kα ray (1.5418 Å) Optical system: Convergent method Slit configuration: Solar slit 4° (both on the incident side and the light-receiving side), divergence slit 1 mm, Kβ filter (Ni plate 0.5%), air scatter screen 3 mm were used Detector: Semiconductor detector Measurement range: 2θ = 10 - 60 deg Step width, scan speed: 0.05 deg, 0.05 deg / second

[0123] 6. Total light transmittance The total light transmittance was measured for the decorated laminates obtained in the examples or comparative examples using a spectrophotometer (UH4150 manufactured by Hitachi High-Technologies Corporation) in accordance with JIS K7375:2008.

[0124] 7. Design evaluation after molding The metal-like articles made using the decorated laminates obtained in the examples and comparative examples were visually observed and evaluated as follows: A - C. A: Presents a metal-like design. B: There are no problems in practical use, but it is inferior to the metal-decorated laminate evaluated as "A" in terms of the metal-like design. C: Does not present a metal-like design or presents a matte feeling.

[0125] 8. Molding property evaluation For the metallic articles produced 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. A: No cloudiness is observed, and no cracks or tears are seen. B: Cloudiness is observed, or cracks or tears have occurred.

[0126] 9.Method of measuring molecular weight The number average molecular weight (Mn), weight average molecular weight (Mw), average molecular weight (Mz) and polydispersity (Mw / Mn) of the fluorine-based resins and acrylic resins used in the examples and comparative examples were determined as follows. Tetrahydrofuran (THF) was added to the sample to be measured, and the concentration was adjusted to 2 mg / mL. The resulting solution was filtered through a membrane filter (PTFE, pore size: 0.45 μm), and the filtrate was subjected to molecular weight measurement by size exclusion chromatography (SEC). The measurement conditions for SEC are as follows: Apparatus: Size exclusion chromatograph (Tosoh HLC-8320GPC) Eluent: tetrahydrofuran (stabilizer-free) Column: TSKgel Super HM-M (two columns in series) Detector: differential refractometer Measurement temperature: 40℃ Flow rate: 0.6mL / min Injection volume: 20μL Molecular weight calculation conditions Relative molecular weight values were calculated based on standard substances. Standard material: 12 standard polystyrenes (molecular weight 504 to 1.09 x 10 6 ) Calibration curve: cubic approximation curve (Materials used) (Fluorine-based resin (Arkema, 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%

[0127] (Example 1) (Manufacture of intermediate laminate containing metal-modified laminate) (Film formation of transparent resin layer) The coating solution for the transparent resin layer described below was applied to a substrate (PET film (G2000 (manufactured by Toyobo Co., Ltd.))). The coating amount was adjusted so that the film thickness of the glossy resin layer after heating would be 30 μm. Immediately after coating, it was heated at 180°C for 2 minutes to form a transparent resin layer on the substrate. Then, it was cooled to room temperature.

[0128] ((Coating solution for transparent resin layer)) 8.75 g of an acrylic resin (manufactured by Asahi Kasei Corporation, SK540) was added to 37.45 g of butyl carbitol acetate (manufactured by Sankyo Kasei Industry Co., Ltd.) and stirred at room temperature to form a uniform solution. Further, other components (0.57 g of an ultraviolet absorber (manufactured by Asahi Kasei Corporation, Tinuvin900) and 0.06 g of a nucleating agent (manufactured by Mitsubishi Chemical Corporation, A-3000)) and 13.16 g of a fluororesin (manufactured by Arkema, kyanr301) were added, and further stirred to obtain a coating solution for a transparent resin layer containing resin component (2).

[0129] In Table 1, the respective contents of the acrylic resin, fluororesin, and other components in resin component (2) were described.

[0130] (Film formation of glossy resin layer) The coating solution for the glossy resin layer described below was applied onto the transparent resin layer of the substrate on which the transparent resin layer was formed above. The coating amount was adjusted so that the film thickness of the glossy resin layer after heating would be 25 μm. It was heated at 180°C for 2 minutes immediately after coating to laminate the light-emitting resin layer. Then, it was cooled to room temperature to produce an intermediate laminate including a metal layer-decorated laminate. The substrate was peeled off from the obtained intermediate laminate, and the transparent resin layer side was subjected to chemical resistance evaluation, weather resistance evaluation, heat resistance evaluation, design evaluation, and total light transmittance measurement. The results are shown in Table 2 together with those of other examples and comparative examples.

[0131] Fig. 3 shows the X-ray diffraction spectrum obtained by XRD measurement of the decorated laminate of Example 1. The XRD measurement results are shown in Fig. 3.

[0132] (Coating liquid for light-emitting resin layer) 8.75 g of an acrylic resin (SK540, manufactured by Asahi Kasei Corporation) was added to 37.45 g of butyl carbitol acetate (manufactured by Sankyo Kasei Kogyo Co., Ltd.), and stirred at room temperature to obtain a uniform solution. Further, other components (0.57 g of an ultraviolet absorber (Tinuvin900, manufactured by BASF Japan Ltd.) and 0.06 g of a nucleating agent (A-3000, manufactured by Mitsubishi Chemical Corporation)) and 13.16 g of a fluororesin (kyanr301, manufactured by Arkema Inc.) were added and stirred to obtain a solution containing resin component (1). To the obtained solution containing resin component (1), 1.13 g of aluminum flakes (FD5060, manufactured by Asahi Kasei Corporation, volume average particle diameter (D 50 ): 6.0 μm) was added, and further stirred to obtain a coating liquid for a light-emitting resin layer.

[0133] Table 1 describes the respective contents of the acrylic resin, fluororesin, and other components in resin component (1), and the amount of use (parts by mass) of the light-emitting material when resin component (1) is 100 parts by mass.

[0134] (Manufacture of metallic article) (Film formation of adhesive layer and base layer) A urethane adhesive for the metallic decorative sheet was used on the photoluminescent resin layer of the intermediate laminate, which was a mixture of a base material consisting of a mixture of polyester-based diol, polycarbonate-based diol, carbodiimide, a silane coupling agent having an epoxy group, and ethyl acetate, and a curing agent consisting of an aliphatic isocyanate.

[0135] TM-K51 (manufactured by Toyo-Morton Co., Ltd.) was used as the polyester-based diol, Duranol T5652 (manufactured by Asahi Kasei Corporation) was used as the polycarbonate-based diol, Carbodilite V-07 (manufactured by Nisshinbo Chemical Inc.) was used as the carbodiimide, KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent having an epoxy group, and CAT-RT85 (manufactured by Toyo-Morton Co., Ltd.) was used as the aliphatic isocyanate.

[0136] A urethane adhesive was applied to the surface of the photoluminescent resin layer using a bar coater so that the dry thickness of the adhesive layer would be approximately 10 μm. The coating was dried at 60°C for 1 minute, and then laminated with a PET film (average thickness 25 μm, Teflex FT3, manufactured by Toyobo) as a base layer to produce a multilayer laminate. The substrate was peeled off from the resulting multilayer laminate to produce a decorative laminate. Using the obtained decorative laminate, a compressed air molding machine was used to clamp the base layer of the decorative laminate into a test mold so that it would become an article.The metallic decorative laminate was then preformed to fit into a mold for injection molding at a preforming temperature of 160°C and a compressed air pressure of 6 bar, and any unnecessary parts that protruded from the mold were trimmed off to obtain a metallic article.

[0137] The decorative laminate and metallic article obtained in Example 1 were evaluated for chemical resistance, weather resistance, heat resistance, design, total light transmittance, post-molding design, and moldability, and the results are shown in Table 2.

[0138] (Comparative Example 1) to (Comparative Example 4) The decorative laminates and metallic articles of Comparative Examples 1 to 4 were manufactured in the same manner as in Example 1, except that the film thickness, the amount of fluorine-based resin used, the amount of acrylic resin used, and the amount of aluminum flakes used were changed as shown in Table 1. In Table 1, The decorative laminates and metallic articles obtained in Comparative Examples 1 to 4 were evaluated for chemical resistance, weather resistance, heat resistance, design, total light transmittance, post-molding design, and moldability, and the results are shown in Table 2.

[0139] Figure 4 shows the X-ray diffraction spectrum obtained by XRD measurement of the decorative laminate of Comparative Example 1, Figure 5 shows the X-ray diffraction spectrum obtained by XRD measurement of the decorative laminate of Comparative Example 3, and Figure 6 shows the X-ray diffraction spectrum obtained by XRD measurement of the decorative laminate of Comparative Example 4.

[0140] [Table 1]

[0141] [Table 2]

[0142] "-" in the table indicates that measurement was not possible or was not performed. The results of Example 1 shown in Table 2 indicate that the metallic decorative laminate of this embodiment exhibits a metallic design and has excellent properties in terms of chemical resistance, weather resistance, heat resistance, and total light transmittance. Furthermore, the results of XRD measurements indicate that these properties, particularly chemical resistance and weather resistance, are achieved by the growth of fluororesin crystals in the photoluminescent resin layer. Furthermore, the environmental impact of wastewater generated by processes such as metal plating was reduced. Furthermore, it was confirmed that all metallic articles containing the metallic decorative laminates present no practical problems.

[0143] In contrast, in Comparative Example 1, the glittering resin layer did not contain a glittering material, so the metallic design was not expressed. Furthermore, the surface of the transparent resin layer of the decorative laminate developed a so-called orange peel pattern. Furthermore, when a moldability evaluation was performed, the surface also developed an orange peel pattern, making it unsuitable for practical use.

[0144] In Comparative Examples 2 and 3, the content of the fluorine-based resin in the resin component (1) (total of fluorine-based resin, acrylic resin, and other components) of the glossy resin layer is 30% by mass or less. When the fluorine-based resin is not included, as in Comparative Example 3, cracks occurred during film formation, and a multilayer laminate could not be obtained. Furthermore, Comparative Example 3 also had poor chemical resistance evaluation results. When the fluorine-based resin content is 30% by mass, as in Comparative Example 2, film formation is possible, but aluminum flakes settle on the transparent resin layer side of the glossy resin layer, forming an aluminum flake layer, which prevents the metallic design from appearing and prevents irradiated light from passing through, making it impossible to measure total light transmittance.

[0145] In Comparative Example 4, the content of the fluorine-based resin in the resin component (2) (total of the fluorine-based resin, the acrylic resin, and other components) of the transparent resin layer is 30 mass % or less. In this case, although a metallic design is produced, the chemical resistance is not at a practical level.

[0146] 3 to 6, the decorative laminate of Example 1 has a smaller peak intensity at 2θ = 10 to 20° than the decorative laminate of the comparative example, indicating that the crystallite diameter of the crystals contained therein is smaller. It was found that the transparent resin layer of the decorative laminate of this embodiment suppresses the growth of fluororesin crystals. It is believed that the small crystallite diameter allows the fluororesin to be uniformly distributed in the transparent resin layer, resulting in superior results in each evaluation item compared to the decorative laminate of the comparative example. [Industrial Applicability]

[0147] The metallic decorative laminate, intermediate laminate, multilayer laminate, decorative laminate, and metallic article of the present embodiment exhibit an excellent metallic design, reduce the environmental load during manufacturing, have chemical resistance and weather resistance, are excellent in productivity, can impart metallic decoration and designability instead of plating and metallic materials, and are suitably used for automobiles, home appliances, information terminals, etc.

Explanation of Signs

[0148] 1: Metallic decorative laminate 2: Intermediate laminate 3: Decorative laminate 4: Multilayer laminate 10: Base material (release layer) 20: Transparent resin layer 30: Glittering resin layer 31: Surface on the side opposite to the article of the glittering resin layer 32: Surface on the article side of the glittering resin layer 40: Adhesive layer 50: Base layer 100: Thickness direction 110: Width direction 120: Longitudinal direction 200: Glittering material 210: Thickness direction of the glittering material 211: Thickness of the glittering material 220: Particle diameter direction of the glittering material 221: Particle diameter of the glittering material

Claims

1. A resin component (1) containing one or more fluorine-based resins and a phosphorescent resin layer containing one or more phosphorescent materials, and a transparent resin layer containing a resin component (2) containing one or more fluorine-based resins, wherein the content of the fluorine-based resin in the resin component (1) in the phosphorescent resin layer is more than 30% by mass, and the content of the fluorine-based resin in the resin component (2) in the transparent resin layer is more than 30% by mass. A metallic decorative laminate.

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 1 or 2, wherein the phosphorescent material in the phosphorescent resin layer is 0.05 parts by mass or more and 20.00 parts by mass or less with respect to 100 parts by mass of the resin component (1).

4. The metallic decorative laminate according to any one of claims 1 to 3, wherein the phosphorescent material contains at least one material selected from flaky or flaky metals, flaky or flaky alloys, flaky or flaky metal oxides, flaky or flaky mica, glass flakes, and film pulverizates.

5. The metallic decorative laminate according to any one of claims 1 to 4, wherein the resin component (2) further contains one or more thermoplastic resins.

6. An intermediate laminate including a substrate on the transparent resin layer side of the metallic decorative laminate according to any one of claims 1 to 5.

7. A multilayer laminate including a base layer on the phosphorescent resin layer side of the intermediate laminate according to claim 6.

8. The multilayer laminate according to claim 7, wherein the base layer contains a pigment.

9. A decorative laminate including a base layer on the phosphorescent resin layer side of the metallic decorative laminate according to any one of claims 1 to 5.

10. The decorative laminate according to claim 9, wherein the base layer contains a pigment.

11. A metallic decorative article including the metallic decorative laminate according to any one of claims 1 to 5.

12. Applying a coating liquid containing one or more fluorine-based resins, applying a coating liquid containing one or more fluorine-based resins and one or more phosphorescent materials, and heating, in this order. A method for manufacturing the intermediate laminate according to claim 6.

13. A method for manufacturing the decorative laminate according to claim 9 or 10, including peeling a substrate from the multilayer laminate according to claim 7 or 8.

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