Metallic-toned decorative laminate, metallic-toned article, and method for producing 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

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

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

[0002] In order to enhance the design of resin molded products, it has been common to impart a metallic luster to the surface of the resin molded product. Metal plating has been used as a means of imparting this metallic luster (Patent Document 1). In addition, for other uses, electromagnetic wave transparent bright coated resin products have been developed (Patent Document 2).

[0003] JP 2002-241948 A JP 2010-030075 A

[0004] The present invention aims to provide a metallic decorative laminate, intermediate laminate, multilayer laminate, decorative laminate and metallic article that exhibits an excellent metallic design, reduces the environmental impact during production, and has 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.

[0005] As a result of intensive research conducted by the present inventors to solve the above-mentioned problems, the present inventors have provided the following [1] to [7]. [1] A metallic decorative laminate comprising a resin component (1) containing one or more fluorine-based resins, a glittering resin layer containing one or more dyes and one or more glittering materials, and a transparent resin layer containing a resin component (2) containing one or more fluorine-based resins. [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 glittering resin layer side of the intermediate laminate described in [2]. [4] A decorative laminate comprising a base layer on the glittering resin layer side of the metallic decorative laminate described in [1]. [5] A metallic article comprising the metallic decorative laminate described in [1]. [6] A method for producing the intermediate laminate according to [2], which comprises, in this order, applying a coating liquid containing one or more fluorine-based resins, applying a coating liquid containing one or more fluorine-based resins, one or more dyes, and one or more luster materials, and heating. [7] A method for producing the decorative laminate according to [4], which comprises peeling off the substrate from the multilayer laminate according to [3].

[0006] According to the present invention, there are provided metallic decorative laminates, intermediate laminates, multilayer laminates, decorative laminates and metallic articles that exhibit excellent metallic designs, reduce the environmental impact during production, and have improved chemical resistance and weather resistance, and there are also provided methods for manufacturing the intermediate laminates and the decorative laminates.

[0007] 1 is a schematic diagram showing an example of a multilayer laminate including the metallic decorative laminate of the present embodiment. FIG. 2 is a schematic diagram showing a glittering material in a glittering resin layer.

[0008] The aforementioned Patent Document 1 describes an invention relating to a plated synthetic resin component for vehicles, which exhibits a metallic luster by plating a synthetic resin component. However, metal plating has problems such as a complicated process, high manufacturing costs, and the generation of waste liquid, which places a burden on the environment. Furthermore, when the surface of a molded product has an uneven shape, it is difficult to apply a uniform and beautiful plating film.

[0009] The aforementioned Patent Document 2 describes an aluminum-look bumper that transmits millimeter waves. However, although this uses aluminum flakes to create a metallic design, the focus is on millimeter wave transmittance, and chemical resistance and weather resistance have not been sufficiently considered.

[0010] In contrast, the metallic decorative laminate of the present disclosure has a specific layer structure, which allows it to exhibit an excellent metallic design and to obtain a metallic decorative laminate with improved chemical resistance and weather resistance.

[0011] In addition, it is possible to provide intermediate laminates, multilayer laminates, decorative laminates, and metallic articles that use the metallic decorative laminate as a component, as well as methods for manufacturing the intermediate laminates and the decorative laminates.

[0012] Hereinafter, the metallic decorative laminate, intermediate laminate, multilayer laminate, decorative laminate, metallic article, metallic article, and method for manufacturing the metallic 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 refers to the stacking 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 perpendicular to the longitudinal direction 120 of the metallic decorative laminate or metallic article. For example, when the intermediate laminate described below is manufactured by roll-to-roll, the longitudinal direction 120 corresponds to the machine direction (MD), and the width direction 110 corresponds to the transverse direction (TD) perpendicular to the MD.

[0014] Hereinafter, an embodiment of the present disclosure (hereinafter, sometimes referred to as "the present embodiment") will be described. Note that in this disclosure, numerical values ​​related to "greater than or equal to," "less than or equal to," "to," etc., in describing a numerical range are numerical values ​​that can be combined arbitrarily.

[0015] Furthermore, preferred provisions can be adopted arbitrarily. That is, one preferred provision can be adopted in combination with one or more other preferred provisions. A combination of preferred provisions is more preferable.

[0016] [Metallic Decorative Laminate] The metallic decorative laminate of this embodiment is a metallic decorative laminate comprising a resin component (1) containing one or more fluorine-based resins, a photoluminescent resin layer containing one or more dyes and one or more photoluminescent 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 photoluminescent resin layer and a transparent resin layer. The photoluminescent resin layer contains a resin component (1), a pigment, and a photoluminescent 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 to decorate resin parts such as car bumpers and metal parts (hereinafter also simply referred to as "articles") by film decoration methods such as insert molding or overlay molding using a multilayer laminate containing the metallic decorative laminate. Furthermore, a multilayer laminate containing the metallic decorative laminate may be used to decorate the surface of an article via an adhesive layer or adhesive layer, and can be used as a surface layer for automotive exteriors such as automobile pillars, door moldings, roof moldings, entire door surfaces, and entire roof surfaces. Furthermore, 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. Furthermore, due to its excellent chemical resistance, it is preferable for use in decorating four-wheeled vehicles, two-wheeled vehicles, pumps, etc. that use lubricating oils.

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

[0020] The layer thickness of the metallic decorative laminate of this embodiment is preferably 20 μm or more in order to improve design and weather resistance, more preferably 30 μm or more, even more preferably 35 μm or more, and even more preferably 40 μm or more, and in order to improve formability, 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 seems that a thicker layer thickness is preferable for chemical resistance, it has been found that if the layer thickness is too thick, it actually deteriorates.

[0021] In order to balance design, weather resistance, and chemical resistance, the thickness is preferably 20 μm or more and 100 μm or less, more preferably 30 μm or more and 80 μm or less, even more preferably 35 μm or more and 70 μm or less, and even more preferably 40 μm or more and 65 μm or less.

[0022] In the present disclosure, "designability" means the property that, when the metallic decorative laminate of the present disclosure is used in an article, the article will exhibit a metallic design and will be able to express the required color tone using the added pigment and lustrous material.

[0023] In the present disclosure, "chemical resistance" refers to the property of suppressing dissolution, expansion, and reaction even when organic solvents or lubricating oils, etc., adhere to the transparent resin layer contained in the metallic decorative laminate of the present disclosure, and refers to properties including oil resistance and solvent resistance, which can be evaluated, for example, by the method described in the examples.

[0024] In the present 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 the present disclosure, "moldability" refers to the property of ease of manufacturing when manufacturing a metallic article using the metallic decorative laminate of the present disclosure. Moldability is preferable because a thicker layer can suppress breakage during molding, and a thinner layer can be preferable because it allows for decoration of even small parts 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 will be described later, the metallic decorative laminate of this embodiment expresses a metallic design due to the contained glittering material and pigment.

[0027] The total light transmittance of the metallic decorative laminate of this embodiment can be adjusted appropriately by the content of the luster material, the shape of the luster material, the content of the pigment, and the like.

[0028] The total light transmittance of the metallic decorative laminate of this embodiment is preferably low because it allows the metallic design to be expressed under strong external light, such as during the day when sunlight is present. The total light transmittance can be adjusted by the content of the luster material and / or pigment. When a light source is installed on the article side of the metallic decorative laminate and color is expressed by light passing through the metallic decorative laminate, a high total light transmittance is preferred. When the content is increased to more strongly express the metallic design using the luster material, the total light transmittance decreases, which is preferable because it shields the color of the article to which the metallic tone is imparted. In addition, the total light transmittance can also be reduced by increasing the content of the pigment to adjust the color tone. In order to achieve such an effect, 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. The upper limit is not particularly limited, but it is sufficient that the metallic design of the metallic decorative laminate of the present disclosure is expressed. 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 it may be so that the color of the article is 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 include only the glittering resin layer and the transparent resin layer described below, but may also include other resin layers described below.

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

[0032] <Glittering resin layer> The shiny resin layer is a layer that imparts metallic luster to the metallic decorative laminate, and is required to contain a resin component (1) containing one or more fluorine-based resins, one or more dyes, and one or more shiny materials.

[0033] The photoluminescent 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 below. The resin component (1) refers to not only the fluororesin but also components excluding the photoluminescent material contained in the photoluminescent resin layer.

[0034] The glittering resin layer may contain only the fluorine-based resin, the thermoplastic resin, the dye, and the glittering material, or may further contain other components described below.

[0035] As described above, it is preferable that the metallic article be laminated in the order of the article, the glittering resin layer, and the transparent resin layer. In particular, it is preferable that the transparent resin layer be the outermost surface of the metallic article. Because 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 article. However, after extensive investigation, it was found that the configuration of the glittering resin layer, which does not directly contact chemicals, is extremely important for improving the chemical resistance and weather resistance of the metallic article. Even when the same transparent resin layer is used, the chemical resistance and weather resistance differ depending on the glittering resin layer combined. The glittering resin layer contains a fluorine-based resin and a glittering material, which can improve the chemical resistance and weather resistance of the metallic article. Because the glittering resin layer does not directly come into contact with the outside air, those skilled in the art would normally believe that it does not contribute to the chemical resistance and weather resistance of the metallic article. However, it was found that the layer configuration of this embodiment improves chemical resistance and weather resistance. The reason for this is not clear, but it is thought that when the photoluminescent resin layer contains a fluororesin and a photoluminescent material, aggregation of the fluororesin in the transparent resin layer is suppressed and the fluororesin is uniformly dispersed within the transparent resin layer, allowing the chemical resistance and weather resistance characteristics of the fluororesin to be expressed on the layer surface.

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

[0037] The thicker the layer thickness of the lustrous resin layer, the greater the amount of lustrous material, thereby improving the design, and since the above-mentioned effects on the transparent resin layer are realized, in order to improve the design, chemical resistance, and weather resistance, the layer thickness 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; and in order to improve chemical resistance and moldability, the layer 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] In order to balance chemical resistance, weather resistance, designability, and moldability, the thickness is preferably 5 μm or more and 100 μm or less, more preferably 8 μm or more and 60 μm or less, even more preferably 10 μm or more and 40 μm or less, and even more preferably 13 μm or more and 35 μm or less.

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

[0040] Although the details of the fluorine-based resin will be described later, only one type of fluorine-based resin may be used, or two or more types may be used in combination. Using only one type is preferable because it is possible to easily produce a uniform metallic decorative laminate, and using two or more types is preferable because it is possible to easily adjust the physical properties such as the melting point of the resin component (1).

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

[0042] The resin component (1) contained in the glittering resin layer may contain other components in addition to the fluorine-based resin. Details of the other components will be described later. In the present disclosure, the components contained in the glittering resin layer other than the glittering material are referred to as resin component (1).

[0043] When the total of the resin component (1) contained in the glittering resin layer is taken as 100% by mass, the total content of the fluororesin and the thermoplastic resin, if contained, 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, and it is preferably substantially 100% by mass. "Substantially" means excluding impurities and the like that are unintentionally contained.

[0044] When the resin component (1) contained in the glittering resin layer contains the fluorine-based resin and the thermoplastic resin, the ratio of the content of the fluorine-based resin in the content of the thermoplastic resin (content (% by mass) of the fluorine-based resin / content (% by mass) of the thermoplastic resin) is preferably 0.30 to 4.00, more preferably 0.80 to 3.00, even more preferably 1.10 to 2.00, and even more preferably 1.30 to 1.80. Even when an acrylic resin described below is used as the thermoplastic resin, the ratio is preferably 0.30 to 4.00, more preferably 0.80 to 3.00, even more preferably 1.10 to 2.70, and even more preferably 1.30 to 2.50.

[0045] By making the content of the fluororesin larger than the content of the thermoplastic resin (for example, acrylic resin), the dispersibility of the fluororesin in the transparent resin layer is improved, and chemical resistance and weather resistance are improved, which is preferable.

[0046] The glittering resin layer contains, in addition to the resin component (1), one or more dyes and one or more glittering materials described below, and the glittering material in the glittering resin layer is preferably 0.01 parts by mass or more to 20.00 parts by mass or less relative to a total of 100 parts by mass of the resin component (1). By setting it to the lower limit or more, the chemical resistance, weather resistance, and design of the metallic decorative laminate are improved, and by setting it to the upper limit or less, the moldability is improved. It is more preferably 0.02 parts by mass or more to 15.00 parts by mass or less, more preferably 0.03 parts by mass or more to 10.00 parts by mass or less, even more preferably 0.05 parts by mass or more to 5.00 parts by mass or less, and even more preferably 0.07 parts by mass or more to 3.00 parts by mass or less, and even more preferably 0.08 parts by mass or more to 2.00 parts by mass or less.

[0047] The pigment in the glittering resin layer is preferably 0.05 parts by mass or more and 20.00 parts by mass or less relative to 100 parts by mass of the resin component (1). By making it equal to or more than the lower limit, the chemical resistance, weather resistance and design of the metallic decorative laminate are improved, and by making it equal to or less than the upper limit, the moldability is improved, and it is more preferably 0.10 parts by mass or more and 15.00 parts by mass or less, more preferably 0.20 parts by mass or more and 13.00 parts by mass or less, even more preferably 0.30 parts by mass or more and 10.00 parts by mass or less, and more preferably 0.35 parts by mass or more and 7.00 parts by mass or less, and even more preferably 0.40 parts by mass or more and 5.00 parts by mass or less.

[0048] The total amount of the glittering material and the pigment in the glittering resin layer is preferably 0.05 parts by mass or more and 20.00 parts by mass or less relative to 100 parts by mass of the resin component (1). By making it equal to or more than the lower limit, the chemical resistance, weather resistance and design of the metallic decorative laminate are improved, and by making it equal to or less than the upper limit, the moldability is improved. It is more preferable that it is 0.10 parts by mass or more and 15.00 parts by mass or less, more preferably 0.20 parts by mass or more and 13.00 parts by mass or less, even more preferably 0.30 parts by mass or more and 10.00 parts by mass or less, and more preferably 0.35 parts by mass or more and 7.00 parts by mass or less, and even more preferably 0.40 parts by mass or more and 5.00 parts by mass or less.

[0049] <<Fluorine-based resin>> The fluorine-based resin is generally added for the purpose of improving chemical resistance, weather resistance, etc. In this embodiment, by including the fluorine-based resin in the resin component (1), the chemical resistance and weather resistance of the metallic article using the same are improved, even though the glittering resin layer does not come into direct contact with chemicals, etc. Furthermore, when the resin component (1) includes a fluorine-based resin, the dispersibility of the glittering material is improved, and the metallic article using the same will have a uniform metallic luster.

[0050] As the fluorine-based resin, any resin generally used as a fluorine-based resin can be used, and preferred examples include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (CTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), perfluoroalkoxy fluorine resin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), etc. In particular, polyvinylidene fluoride (PVDF) is preferred because it can be used as the resin component to form a photoluminescent resin layer that is excellent in film-forming properties and excellent in the dispersibility of photoluminescent materials.

[0051] When a thermoplastic resin (acrylic resin) described below is used, the mass 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, even more preferably 1,300 or more and 2,000 or less, and even more preferably 1,500 or more and 1,700 or less, in order to facilitate the formation of a polymer alloy.

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

[0053] The content of the fluorine-based resin in the resin component (1) in the glittering resin layer is preferably from 30.00% by mass to 80.00% by mass, more preferably from 35.00% by mass to 80.00% by mass, even more preferably from 40.00% by mass to 75.00% by mass, still more preferably from 50.00% by mass to 70.00% by mass, and even more preferably from 55.00% by mass to 65.00% by mass.

[0054] <<Dye>> The dye is dispersed in the resin composition to express a color design that cannot be expressed by the luster material alone, which will be described later, and is exclusive of the luster material described later.

[0055] The dye does not reflect external light (incident light) but absorbs light of a specific wavelength to adjust the hue of the glittering resin layer.

[0056] The pigment contained in the glittering resin layer is one commonly used in the technical field. It 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 or organic compound, or a natural or synthetic pigment, as long as it absorbs visible light. Synthetic pigments are preferred, particularly when used outdoors and weather resistance is required, and organic pigments are preferred to improve color development. The pigment preferably contains an inorganic or organic pigment, and is preferably an inorganic or organic pigment. More specifically, preferred pigments include inorganic pigments such as titanium white (titanium oxide), zinc white, red iron oxide, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, and carbon black; and organic pigments (including dyes) such as isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene blue RS, and aniline black.

[0057] <<Glittering material>> The lustrous material is not particularly limited as long as it is dispersed in the resin composition to reflect external light (incident light), impart a metallic luster to the lustrous resin layer, and be contained in order to express the design properties of the metallic decorative laminate. The lustrous material may be an inorganic pigment or an organic pigment, and may be a natural material or a synthetic material, but is preferably an inorganic pigment in order to improve the reflectivity of external light.

[0058] The surface of the photoluminescent material may be coated with an organic material such as silicone, or an inorganic material such as silica gel or alumina.

[0059] The lustrous material preferably contains at least one material selected from scaly or flaky metal, scaly or flaky composite metal, scaly or flaky metal oxide, scaly or flaky mica, glass flakes, and pulverized film. Any material may be contained in the resin composition as long as it exhibits lustrous properties, but for reasons of ease of availability and improved design, scaly or flaky metal, scaly or flaky mica, or pulverized film are more preferred, scaly or flaky metal or scaly or flaky mica are even more preferred, and scaly or flaky metal is even more preferred.

[0060] The scale-like or flake-like metal is a particle obtained by thinning a metal powder. As the metal, any metal commonly used for scale-like or flake-like metal is preferably used, but aluminum, iron, copper, nickel, zinc, gold, silver, oxides of these metals, and alloys containing these metals are more preferred. Examples of scale-like or flake-like metals include aluminum flakes, stainless steel flakes, copper flakes, and nickel flakes. In order to obtain a metallic decorative laminate having excellent metallic design, the scale-like or flake-like metal is preferably flakes of aluminum or its alloy, and more preferably aluminum flakes.

[0061] Examples of scaly or flake mica include white pearl pigments, interference pearl pigments, and colored pearl pigments.

[0062] The white pearl pigment is a scaly base material such as mica, aluminum, or glass covered 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 about 0.1 μm or more and 0.15 μm or less.

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

[0064] The photoluminescent material is preferably sufficiently uniformly dispersed in the resin component in the photoluminescent resin layer 30 in Figure 2, and oriented so that the thickness direction 210 of the photoluminescent material is approximately parallel to the thickness direction 100. While Figure 2 shows the photoluminescent material as a schematic disc, this is not limited thereto. The longest length in the planar direction of the photoluminescent material 200 (particle diameter direction 220 of the photoluminescent material) is taken as the particle diameter 221 of the photoluminescent material, and the average thickness in the thickness direction of the photoluminescent material perpendicular to the planar direction is taken as the thickness 211 of the photoluminescent material. These are average values ​​measured under an optical microscope by randomly sampling 20 particles of the photoluminescent material. The particle diameter 221 of the photoluminescent material is the volume average particle diameter (D ５０ ) can be substituted. ５０ The volume average particle diameter (D) is preferably 3 μm or more, more preferably 4 μm or more, and even more preferably 5 μm or more in terms of ease of availability and the ability to exhibit a metallic design, and is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, even more preferably 15 μm or less, and even more preferably 10 μm or less in terms of improving the amount of transmitted light and improving chemical resistance and weather resistance. ５０ ) can be measured by a standard method.

[0065] In order to balance chemical resistance, weather resistance, designability, and moldability, the thickness is preferably 3 μm or more and 50 μm or less, more preferably 3 μm or more and 30 μm or less, even more preferably 4 μm or more and 20 μm or less, even more preferably 4 μm or more and 15 μm or less, and even more preferably 5 μm or more and 10 μm or less.

[0066] In order to achieve both chemical resistance, weather resistance, designability, and moldability, the thickness 211 of the lustrous material is preferably 0.05 μm or more and 1.00 μm or less, more preferably 0.10 μm or more and 0.80 μm or less, and even more preferably 0.10 μm or more and 0.50 μm or less.

[0067] Particle diameter of the glittering material 221 (D ５０The ratio of the particle diameter 211 to the thickness 211 of the lustrous material (=particle diameter / 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 tend to aggregate easily. Aggregation can easily result in the formation of minute particulates (hereinafter referred to as aggregates). These aggregates tend to reduce compatibility with other resin components and prevent the fluororesin from being uniformly dispersed. Even if the aggregates are pulverized and then stirred with, for example, a thermoplastic resin, they re-aggregate within the resin composition, resulting in an unevenly dispersed resin composition. When the resin composition is applied, the aggregates tend to be unevenly distributed on the coated surface. This uneven state prevents the fluororesin from fully exhibiting its properties. To prevent this growth, a method of adding a nucleating agent (described below) is known. The addition of a nucleating agent has the effect of suppressing the growth of particle size even if aggregates are formed. However, increasing the amount of nucleating agent used can result in a decrease in weather resistance and moldability. Luminous materials are added to improve design, but when used with fluororesins, they have been shown to suppress the growth of fluororesin aggregates. Furthermore, since the fluororesin improves the dispersibility of the luster material, the use of both the fluororesin and the luster material produces a synergistic effect, resulting in a uniform layer structure of the luster resin layer.

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

[0070] The total content of the thermoplastic resin in the resin component (1) in the glittering 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, with polyolefin resins being preferred due to their good moldability.

[0072] In order to improve impact resistance, 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, even more preferably 70,000 or more and 200,000 or less, and even more preferably 90,000 or more and 100,000 or less.

[0073] In order to improve impact resistance, 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, even more preferably 1.7 or more and 3.0 or less, and even more preferably 1.9 or more and 2.2 or less.

[0074] In order to improve impact resistance, the glass transition point (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.

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

[0076] (Acrylic Resin) The polyolefin resin is preferably an acrylic resin. As the acrylic resin, those used as polymers and copolymers of acrylic acid derivatives such as acrylic acid and its esters, and methacrylic acid derivatives such as methyl methacrylate can be used. More specifically, polyethyl methacrylate (PEMA), polybutyl methacrylate (PBMA), polycyclohexyl methacrylate (PCHMA), polyethylhexyl methacrylate (PEHMA), etc. are preferably mentioned. In particular, polymethyl methacrylate resin (PMMA) is useful as a resin component because it has high transparency and high hardness, making it excellent in scratch resistance, and can be processed into complex shapes due to its thermoplasticity.

[0077] In order to facilitate the formation of a polymer alloy with the fluororesin, 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, even more preferably 70,000 or more and 200,000 or less, and even more preferably 90,000 or more and 100,000 or less.

[0078] In order to facilitate the formation of a polymer alloy with the fluororesin, 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, even more preferably 1.7 or more and 3.0 or less, and still more preferably 1.9 or more and 2.2 or less.

[0079] The glass transition point (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 still more preferably 117°C or higher, in order to form a resin component with the fluororesin more uniformly and to suppress the crystallinity of the fluororesin.

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

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

[0082] <<Other Components>> As the other components, nucleating agents, ultraviolet absorbers, antioxidants, pigments, antistatic agents, leveling agents, antifoaming agents, and the like may be used as needed.

[0083] (Nucleating Agent) As described above, the use of a nucleating agent is preferable because it can control the aggregation of the glittering resin layer. Fluorine-based resins are crystalline resins and are known to crystallize within the resin layer. When aggregation occurs within the resin layer, crystals are generated and the crystallite size grows, which can cause the resin layer to become cloudy due to scattering by the crystals. The use of the nucleating agent is preferable because it can reduce the crystallite size. Various nucleating agents can be selected depending on the resin components used, but the use of acrylic-modified polytetrafluoroethylene is preferable because it can control the crystallite size of the fluorine-based resin.

[0084] 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 preferred.

[0085] <Transparent Resin Layer> The transparent resin layer is a layer laminated on the opposite side of the glittering resin layer from the article, and is preferably the layer that becomes the outermost surface when the metallic article is formed. The transparent resin layer is required to contain a resin component (2) containing one or more fluorine-based resins.

[0086] The transparent resin layer and the glittering resin layer differ in whether or not they contain a glittering material.

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

[0088] In the metallic decorative laminate, external light passes through the transparent resin layer, a portion of which is reflected by the metallic resin layer, and then passes through the transparent resin layer again, allowing the viewer of the metallic article to perceive the 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. The upper limit is not particularly limited, as long as the metallic design of the metallic decorative laminate of the present 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 a layer that becomes the outermost surface when the metal-like article is formed 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 large, and in order to improve designability and moldability, it is preferable that the upper limit of the layer thickness is small, and it is 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. 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] In order to balance chemical resistance, weather resistance, designability, and moldability, the thickness is preferably 5 μm or more and 100 μm or less, more preferably 10 μm or more and 60 μm or less, even more preferably 20 μm or more and 40 μm or less, and even more preferably 25 μm or more and 35 μm or less.

[0091] When the glittering resin layer is used as the outermost surface of the metallic decorative laminate, the surface may be embossed to have various patterns, or may have fine irregularities to give it a matte finish. Furthermore, a hairline design may be imparted to the surface by hairline processing.

[0092] The fluorine-based resin, 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 in the resin component (1).

[0093] <Configuration of Other Layers> The metallic decorative laminate may further include other layers.

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

[0095] As the surface protective 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, etc. can be used, and as 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 the present embodiment is required to further include a substrate, which will be described later, on the transparent resin layer side of the metallic decorative laminate.

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

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

[0099] 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, even more preferably 80 μm or more and 140 μm or less, and even more preferably 100 μm or more and 120 μm or less.

[0100] <Substrate> The substrate is used to apply a coating liquid for forming a transparent resin layer to a metallic decorative laminate when producing the metallic decorative laminate as described below, and is a layer for protecting the outermost surface on the transparent resin layer side when transporting or storing the multilayer laminate described below. Since it is peeled off at any stage in the production process of the metallic article, it also serves as a release layer.

[0101] The substrate may be any substrate used in the art, and may be appropriately selected from polyethylene substrates, polyester substrates (including polyethylene terephthalate (PET) substrates), polycarbonate substrates, etc. PET is more preferred in view of requirements such as ease of handling during production and availability.

[0102] The thickness of the substrate may be in any range that does not interfere with the manufacturing process, but generally, a thickness of 10 μm or more and 150 μm or less can be used.

[0103] [Multilayer Laminate] The multilayer laminate must include a base layer on the side of the intermediate laminate facing the glitter resin layer. An adhesive layer may be further provided between the intermediate laminate and the base layer, and the intermediate laminate and the base layer are preferably bonded together by an adhesive layer, and the multilayer laminate may further include the other layers described above.

[0104] The layer thickness of the multilayer laminate may be adjusted appropriately.

[0105] The multilayer laminate is preferably one of the following (1) to (4), and (1) and (2) are more preferred, with (2) being even more preferred, as this facilitates the production of each laminate and metallic article. Note that " / " indicates the relationship between layers. The relationship between each layer may not be clear due to partial penetration, and can be considered a manufacturing configuration. (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> The 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 effect on design, heat resistance to the temperature when molding into a shiny decorative molded product, compatibility with injection molding resins in insert injection molding, etc.

[0107] The thickness of the base layer can be, for example, 50 μm to 1000 μm, which is a typical thickness for a decorative laminate. Having the thickness of the base layer in this range is preferable because it can prevent defects such as wrinkles from occurring during film formation and also prevent breakage of the metallic decorative laminate during molding of the metallic article. Furthermore, if the thickness of the base layer exceeds 1000 μm, the moldability of the metallic article may be reduced.

[0108] It is also preferable that the base layer contains a pigment, which can suppress the influence of the color of the article on the metallic article and enable the expression of a color gamut, thereby improving the design.

[0109] [Decorative Laminate] The decorative laminate is obtained by peeling the base material (peeling layer) from the multilayer laminate, and is required to include a base layer on the shiny resin layer side of the metallic decorative laminate.

[0110] As will be described later, the metallic article is produced using the decorative laminate.

[0111] The base layer may contain a pigment.

[0112] [Metallic Article] The metallic article of this embodiment is required to include the metallic decorative laminate.

[0113] The metallic article of this embodiment is manufactured using the metallic decorative laminate by, for example, the manufacturing method described below, and is molded into a desired shape depending on the purpose. For example, it can be used for housings or decorative parts of smartphones, mobile phones, automobile bumpers, emblems, door mirror housings, front grilles, door handles, center wheel caps, emblems, ornaments, garnishes, lamp reflectors, center consoles, installation panels, etc., housings or decorative parts of home appliances such as personal computers, TVs, washing machines, and refrigerators, housings or decorative parts of pachinko, pachinko slot machines, and game machines, or general-purpose items such as carry-on bags and suitcases, and can be used to impart metallic decorativeness and design properties instead 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, the "article" refers to a precursor of a metallic article, which becomes a metallic article by being decorated with the decorative laminate.

[0115] The metallic article of this embodiment may have other configurations in addition to the above configurations. For example, until the metallic article of this embodiment is used, a release paper, a protective film, or the like may be provided on 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 it from becoming dirty.

[0116] [Methods for manufacturing intermediate laminate, multilayer laminate, decorative laminate, and metallic article] 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 process of manufacturing the intermediate laminate.

[0117] The method for producing the intermediate laminate of this embodiment is required to include, in this order: applying a coating liquid containing one or more of the fluororesins; applying a coating liquid containing one or more of the fluororesins, one or more dyes, and one or more of the luster materials; and heating.

[0118] The fluororesin, the luster material, the thermoplastic resin, the other components, the metallic decorative laminate, the intermediate laminate, the multilayer laminate, the decorative laminate, and the metallic article have already been explained, so they will not be explained here.

[0119] (Coating liquid containing one or more of the above-described fluororesins) The coating liquid containing one or more of the above-described fluororesins is a coating liquid for forming a transparent resin layer, and may further contain the above-described 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 solvent may be any solvent generally used in the relevant field. 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.

[0122] In the method for producing the metallic decorative laminate of this embodiment, it is preferable that the solvent exhibits poor solvent properties for fluorine-based resins and good solvent properties for acrylic resins. If the fluorine-based resin is not dissolved in the coating liquid before heating as described below, it will not react with the acrylic resin before heating, and lumps of the reaction product of the fluorine-based resin and the acrylic resin will not form in the coating liquid, which is preferable. Since such lumps do not form, uneven coating does not occur during application, and a uniform glittering resin layer can be produced. Butyl carbitol acetate is a preferred example of a solvent with such properties.

[0123] When the solvent is used, in order to shorten the heating treatment time described below and improve the coatability of the coating liquid to a substrate, the amount of the solvent 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, relative to 100 parts by mass of the total amount of the fluorine-based resin and the acrylic resin.

[0124] (Coating liquid containing one or more of the above-mentioned fluorine-based resins, one or more of the above-mentioned dyes, and one or more of the above-mentioned luster materials) The coating liquid containing one or more of the above-mentioned fluorine-based resins, one or more of the above-mentioned dyes, and one or more of the above-mentioned luster materials is a coating liquid for forming a luster resin layer, and may further contain the above-mentioned 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] <Coating> The coating can be performed by applying the coating liquid to the substrate or to a resin layer formed on the substrate using a known means such as a gravure coater, a reverse coater, a die coater, a knife coater, or a roll coater.

[0127] <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 the substrate in a state where the coating liquid is present on the substrate. The heating also includes a case where the substrate is preheated, then coated, and then further heated.

[0128] When a solvent is used in the coating liquid, the heating evaporates the solvent. By heating the resin component to a temperature equal to or higher than the Tg of the resin component contained therein, the resin component can be mixed with the fluororesin. This is preferable because it prevents the crystallite size of the fluororesin from growing, suppresses precipitation of the fluororesin from the resin component, and allows the luster material to be uniformly dispersed.

[0129] The heating temperature can be appropriately selected depending on the heating time, the fluorine-based resin, pigment, 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.

[0130] 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.

[0131] The heating time can be appropriately selected 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.

[0132] <Removing the Substrate> The method for producing the decorative laminate of this embodiment must include removing the substrate from the multilayer laminate.

[0133] 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).

[0134] The peeling method is not particularly limited as long as it is a method commonly used in the relevant field.

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

[0136] 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 of the decorative laminate faces the article, and the decorative laminate is molded onto the surface of the article to obtain a metallic article.

[0137] (Molding process) In order to thermoform the decorative laminate, the surface temperature of the decorative laminate is 150°C to 200°C, so that the decorative laminate does not draw down during molding and whitening phenomena do not occur, thereby achieving good moldability. Such a surface temperature of 150°C or higher softens the decorative laminate sufficiently, preventing the decorative laminate from sagging and deforming due to the drawdown phenomenon, making processing and molding difficult. Furthermore, such a surface temperature of 200°C or lower prevents the decorative laminate from becoming too soft due to being in a molten state, making molding difficult, or from easily causing whitening phenomena.

[0138] 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.

[0139] As a method for adhering the decorative laminate to a mold, any method can be adopted taking into consideration ease of molding, cost, etc., such as straight molding using a female mold, drape molding using a male mold, and 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 adopted. 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.

[0140] (Clamping step) The manufacturing method of 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 that can grip both sides of the decorative laminate, for example, by gripping both ends of the decorative laminate. Gripping of the decorative laminate is not limited to both ends of the decorative laminate, and any part of the decorative laminate can be gripped. Usually, 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 decorative laminate cut to a predetermined length, the ends of the four sides can be gripped by upper and lower frames.

[0141] (Heating Step) 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.

[0142] (Other Steps) 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.

[0143] The metallic decorative laminate, intermediate laminate, multilayer laminate, decorative laminate, metallic article, and method for manufacturing the intermediate laminate and the decorative laminate according to this embodiment are preferably the following [1] to

[13] . [1] A metallic decorative laminate comprising a resin component (1) containing one or more fluorine-based resins, a photoluminescent resin layer containing one or more dyes and one or more photoluminescent materials, and a transparent resin layer containing a resin component (2) containing one or more fluorine-based resins. [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 photoluminescent material in the photoluminescent resin layer is 0.01 to 20.00 parts by mass 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 glittering material contains at least one material selected from the group consisting of scaly or flaky metal, scaly or flaky alloy metal, scaly or flaky metal oxide, scaly or flaky mica, glass flakes, and pulverized film. [5] The metallic decorative laminate according to any one of [1] to [4], wherein the pigment 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). [6] The metallic decorative laminate according to any one of [1] to [5], wherein the pigment 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 substrate on the transparent resin layer side of the metallic decorative laminate according to any one of [1] to [7]. [9] A multilayer laminate comprising a base layer on the glossy resin layer side of the intermediate laminate according to [8].

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

[11] A metallic article comprising the metallic decorative laminate according to any one of [1] to [7].

[12] A method for producing the intermediate laminate according to [8], comprising, in this order: applying a coating liquid containing one or more fluorine-based resins; applying a coating liquid containing one or more fluorine-based resins, one or more dyes, and one or more luster materials; and heating.

[13] A method for producing the decorative laminate according to

[10] , comprising peeling off the substrate from the multilayer laminate according to [9].

[0144] The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples.

[0145] (Evaluation Method) 1. Chemical Resistance Evaluation Chemical resistance evaluation was performed using a commercially available brake fluid (manufactured by XX Co., Ltd., product name: XX) primarily composed of polyethylene glycol monoether, assuming use in four-wheeled or two-wheeled vehicles, vacuum pumps, etc. A 25 cm x 25 cm sample of the decorative laminate obtained in the Examples and Comparative Examples was prepared as a test sample. At 25°C, 1 mL of the brake fluid was dropped onto the transparent resin layer side of the decorative laminate at nine points (3 x 3) using a dropper. After leaving the sample to stand for 5 hours, the brake fluid was washed off with toluene, and the sample was left at 25°C for 1 hour. After confirming that the toluene had dried, the surface condition was visually observed and rated as A to D as follows: A: No change was observed from before the test at all nine points. B: Brake fluid drip marks were visible in areas less than four points. C: Brake fluid drip marks were visible in areas between four and eight points. D: Brake fluid drip marks can be seen in areas with 8 or more points.

[0146] 2. Weather resistance evaluation: A xenon weather meter SX75 7.5 kW (manufactured by Suga Test Instruments) was used. The treatment conditions were: black panel temperature 63±2°C, humidity 50% RH, rainfall cycle (non-rainfall time / rainfall time) 102 min / 18 min, illuminance 180 W / m ２ , tank temperature 25-35℃, 500MJ / m ２The 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 evaluated as A to C as follows. A: When ΔE* = 3.0 or less, it was evaluated as having very good weather resistance. B: When ΔE* was greater than 3.0 and less than or equal to 5.0, it was evaluated as having good weather resistance. C: When ΔE* was greater than 5.0, it was evaluated as having no weather resistance.

[0147] 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 on 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 the results were evaluated as A to C as follows. A: When Δb* = 1.0 or less and there are no defects such as peeling of the decorative sheet, the sample was evaluated as having very good heat resistance. B: When Δb* is greater than 1.0 and less than 3.0 and there are only slight defects such as peeling of the decorative sheet, the sample was evaluated as having good heat resistance. C: When Δb* is greater than 5.0 and major defects such as peeling of the decorative sheet are observed, the sample was evaluated as having poor 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 rated as A or B below. A: Presents a metallic design. B: Presents no metallic design or presents a matte finish.

[0149] 5. Total Light Transmittance The total light transmittance of the decorative laminate obtained in the Examples or Comparative Examples was measured using a spectrophotometer (UH4150, manufactured by Hitachi High-Tech Science Corporation) in accordance with JIS K7375:2008.

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

[0151] 7. Evaluation of Moldability For 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 the original length before stretching) at the corner of the mold after the molding process was cloudy.

[0152] (Materials used) (Fluorine-based resin (Kyanr301, manufactured by Arkema Co., Ltd.)) 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 (SK540, manufactured by Asahi Kasei Corporation)) 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 Color Co., Ltd.) (Pigment 4) Red pigment MHI Red #CC361 (manufactured by Mikuni Color Co., Ltd.) (Glossy material 1) Pearl pigment TWINCLEPEARL SXC-SO (manufactured by Nihon Koken Kogyo Co., Ltd., volume average particle diameter (D ５０ (Photo-luminescent material 2) Aluminum flake GX40A (manufactured by Asahi Kasei Corporation, volume average particle diameter (D ５０ (Glittering material 3) Pearl pigment TWINCLEPEARL (registered trademark) BXC-SO (manufactured by Nihon Koken Kogyo Co., Ltd., volume average particle diameter (D ５０ ): 22 μm)

[0153] (Example 1) <Production of intermediate laminate including metallic decorative laminate> (Formation of transparent resin layer) The coating liquid for the transparent resin layer described below was applied to a substrate (PET film (G2000 (manufactured by Toyobo Co., Ltd.))). The amount of coating was adjusted so that the film thickness of the glittering resin layer after heating would be 30 μm. Immediately after coating, the substrate was heated at 180° C. for 2 minutes, and a transparent resin layer was formed on the substrate. The substrate was then cooled to room temperature.

[0154] ((Transparent Resin Layer Coating Liquid)) 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 Sangyo Co., Ltd.), and the mixture was stirred at room temperature to obtain a uniform solution. Further, other components (0.57 g of an ultraviolet absorber (Tinuvin 900, 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 fluorine-based resin (Kyanr301, manufactured by Arkema Co., Ltd.) were added, and the mixture was further stirred to obtain a transparent resin layer coating liquid containing resin component (2).

[0155] Tables 1 and 2 show the contents of the acrylic resin, fluorine-based resin, and other components in the resin component (2) used in the examples and comparative examples.

[0156] (Formation of Glossy Resin Layer) The coating liquid for the glossy resin layer, which will be described later, was applied onto the transparent resin layer of the substrate on which the transparent resin layer had been formed as described above. The amount of coating was adjusted so that the thickness of the glossy resin layer after heating would be 30 μm.

[0157] Immediately after application, the coating was heated at 180° C. for 2 minutes to laminate a glittering resin layer, and then cooled to room temperature to produce an intermediate laminate including a metallic decorative laminate.

[0158] The substrate was peeled off from the obtained intermediate laminate, and the transparent resin layer side was evaluated for chemical resistance, weather resistance, heat resistance, and design, and total light transmittance was measured. The results are shown in Tables 3 and 4 together with those of other Examples and Comparative Examples.

[0159] (Coating liquid for photoluminescent resin layer) 8.75 g of acrylic resin (SK540 manufactured by Asahi Kasei Corporation) was added to 37.45 g of butyl carbitol acetate (manufactured by Sankyo Kasei Sangyo Co., Ltd.) and stirred at room temperature to obtain a uniform solution. Further, other components (0.57 g of ultraviolet absorber (Tinuvin 900 manufactured by BASF Japan Co., Ltd.) and 0.06 g of nucleating agent (A-3000 manufactured by Mitsubishi Chemical Corporation)), dye 1 (the dye component was used so that it was 2.00 parts by mass per 100 parts by mass of resin component 1), and 13.16 g of fluorine-based resin (Kyanr301 manufactured by Arkema Co., Ltd.) were added and stirred to obtain a solution containing resin component (1). 1.13 g of photoluminescent material 1 was added to the obtained solution containing resin component (1), and further stirred to obtain a coating liquid for photoluminescent resin layer.

[0160] Tables 1 and 2 show the contents of the acrylic resin, fluorine-based resin, and other components in the resin component (1) used in the examples and comparative examples.

[0161] Tables 1 and 2 show the contents of the acrylic resin, fluorine-based resin, and other components in resin components (1) and (2), and also show the amounts (parts by mass) of pigment and luster material used per 100 parts by mass of resin component (1). In the tables, "-" means that the material was not used.

[0162]

[0163]

[0164] <Production of metallic articles> (Formation of adhesive layer and base layer) A mixture of a base agent 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 was used as a urethane-based adhesive for metallic decorative sheets on the photoluminescent resin layer of the intermediate laminate.

[0165] TM-K51 (manufactured by Toyo-Morton Co., Ltd.) was used as the polyester diol, Duranol T5652 (manufactured by Asahi Kasei Corporation) was used as the polycarbonate 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.

[0166] A urethane 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 would be approximately 10 μm, and the applied product was dried at 60° C. for 1 minute. After that, the applied product was laminated with a PET film (average thickness 25 μm, Teflex FT3, manufactured by Toyobo Co., Ltd.) 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 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.

[0169] The decorative laminate and metallic article obtained in Example 1 were evaluated for chemical resistance, weather resistance, heat resistance, and design, and total light transmittance was measured. The results are shown in Tables 3 and 4.

[0170] The post-molding design evaluation and moldability evaluation were both satisfactory for practical use. (Examples 2) to (Example 6) and (Comparative Examples 1) to (Comparative Examples 5) The decorative laminates and metallic articles of Examples 2 to 6 and Comparative Examples 1 to 5 were produced in the same manner as Example 1, except that the film thickness, amount of fluorine-based resin used, amount of acrylic resin used, type of pigment, amount of pigment used, type of luster material, and amount of luster material used were changed as shown in Tables 1 and 2. In Tables 1 and 2, the "pigment" and "luster material" columns show the material used in the upper row and the amount used (parts by mass) per 100 parts by mass of resin component (1) in the lower row.

[0171] The decorative laminates and metallic articles obtained in Examples 2 to 6 and Comparative Examples 1 to 5 were evaluated for chemical resistance, weather resistance, heat resistance, and design, and total light transmittance was measured. The results are shown in Tables 3 and 4.

[0172] The evaluation of the design and moldability after molding showed that there were no practical problems.

[0173]

[0174]

[0175] The results of Examples 1 to 6 shown in Tables 3 and 4 demonstrate that the metallic decorative laminate of this embodiment exhibits a metallic design and has excellent properties in chemical resistance, weather resistance, heat resistance, and total light transmittance. Furthermore, the environmental impact of waste liquids generated by metal plating was reduced.

[0176] Furthermore, it was confirmed that all metallic articles containing the metallic decorative laminates present no practical problems.

[0177] In contrast to this, in Comparative Examples 1 to 5, the glittering resin layer did not contain a glittering material, and therefore the metallic design was not exhibited.

[0178] The metallic decorative laminate, intermediate laminate, multilayer laminate, decorative laminate, and metallic article of this embodiment exhibit an excellent metallic design, reduce the environmental impact during production, have chemical resistance and weather resistance, and further have excellent productivity. They can be used to impart metallic decorativeness and design properties in place of plating or metal materials, and are suitable for use in automobiles, home appliances, information terminals, etc.

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

Claims

1. A metallic decorative laminate comprising a resin component (1) containing one or more fluororesins, a luminescent resin layer containing one or more pigments and one or more luminescent materials, and a transparent resin layer containing a resin component (2) containing one or more fluororesins.

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 luminescent material in the luminescent resin layer is 0.01 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 claim 1, wherein the luminescent material contains 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 pulverizates.

5. The metallic decorative laminate according to claim 1, wherein the pigment in the luminescent 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).

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

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

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

9. A multilayer laminate including a base layer on the luminescent resin layer side of the intermediate laminate according to claim 8.

10. A decorative laminate including a base layer on the luminescent resin layer side of the metallic decorative laminate according to claim 1.

11. A metallic decorative article comprising the metallic decorative laminate according to claim 1.

12. A method for manufacturing the intermediate laminate according to claim 8, including, in this order, applying a coating liquid containing one or more fluororesins, applying a coating liquid containing one or more fluororesins, one or more pigments, and one or more luminescent materials, and heating.

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

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