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

Abstract

To provide a metallic decorative laminate which exhibits an excellent metallic design, is excellent in millimeter wave transmission properties, and is easily manufactured, a metallic article including the metallic decorative laminate, and a method for manufacturing the metallic decorative laminate.SOLUTION: Provided are a metallic decorative laminate 10 that includes a brightening resin layer containing a resin component 20 containing one or more types of fluorine-based resins and one or more types of acrylic resins, and one or more types of brightening materials 30, wherein the brightening resin layer has a layer thickness of 20 μm or more and 100 μm or less, and thus exhibits an excellent metallic design, has excellent millimeter wave transparency, and is easy to produce, a metallic article including the metallic decorative laminate, and a method for producing the metallic decorative laminate.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a metallic decorative laminate, a metallic article, and a method for manufacturing a metallic decorative laminate. [Background technology]

[0002] Sensors such as millimeter-wave radar are used to detect obstacles around automobiles and other vehicles. Millimeter-wave radar measures the distance to an obstacle by irradiating the obstacle with radio waves with a wavelength of 1 to 10 mm and measuring the time it takes for the radio waves to reflect off the obstacle and return. Millimeter-wave radar is less affected by weather conditions such as rain or fog and can detect obstacles at a distance, which is why it has been adopted by many automobile manufacturers. Automotive millimeter-wave radar uses the millimeter-wave band in the 76 to 77 GHz range. The millimeter-wave radar device itself is mounted, for example, behind the bumper on the front or rear of the automobile body, and millimeter waves are transmitted from the device itself through the bumper and irradiated onto obstacles. Typically, automobile bumpers are manufactured by painting molded parts made from resins such as polypropylene or polycarbonate. However, for automobiles with metallic-finish paint on the body, the bumper also needs to have a metallic appearance and be able to transmit millimeter waves (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-030075 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention aims to provide a metallic decorative laminate that exhibits an excellent metallic design, has excellent transmittance for radio waves classified as millimeter waves (hereinafter referred to as millimeter wave transmittance), and is easy to manufacture, a metallic article including the metallic decorative laminate, and a method for manufacturing the metallic decorative laminate. [Means for solving the problem]

[0005] As a result of extensive research into solving the above problems, the present inventors provide the following [1] to [3]. [1] A metallic decorative laminate comprising a resin component containing one or more fluorine-based resins and one or more acrylic resins, and a photoluminescent resin layer containing one or more photoluminescent materials, wherein the layer thickness of the photoluminescent resin layer is 20 μm or more and 100 μm or less. [2] A metallic product using the metallic decorative laminate described in [1] above. [3] A method for producing the metallic decorative laminate described in [1], which comprises applying a coating liquid containing a fluorine-based resin, an acrylic resin, and a lustrous material to a substrate and heating the coating liquid, in this order. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a metallic decorative laminate that exhibits an excellent metallic design, has excellent millimeter wave transmittance, and is easy to manufacture, a metallic article that includes the metallic decorative laminate, and a method for manufacturing the metallic decorative laminate. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a schematic diagram of a metallic decorative laminate according to an embodiment of the present invention; [Figure 2] FIG. 1 is a schematic diagram of an electromagnetic wave transmitting bright coated resin product (three layers laminated) described in Patent Document 1. [Figure 3] FIG. 2 is a schematic diagram of a photoluminescent material in a photoluminescent resin layer. DETAILED DESCRIPTION OF THE INVENTION

[0008] Patent Document 1 discloses a method for producing an aluminum-look bumper that transmits millimeter waves, in which a resin substrate is coated with paint containing flat, lustrous aluminum material (aluminum flakes). In a method for producing a metallic design using aluminum flakes, the aluminum flakes cause millimeter waves to be reflected. A known method for suppressing this reflection and improving millimeter wave transmittance is to increase the distance between aluminum flakes (Patent Document 1). However, with the method described in Patent Document 1, if the thickness of the lustrous resin layer that can be produced by applying a single coat of paint exceeds 10 μm, the aluminum flakes settle in the coating film before the coating film hardens, making it impossible to ensure a sufficient distance between the aluminum flakes, and thus failing to sufficiently suppress the reflection.

[0009] Furthermore, in Patent Document 1, a sufficient amount of aluminum flakes is required for the glossy resin layer to express a metallic design. However, if the content of aluminum flakes in the glossy resin layer is increased to achieve this, the distance between the aluminum flakes becomes smaller, resulting in a decrease in millimeter wave transmittance.

[0010] Although a certain film thickness is preferable for achieving a metallic design, the manufacturing method of the glossy resin layer described in Patent Document 1 requires the film to be formed to a thickness of 10 μm or less in order to ensure sufficient distance between the aluminum flakes due to the aforementioned settling of aluminum flakes in the coating film. Due to this constraint, it was not possible to manufacture a single glossy resin layer with a thickness of 20 μm or more. To achieve a thickness of 20 μm or more, at least two glossy resin layers had to be stacked. Thus, to obtain a glossy resin layer with a thickness of 20 μm or more using the manufacturing method described in Patent Document 1, the coating film formation process had to be performed at least twice, making the process complicated.

[0011] Furthermore, as described in Patent Document 1, when a photoluminescent resin layer is manufactured using an acrylic urethane paint containing aluminum flakes, the aluminum flakes are insoluble in the acrylic urethane paint and have low dispersibility. Therefore, during the manufacturing process, the aluminum flakes, which have a high specific gravity, settle due to differences in specific gravity, resulting in a distribution of content in each photoluminescent resin layer in which the content increases from the upper surface to the lower surface in the thickness direction (see FIG. 2, where a region with a high photoluminescent material content, such as region 122 with a high photoluminescent material content, is formed in contrast to region 121 with a low photoluminescent material content in photoluminescent resin layer (1) 110). For this reason, for example, when manufacturing a photoluminescent resin layer by laminating three layers (see FIG. 2), the aluminum flakes (photoluminescent material 120) settle due to differences in specific gravity on the resin substrate 130 side of each photoluminescent resin layer (photoluminescent resin layers (1) to (3)), forming region 122 with a high aluminum flake content, resulting in a decrease in design radio wave transmittance.

[0012] In contrast, the metallic decorative laminate of the present disclosure has excellent dispersibility of the photoluminescent material, allowing for a thicker layer of each photoluminescent resin layer. Furthermore, since the thickness can be increased to 20 μm or more without stacking multiple photoluminescent resin layers, regions with a high photoluminescent material content (such as region 122 with a high photoluminescent material content in photoluminescent resin layer (2) 111 in FIG. 2) are not formed in between. This allows for a metallic decorative laminate to be obtained that exhibits an excellent metallic design (hereinafter also referred to as excellent design) and has excellent millimeter wave transmittance.

[0013] In addition, in Patent Document 1, the glittering resin layer does not contain a component corresponding to the fluorine-based resin in this embodiment, so there is room for improvement in terms of anti-fouling properties and chemical resistance. In contrast, the metallic decorative laminate of the present disclosure contains a fluorine-based resin in the glittering resin layer, so it also has the properties of excellent anti-fouling properties and chemical resistance. Furthermore, when the metallic decorative laminate is formed on a substrate, it can be easily peeled from the substrate (hereinafter also referred to as peelability from the substrate), so it also has the characteristic of excellent film-forming properties.

[0014] The metallic decorative laminate, metallic article, and method for manufacturing the metallic decorative laminate according to the present invention will be described below. Note that the present invention is not limited to the following examples.

[0015] In the present disclosure, the thickness direction 1 refers to the stacking direction of the metallic decorative laminate or metallic article, as shown in FIG. 3, and the width direction 2 refers to a direction different from the thickness direction and perpendicular to the longitudinal direction 3 of the metallic decorative laminate or metallic article.

[0016] 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 can be arbitrarily combined.

[0017] 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 can be considered more preferable.

[0018] [Metallic decorative laminate] The metallic decorative laminate of this embodiment is required to be a metallic decorative laminate that includes a resin component containing one or more fluorine-based resins and one or more acrylic resins, and a photoluminescent resin layer containing one or more photoluminescent materials, and the layer thickness of the photoluminescent resin layer is 20 μm or more and 100 μm or less.

[0019] The metallic decorative laminate of this embodiment can be used to decorate plastic parts and metal parts (hereinafter simply referred to as "articles") such as car bumpers using laminate decoration methods such as insert molding and overlay molding. The metallic decorative laminate can also be used to decorate the surface of an article via an adhesive layer or bonding layer, for example, as a surface layer on automotive exteriors such as automobile pillars, door moldings, roof moldings, entire door surfaces, and entire roof surfaces. Thus, the metallic decorative laminate of this embodiment is particularly preferable when used to decorate plastic parts such as car bumpers, because it exhibits an excellent metallic design and has excellent transmittance for radio waves classified as millimeter waves (unless otherwise specified, in this disclosure, radio waves refer to radio waves classified as millimeter waves). This allows for the installation of a millimeter-wave radar directly below the bumper to detect objects. Furthermore, as will be described in more detail below, the metallic decorative laminate of this embodiment is preferable because it is easy to manufacture and therefore suitable for mass production.

[0020] The layer thickness of the metallic decorative laminate of this embodiment is preferably 20 μm or more in order to improve the design, more preferably 50 μm or more, and even more preferably 80 μm or more, and in order to improve millimeter wave transmittance, it is preferably 250 μm or less, more preferably 200 μm or less, even more preferably 150 μm or less, even more preferably 120 μm or less, and particularly preferably 100 μm or less.

[0021] To achieve a balance between design and millimeter wave transmittance, the thickness is preferably 20 μm or more and 250 μm or less, more preferably 50 μm or more and 200 μm or less, and even more preferably 80 μm or more and 100 μm or less.

[0022] When the metallic decorative laminate is used for insert molding, the glittering resin layer may be used together with a backer layer for reinforcement. When the metallic decorative laminate of this embodiment has a backer layer, the thickness of the metallic decorative laminate is preferably 300 μm or more and 600 μm or less, more preferably 400 μm or more and 550 μm or less, and even more preferably 450 μm or more and 520 μm or less.

[0023] The backer layer is preferably made of ABS resin or polypropylene resin, and the thickness thereof is preferably 250 μm or more and 400 μm or less.

[0024] In the present disclosure, "designability" refers to the property of an article that exhibits a metallic design when the metallic decorative laminate of the present disclosure is used in the article.

[0025] The millimeter wave transmittance of the metallic decorative laminate of this embodiment can be evaluated by the attenuation of 76.5 GHz radio waves (hereinafter referred to as millimeter wave transmission attenuation, and the attenuation is stated as an absolute value). When used with a millimeter wave radar, the metallic decorative laminate is placed on the path of millimeter wave irradiation and reflection, and in order to maintain a high level of detection sensitivity of the millimeter wave radar, the transmittance is preferably 1.0 dB or less, and more preferably 0.5 dB or less. There is no particular limit to the lower limit, and 0.0 dB is preferred, but since attenuation also occurs due to resin components, etc., it is essentially 0.1 dB or more.

[0026] The total light transmittance of the metallic decorative laminate of this embodiment can be adjusted as needed. As described later, the metallic decorative laminate of this embodiment expresses a metallic design due to the contained lustrous material, but it is also preferable from the viewpoint of expressing a design to adjust the color tone by adding a pigment or the like as described later as needed.

[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] If the pigment is not contained or if the pigment content is low, the total light transmittance can be increased. This is preferable because it allows a metallic design to be produced when external light is strong, such as during the day when sunlight is present, and when external light is weak, such as at night, light from an LED or the like can be transmitted from the side opposite the viewer of the metallic decorative laminate, allowing the metallic design to be produced even in weak external light conditions. The total light transmittance is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and even more preferably 98% or more. There is no particular upper limit, but it is sufficient to provide the metallic design and the millimeter wave transmittance and other properties of the metallic decorative laminate of the present disclosure.

[0029] When the content of the luster material is increased to more strongly express the metallic design by the luster material, the total light transmittance is lowered, which is preferable because it masks the color of the article to which the metallic finish is imparted and makes the millimeter wave irradiation device mounted behind the bumper on the front and rear sides of the vehicle body invisible. To achieve this effect, the total light transmittance is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. There is no particular upper limit, as long as the metallic design and millimeter wave transmittance properties of the metallic decorative laminate of the present disclosure are exhibited. However, it is preferable that the total light transmittance be 40% or less, more preferably 30% or less, even more preferably 20% or less, and even more preferably 10% or less, so that the color of the article is substantially not recognizable from the metallic decorative laminate side.

[0030] When a pigment or the like is contained in addition to the glittering material, the absorption of millimeter waves by the pigment or the like is small and can usually be ignored.

[0031] The total light transmittance can be measured, for example, by the method described in the Examples.

[0032] The metallic decorative laminate of this embodiment may include only the glittering resin layer, but may also include other resin layers described below.

[0033] The metallic decorative laminate of this embodiment may include two or more layers of the glittering resin layer described below, but preferably includes only one layer. The metallic decorative laminate of this embodiment is preferred because the glittering resin layer can have a thickness of 20 μm or more, allowing the desired design to be achieved with just one layer.

[0034] <Glitter resin layer> The photoluminescent resin layer must contain a resin component containing one or more fluorine-based resins and one or more acrylic resins, as well as one or more photoluminescent materials, and must have a layer thickness of 20 μm or more and 100 μm or less.

[0035] The glittering resin layer may contain only the resin component and the glittering material, but may also contain other components described below as the resin component.

[0036] The thickness of the glittering resin layer is preferably 23 μm or more, more preferably 25 μm or more, and even more preferably 28 μm or more in order to improve design, and is preferably 80 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less in order to improve millimeter wave transmittance.

[0037] In order to strike a balance between design and millimeter wave transmittance, the thickness is preferably 23 μm or more and 80 μm or less, more preferably 25 μm or more and 60 μm or less, and even more preferably 28 μm or more and 50 μm or less.

[0038] 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.

[0039] (resin component) As described above, the glittering resin layer contains a resin component containing one or more fluorine-based resins and one or more acrylic resins, and one or more glittering materials.

[0040] The resin component derived from one or more fluorine-based resins and one or more acrylic resins may be a mixture (polymer alloy) of one or more fluorine-based resins and one or more acrylic resins, or a reaction product of one or more fluorine-based resins and one or more acrylic resins. However, in order to improve the strength of the metallic decorative laminate and the dispersibility of the lustrous material, it is more preferable that it be a mixture (polymer alloy) of one or more fluorine-based resins and one or more acrylic resins.

[0041] Although the details of the fluorine-based resin will be described later, a single fluorine-based resin may be used alone, or two or more types may be used in combination. Using only one type is preferred because it allows for easy production of a uniform metallic decorative laminate, while using two or more types is preferred because it allows for easy adjustment of physical properties such as the melting point of the resin component.

[0042] Although the details of the acrylic resin will be described later, a single acrylic resin may be used alone, or two or more may be used in combination. Using only one type is preferred because a uniform metallic decorative laminate can be easily produced, while using two or more types is preferred because the physical properties such as the melting point of the resin component can be easily adjusted.

[0043] The resin component is a resin component derived from a fluorine-based resin and an acrylic resin, which will be described later, but may contain other resins. The other resins are preferably resins constituting the other resin layers, which will be described later. The content of the fluorine-based resin and the acrylic resin, based on 100 parts by mass of the resin component, is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, even more preferably 95 parts by mass or more, even more preferably 98 parts by mass or more, and even more preferably substantially 100 parts by mass. "Substantially" means excluding impurities and the like that are unintentionally contained. The upper limit is not particularly limited, and it is preferably substantially 100 parts by mass.

[0044] The resin components contained in the glossy resin layer include the fluorine-based resin and the acrylic resin, and the ratio of the content of the fluorine-based resin to the content of the acrylic resin (content of the fluorine-based resin / content of the acrylic resin) is preferably 1.0 or more and 5.0 or less, more preferably 1.1 or more and 2.5, even more preferably 1.2 or more and 2.0, and even more preferably 1.3 or more and 1.7.

[0045] By increasing the content of the fluororesin relative to the content of the acrylic resin, the dispersibility of the glittering material described below is improved, the glittering material is uniformly dispersed in the glittering resin layer, and the design and millimeter wave transmittance of the metallic decorative laminate are improved, which is preferable. In addition, the peelability from the substrate is improved, which is preferable because it facilitates production.

[0046] The resin component preferably further contains other components described below.

[0047] When the total amount of the resin components is 100 parts by mass, the total amount of the fluorine-based resin and the acrylic resin is preferably 90 parts by mass or more, more preferably 94 parts by mass or more, and even more preferably 96 parts by mass or more, in order to give the photoluminescent resin layer high strength and increase the dispersibility of the photoluminescent material. There is no particular upper limit and it may be 100 parts by mass, but when other components are added as necessary, it is preferably 99 parts by mass or less, and more preferably 98 parts by mass or less.

[0048] (Fluorine-based resin) The fluorine-based resin generally has excellent chemical resistance and weather resistance. Furthermore, by using it as the resin component, in addition to the above properties, the peelability from the substrate is improved, making it easier to manufacture the metallic decorative laminate. Furthermore, the dispersion of the glittering material in the glittering resin layer is improved, resulting in a homogeneous glittering resin layer, which exhibits an excellent metallic design and excellent millimeter wave transmittance. To utilize these properties, it can be used as the outermost surface of the metallic decorative laminate of this embodiment.

[0049] The fluorine-based resin may be any resin commonly used as a fluorine-based resin, and preferred examples include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (CTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), perfluoroalkoxy fluorine-based resin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), etc. In particular, polyvinylidene fluoride (PVDF) is preferred because its use as the resin component results in a photoluminescent resin layer that has excellent film-forming properties and excellent dispersibility of photoluminescent materials.

[0050] In order to facilitate the formation of a polymer alloy with the acrylic resin described below, 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.

[0051] 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, in order to facilitate the formation of a polymer alloy with the acrylic resin described below.

[0052] (acrylic resin) The acrylic resin may be any resin generally used as a polymer or copolymer acrylic resin of acrylic acid and its derivatives such as esters, and methacrylic acid derivatives such as methyl methacrylate. More specifically, preferred examples include polyethyl methacrylate (PEMA), polybutyl methacrylate (PBMA), polycyclohexyl methacrylate (PCHMA), and polyethylhexyl methacrylate (PEHMA). Polymethyl methacrylate resin (PMMA) is particularly useful as a resin component because it has high transparency, excellent scratch resistance due to its high hardness, and thermoplasticity that allows it to be processed into complex shapes.

[0053] 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.

[0054] 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 even more preferably 1.9 or more and 2.2 or less.

[0055] 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 even more preferably 117°C or higher, in order to form a resin component with the fluororesin more uniformly and suppress the crystallinity of the fluororesin.

[0056] The upper limit of 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.

[0057] The acrylic resin preferably has an imide skeleton in its structure in order to achieve the above Tg range.

[0058] <<Glitter 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.It may be an inorganic pigment or an organic pigment, and may be a natural material or a synthetic material, but it is preferable that it is an inorganic pigment in order to improve the reflective performance of external light.

[0059] The lustrous material preferably contains at least one material selected from scaly or flaky metal, scaly or flaky alloy 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, colored pearl pigments, etc. Flake mica may be used alone, but is preferably used together with a dye described below, since this allows for the expression of a wider range of color tones.

[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 uniformly dispersed in the resin component within the photoluminescent resin layer 20 in FIG. 3 and oriented so that the thickness direction 31 of the photoluminescent material is approximately parallel to the thickness direction 1. While FIG. 3 shows the photoluminescent material as a disk-shaped material, the present invention is not limited to this. The longest length in the planar direction of the photoluminescent material 30 (particle diameter direction 33 of the photoluminescent material) is defined as the particle diameter 34 of the photoluminescent material, and the average thickness in the thickness direction of the photoluminescent material perpendicular to the planar direction is defined as the thickness 32 of the photoluminescent material. These values ​​are the average values ​​measured under an optical microscope by randomly sampling 20 particles of the photoluminescent material. The particle diameter 34 of the photoluminescent material is the volume average particle diameter (D 50 ) can be substituted. The particle diameter of the luminescent material is 34 (D 50 ) 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 in terms of expressing 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.

[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 32 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] Photoluminescent material particle diameter 34 (D 50 The ratio of the particle diameter to the thickness 32 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 lead to the formation of minute particulate forms (hereinafter referred to as aggregates). These aggregates tend to reduce compatibility with other resin components and prevent the fluororesin from being uniformly distributed. Even if the aggregates are pulverized and then mixed with, for example, a thermoplastic resin, they tend to re-aggregate within the resin composition, resulting in a non-uniform dispersion of the resin composition. When the resin components are applied, the aggregates tend to be distributed unevenly on the coating surface. This non-uniform state can prevent the fluororesin from fully exhibiting its properties. To prevent this growth, a nucleating agent (described below) is added. 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 reduced 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] The total content of the glittering materials per 100 parts by mass of the resin component in the glittering resin layer is preferably 0.10 parts by mass or more, more preferably 0.30 parts by mass or more, even more preferably 0.50 parts by mass or more, and even more preferably 0.70 parts by mass or more in order to shield the article and express a metallic design, and is preferably 30.00 parts by mass or less, more preferably 25.00 parts by mass or less, even more preferably 20.00 parts by mass or less, and even more preferably 18.00 parts by mass or less in order to express excellent millimeter wave transmittance.

[0070] To achieve both metallic design and millimeter wave transmittance, the content is preferably 0.10 parts by mass or more and 30.00 parts by mass or less, more preferably 0.50 parts by mass or more and 10.00 parts by mass or less, even more preferably 1.00 parts by mass or more and 8.00 parts by mass or less, and even more preferably 1.50 parts by mass or more and 6.00 parts by mass or less.

[0071] When focusing particularly on millimeter wave transmittance, the content is preferably 0.10 parts by mass or more and 10.00 parts by mass or less, more preferably 0.50 parts by mass or more and 8.00 parts by mass or less, even more preferably 1.00 parts by mass or more and 6.00 parts by mass or less, and even more preferably 1.50 parts by mass or more and 5.00 parts by mass or less.

[0072] 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.

[0073] <<Other ingredients>> As the other components, nucleating agents, ultraviolet absorbers, antioxidants, dyes, antistatic agents, leveling agents, antifoaming agents, etc. may be used as necessary.

[0074] (nucleating agent) The use of the nucleating agent is preferred because it allows the crystal size of the glittering resin layer to be controlled. Fluorine-based resins are crystalline resins and are known to crystallize within the resin layer. When crystals form within the resin layer and the crystal size grows, the resin layer may become cloudy due to scattering by the crystals. The use of the nucleating agent is preferred because it allows the crystal size to be reduced. Various nucleating agents can be selected depending on the resin components used, but the use of acrylic-modified polytetrafluoroethylene is preferred because it allows the crystal size of the fluorine-based resin to be controlled.

[0075] (dye) The pigment contained in the first pigment-containing adhesive layer is one commonly used in the technical field, and is not particularly limited as long as it allows the metallic decorative laminate to exhibit 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 for outdoor use requiring weather resistance. More specifically, preferred pigments include inorganic pigments such as titanium white, 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.

[0076] The total content of the pigments in the glittering resin layer is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, more preferably 0.2 parts by mass or more and 5.0 parts by mass or less, even more preferably 0.3 parts by mass or more and 4.0 parts by mass or less, and even more preferably 0.4 parts by mass or more and 3.0 parts by mass or less, relative to 100 parts by mass of the total content of the resin components.

[0077] 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.

[0078] <Other resin layers> The other resin layers may include a surface protection layer, a primer layer, an adhesive layer, and the like, as required.

[0079] For the surface protection layer and 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 for the adhesive layer, a polyurethane-based adhesive layer is preferred in order to obtain sufficient transparency and adhesive strength.

[0080] [Metal-like articles] The metallic article of this embodiment is required to be a metallic article using the metallic decorative laminate.

[0081] For example, the metallic decorative laminate is manufactured by the manufacturing method described below and molded into a desired shape depending on the purpose. For example, it can be used for housings of smartphones and 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 and decorative parts of personal computers, TVs, and home appliances, housings and decorative parts of pachinko, pachinko slot machines, game machines, etc., or general-purpose items such as carry-on bags and suitcases, and can be used to impart metallic decorativeness and design properties in place of plating or metal materials.

[0082] In particular, the metallic decorative laminate of this embodiment not only imparts a metallic design to an article, but also has excellent millimeter wave transmittance. Therefore, even when placed between a millimeter wave radar and the object to be detected, it can transmit millimeter waves irradiated by the millimeter wave radar and reflected from the object, making it preferable for use as an automobile bumper or emblem. For example, if the metallic decorative laminate is used in an automobile bumper, the millimeter wave radar can be installed on the inside of the bumper facing the vehicle, and the millimeter wave radar can be installed in a part that cannot be seen from the outside of the automobile, allowing for greater freedom in automobile design. The design and millimeter wave transmittance are as described for the metallic decorative laminate of this embodiment, so they will not be described here.

[0083] 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 laminate, 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 staining.

[0084] [Method for manufacturing metallic decorative laminate] The method for manufacturing the metallic decorative laminate of this embodiment is required to be a method for manufacturing the metallic decorative laminate that includes, in this order, applying a coating liquid containing the fluorine-based resin, the acrylic resin, and the lustrous material to a substrate and heating the coating liquid.

[0085] <Applying> A coating liquid containing the fluorine-based resin, the acrylic resin, and the luster material is applied to a substrate described below. The fluorine-based resin, the acrylic resin, and the luster material are as described above, and therefore will not be described here.

[0086] The coating liquid may contain a fluorine-based resin, an acrylic resin, and a luster material, and may further contain the other components and a solvent as necessary. Because the coating liquid contains the luster material, it is not a homogeneous solution but a slurry containing the luster material.

[0087] The coating can be carried out by applying the coating liquid to the substrate using a known means such as a gravure coater, a reverse coater, a die coater, a knife coater, or a roll coater.

[0088] (solvent) The solvent may be any solvent generally used in the art, and may be selected from 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, among others, with polar solvents such as ester solvents, ether solvents, and ketone solvents being preferred.

[0089] 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.

[0090] 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.

[0091] (base material) The substrate can be any substrate used in the relevant technical field, and can be appropriately selected from polyethylene substrates, polyester substrates (including polyethylene terephthalate (PET) substrates), polycarbonate substrates, etc. The thickness of the substrate may be within a range that does not interfere with the manufacturing process, and generally, a substrate having a thickness of 10 μm or more and 500 μm or less can be used.

[0092] <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 with the coating liquid on it. The heating also includes the case where the substrate is preheated, then coated, and then further heated.

[0093] 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 acrylic resin contained therein, the resin component can be mixed with the fluororesin. This is preferable because it prevents the crystal size of the fluororesin from growing, suppresses precipitation of the fluororesin from the resin component, and allows the luster material to be uniformly dispersed.

[0094] The heating temperature can be selected appropriately depending on the heating time, the fluorine-based resin, acrylic resin, solvent, and substrate used, etc., but in order to obtain a metallic decorative laminate with excellent design and excellent millimeter wave transmittance, the heating temperature is preferably 80°C or higher, more preferably 100°C or higher, even more preferably 110°C or higher, preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 130°C or lower.

[0095] 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.

[0096] The heating time can be selected appropriately depending on the size of the metallic decorative laminate to be produced, the heating temperature, the fluorine-based resin, acrylic resin, solvent, and base material 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.

[0097] <Removing the substrate> It is also preferable that the method for producing the metallic decorative laminate of the present embodiment further includes peeling off the substrate after the heating.

[0098] The metallic decorative laminate produced by the method for producing the metallic decorative laminate is formed on a substrate, and therefore, the metallic decorative laminate of this embodiment can be obtained by peeling the metallic decorative laminate produced by heating from the substrate.

[0099] The peeling method is not particularly limited as long as it is a method commonly used in the relevant field.

[0100] [Method for manufacturing metallic articles] The metallic article of this embodiment can be produced, for example, by the following method.

[0101] The method includes a molding step in which the surface temperature of the metallic decorative laminate is set to 150°C to 200°C, the metallic decorative laminate is brought into close contact with a mold, and the metallic decorative laminate is molded onto the surface of the article to obtain a metallic article.

[0102] (molding process) When the metallic decorative laminate is thermoformed, the surface temperature of the metallic decorative laminate is 150°C to 200°C, so that the metallic decorative laminate does not draw down during molding and whitening does not occur, resulting in good moldability. A surface temperature of 150°C or higher sufficiently softens the metallic decorative laminate, preventing it from sagging and deforming due to the drawdown phenomenon, making processing and molding difficult. Furthermore, a surface temperature of 200°C or lower prevents the metallic decorative laminate from entering a molten state, resulting in excessive softening that makes molding difficult, or whitening and other phenomena becoming more likely to occur.

[0103] The shape of the mold to which the metallic decorative laminate is attached 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 metallic decorative laminate and control of the cooling conditions of the metallic article after the molding process.

[0104] As a method for adhering the metallic 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 metallic decorative laminate and the mold is improved, allowing it to be processed into a more precise shape.

[0105] (Clamping process) The method for manufacturing the metallic article can include a clamping step of clamping the metallic decorative laminate prior to the molding step. This step allows the metallic 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 metallic decorative laminate, for example, by gripping both ends of the metallic decorative laminate. Grip of the metallic decorative laminate is not limited to both ends of the metallic decorative laminate, and any part of the metallic decorative laminate can be gripped. Typically, when metallic articles are continuously produced, both ends of the metallic decorative laminate in the width direction can be gripped. Furthermore, when metallic articles are batch-produced using rectangular metallic decorative laminates cut to a predetermined length, the ends of the four sides can be gripped by upper and lower frames.

[0106] (Heating process) The method for producing the metallic article can also include a heating step of heating the metallic decorative laminate after the clamping step. For example, after clamping the metallic 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 metallic decorative laminate to uniformly heat both sides of the metallic decorative laminate simultaneously. This heating step can control the surface temperature of the metallic decorative laminate to 150°C to 200°C.

[0107] (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.

[0108] The metallic decorative laminate of this embodiment, the metallic article including the metallic decorative laminate of this embodiment, and the method for producing the metallic decorative laminate of this embodiment are preferably the following [1] to

[13] . [1] A metallic decorative laminate comprising a resin component containing one or more fluorine-based resins and one or more acrylic resins, and a photoluminescent resin layer containing one or more photoluminescent materials, wherein the photoluminescent resin layer has a thickness of 20 μm or more and 100 μm or less. [2] The metallic decorative laminate according to [1], 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. [3] The metallic decorative laminate according to [1] or [2], wherein the particle diameter of the glittering material is 3 μm or more and 50 μm or less. [4] The metallic decorative laminate according to any one of [1] to [3], wherein the thickness of the glittering material is 0.05 μm or more and 1.00 μm or less. [5] The metallic decorative laminate according to any one of [1] to [4], wherein the surface of the glittering material is coated. [6] The metallic decorative laminate according to any one of [1] to [5], wherein the amount of the glittering material in the glittering resin layer is 0.10 parts by mass or more and 30.00 parts by mass or less per 100 parts by mass of the total of the resin components. [7] The metallic decorative laminate according to any one of [1] to [6], wherein the acrylic resin has a glass transition point (Tg) of 100° C. or higher. [8] The metallic decorative laminate according to any one of [1] to [7], wherein the acrylic resin has an imide skeleton. [9] The metallic decorative laminate according to any one of [1] to [8], wherein the ratio of the content of the fluororesin to the content of the acrylic resin contained in the resin component (content of the fluororesin / content of the acrylic resin) is 1.0 or more and 5.0 or less.

[10] The metallic decorative laminate according to any one of [1] to [9], wherein the glittering resin layer is only one layer.

[11] A metallic article using the metallic decorative laminate according to any one of [1] to

[10] .

[12] Applying a coating liquid containing a fluorine-based resin, an acrylic resin, and a photoluminescent material to a substrate;

[0023] The method for producing a metallic decorative laminate according to any one of [1] to

[10] , which comprises, in this order,

[13] The method for producing the metallic decorative laminate according to

[12] , further comprising peeling off the substrate after the heating. [Example]

[0109] The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples.

[0110] (Evaluation method) 1. Millimeter wave transmittance (transmission attenuation) The millimeter wave transmission attenuation of the metallic multilayer laminate 100 at a frequency of 76.5 GHz was measured using a KEYCOM RAS (SM5899). The metallic decorative laminate was set in the device so that millimeter waves would transmit from the surface 21 of the glittering resin layer opposite the product to the surface 22 of the glittering resin layer facing the product, as shown in Figure 3. The measurement was performed 250 times, and the average absolute value of the 250 measurements was taken as the transmission attenuation (dB). The millimeter wave transmittance was evaluated as "A" if it was excellent (2 dB or less), "B" if it was at a level that was acceptable for practical use (less than 5 dB), and "C" if it did not have sufficient millimeter wave transmittance (5.00 dB or more). A and B were judged as passing, and C was judged as failing. 2. Substrate peelability A 20 cm x 20 cm sample was cut from the pre-peeling substrate obtained in each Example and Comparative Example, as described below, to prepare a substrate peelability test sample. A portion of the metallic decorative laminate was peeled from one corner of the substrate peelability test sample, and the peeled portion was pinched and peeled toward the diagonal corner. The peeled metallic decorative laminate was visually observed, and if there were no defects, it was rated "A," and if there were defects, it was rated "C." A was judged as passing, and C was judged as failing. 3.Pre-molding appearance evaluation The metallic decorative laminates obtained in each example and comparative example were visually observed, and if they exhibited a metallic design, they were rated as "A," and if they did not exhibit a metallic design or had a matte finish, they were rated as "C." A was judged as passing, and C was judged as failing. 4. Post-molding appearance evaluation The metallic articles made using the metallic decorative laminates obtained in each Example and Comparative Example were visually observed and rated as "A" if they exhibited a metallic design, "B" if they were suitable for practical use but had an inferior metallic design compared to metallic decorative laminates rated "A," and "C" if they did not exhibit a metallic design or had a matte finish. A and B were judged as passing, and C was judged as failing. 5.Total light transmittance The total light transmittance was measured using a spectrophotometer (UH4150, manufactured by Hitachi High-Tech Science Corporation) in accordance with JIS K7375:2008. 6. Molecular weight measurement method The number average molecular weight (Mn), weight average molecular weight (Mw), average molecular weight (Mz) and polydispersity (Mw / Mn) of the fluorine-based resin and acrylic resin used in each of the examples and comparative examples were determined as follows.

[0111] 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 (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% (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%

[0112] Example 1 (Manufacturing metallic decorative laminates) The coating liquid described below was applied to a substrate (PET film (G2000 (manufactured by Toyobo Co., Ltd.))) The amount of coating was adjusted so that the thickness of the glittering resin layer after heating would be 30 μm.

[0113] Immediately after application, the substrate was heated at 120°C for 2 minutes to form a glittering resin layer on the substrate (substrate before peeling). The substrate before peeling was cooled to room temperature, and the substrate was peeled off to produce a metallic decorative laminate.

[0114] (Coating liquid (1)) 8.75 g of acrylic resin (SK540, Asahi Kasei Corporation) was added to 37.45 g of butyl carbitol acetate (Sankyo Kasei Sangyo Co., Ltd.) and stirred at room temperature to form a homogeneous solution. 0.57 g of ultraviolet absorber (Tinuvin 900, Asahi Kasei Corporation), 0.06 g of nucleating agent (A-3000, Mitsubishi Chemical Corporation), 13.16 g of fluorine-based resin (Kyanr 301, Arkema Co., Ltd.), and the amount (g) of aluminum flakes (FD5060, Asahi Kasei Corporation) listed in Table 1 as a photoluminescent material were added and further stirred to form coating solution (1).

[0115] Table 1 lists the product number, particle size (μm), and thickness (μm) of the aluminum flakes.

[0116] (Manufacturing of metallic products) Using a compressed air molding machine, the metallic decorative laminate was clamped, and then the metallic decorative laminate was preformed to fit a mold for injection molding at a preforming temperature of 200°C and a compressed air pressure of 6 bar. Unnecessary parts that protruded from the mold were trimmed off to obtain a metallic product.

[0117] Table 3 shows the results of the substrate peelability, transmission attenuation (dB) of the obtained metallic decorative laminate, and the appearance evaluation before molding and the appearance evaluation after molding of the metallic article.

[0118] In the table, the unit of transmission attenuation is dB as described above, and "A," "B," and "C" have the same meanings as above.

[0119] (Example 2) to (Example 10) In Example 1, the metallic decorative laminates of Examples 2 to 10 were produced in the same manner as in Example 1, except that the lustrous material (aluminum flakes; all aluminum flakes listed in Table 1 are manufactured by Asahi Kasei Corporation) of the coating liquid (1) and its amount were as listed in Tables 1 and 3.

[0120] The results of evaluation of the substrate peelability, transmission attenuation, pre-molding appearance of the obtained metallic decorative laminate, and post-molding appearance of the metallic article are summarized in Tables 2 and 4. (Comparative Example 1) A metallic decorative laminate of Comparative Example 1 was produced in the same manner as in Example 1, except that the coating liquid of Example 1 did not use a fluorine-based resin.

[0121] The results of evaluation of the substrate peelability, transmission attenuation, pre-molding appearance of the obtained metallic decorative laminate, and post-molding appearance of the metallic article are summarized in Table 4.

[0122] [Table 1]

[0123] [Table 2]

[0124] [Table 3]

[0125] [Table 4]

[0126] (Example 11) to (Example 13) Metallic decorative laminates of Examples 11 to 13 were produced in the same manner as in Example 1, except that the following coating liquid (2) was used.

[0127] The results of evaluation of the substrate peelability, transmission attenuation, pre-molding appearance of the obtained metallic decorative laminate, and post-molding appearance of the metallic article are summarized in Table 6.

[0128] (Coating liquid (2)) 8.75 g of acrylic resin (SK540, Asahi Kasei Corporation) was added to 37.45 g of butyl carbitol acetate (Sankyo Kasei Sangyo Co., Ltd.) and stirred at room temperature to form a homogeneous solution. 0.57 g of ultraviolet absorber (Tinuvin 900, Asahi Kasei Corporation), 0.06 g of nucleating agent (A-3000, Mitsubishi Chemical Corporation), 13.16 g of fluorine-based resin (Kyanr 301, Arkema Corporation), synthetic mica pearl (product name: SC-100ST, Nippon Koken Kogyo Co., Ltd., particle size 22 μm) as a glittering material in the amount (g) shown in Table 5, and MHI White #148 (Mikuni Pigment Co., Ltd.) as a pigment in the amount (g) shown in Table 5 were added and further stirred to form coating solution (2).

[0129] [Table 5]

[0130] [Table 6]

[0131] From the results of Examples 1 to 13 shown in Tables 2, 4, and 6, it was confirmed that the metallic decorative laminates exhibited metallic designs and had excellent millimeter wave transmittance. It was also confirmed that they had excellent substrate peelability and film-forming properties. Furthermore, it was confirmed that all of the metallic articles had no practical problems.

[0132] In contrast, the metallic decorative laminate of Comparative Example 1 was found to have inferior design and millimeter wave transmittance compared to the metallic decorative laminate of this embodiment. It was also confirmed that the substrate peelability was also inferior. It was also found that the metallic article using the metallic decorative laminate of Comparative Example 1 also had inferior design. [Industrial Applicability]

[0133] The metallic decorative laminate of this embodiment and the metallic article including the metallic decorative laminate of this embodiment exhibit an excellent metallic design, have excellent millimeter wave transmittance, and are easy to manufacture. Furthermore, the metallic decorative laminate can be easily manufactured by the manufacturing method of the metallic decorative laminate of this embodiment.

[0134] The metallic decorative laminate of this embodiment is suitable for use in resin parts such as car bumpers. [Explanation of symbols]

[0135] 1 Thickness direction 2 Width direction 3 Longitudinal direction 10 Metallic decorative laminate 20 Bright resin layer 21 Surface of the photoluminescent resin layer opposite to the article 22. Surface of the glittering resin layer on the product side 30 Photoluminescent materials 31 Photoluminescent material thickness direction 32 Thickness of photoluminescent material 33 Particle diameter direction of photoluminescent material 34 Particle size of photoluminescent material 100mm transparent bright coating resin product 110 Bright resin layer (1) 111 Bright resin layer (2) 112 Glitter resin layer (3) 120 Glitter material 121 Areas with low content of photoluminescent materials 122 Areas with high content of photoluminescent materials 130 Resin substrate

Claims

1. A metallic decorative laminate comprising a resin component containing one or more fluorine-based resins and one or more acrylic resins, and a photoluminescent resin layer containing one or more photoluminescent materials, wherein the photoluminescent resin layer has a thickness of 20 μm or more and 100 μm or less.

2. The metallic decorative laminate according to claim 1, wherein the lustrous material contains at least one material selected from the group consisting of scaly or flaky metals, scaly or flaky alloys, scaly or flaky metal oxides, scaly or flaky mica, glass flakes, and pulverized films.

3. The metallic decorative laminate according to claim 1 or 2, wherein the particle diameter of the glittering material is 3 μm or more and 50 μm or less.

4. The metallic decorative laminate according to any one of claims 1 to 3, wherein the thickness of the glittering material is 0.05 μm or more and 1.00 μm or less.

5. The metallic decorative laminate according to any one of claims 1 to 4, wherein the surface of the glittering material is coated.

6. The metallic decorative laminate according to any one of claims 1 to 5, wherein the photoluminescent material in the photoluminescent resin layer is 0.10 parts by mass or more and 30.00 parts by mass or less with respect to a total of 100 parts by mass of the resin components.

7. The metallic decorative laminate according to any one of claims 1 to 6, wherein the acrylic resin has a glass transition point (Tg) of 100 ° C. or higher.

8. The metallic decorative laminate according to any one of claims 1 to 7, wherein the acrylic resin has an imide skeleton.

9. The ratio of the content of the fluorine-based resin to the content of the acrylic resin contained in the resin component (content of the fluorine-based resin / content of the acrylic resin) is 1.0 or more and 5.0 or less. The metallic decorative laminate according to any one of claims 1 to 8.

10. The metallic decorative laminate according to any one of claims 1 to 9, wherein the glittering resin layer is only one layer.

11. A metallic decorative article using the metallic decorative laminate according to any one of claims 1 to 10.

12. applying a coating liquid containing a fluorine-based resin, an acrylic resin, and a photoluminescent material to a substrate; The method for producing a metallic decorative laminate according to any one of claims 1 to 10, comprising the steps of:

13. The method for producing a metallic decorative laminate according to claim 12, further comprising peeling off the substrate after the heating.

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