Metallic decorative laminate, multilayer laminate, metallic article, and method for producing the multilayer laminate

Abstract

To provide a metallic decorative laminate which exhibits an excellent metallic design, reduces an environmental load, and is easily manufactured, a multilayer laminate, a metallic article, and a method for manufacturing the multilayer laminate.SOLUTION: Provided are a metallic decorative laminate including a bright resin layer containing a resin component containing one or more fluororesins and one or more bright materials, and a base layer, and including a design layer on at least one side of the base layer, a multilayer laminate including the metallic decorative laminate, and a metallic article.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[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). As another means, electromagnetic wave transparent bright coated resin products have been developed (Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-241948 [Patent Document 2] 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, a multilayer laminate, a metallic article, and a method for manufacturing the multilayer laminate, which exhibit an excellent metallic design, reduce the environmental load, and are easy to manufacture. [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 [4]. [1] A metallic decorative laminate comprising a resin component containing one or more fluorine-based resins and a photoluminescent resin layer containing one or more photoluminescent materials, and a base layer, and a design layer on at least one side of the base layer. [2] A multilayer laminate comprising the metallic decorative laminate according to [1], further comprising a substrate layer on the opposite side of the base layer of the glittering resin layer. [3] A metallic article comprising the metallic decorative laminate described in [1]. [4] A method for producing the multilayer laminate described in [2], which comprises, in this order, applying a coating liquid containing one or more fluorine-based resins and one or more luster materials to a substrate, heating the coating liquid, and providing a base layer including a design layer. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a metallic decorative laminate, a multilayer laminate, a metallic article, and a method for manufacturing the multilayer laminate, which exhibit an excellent metallic design, reduce the environmental load, and are easy to manufacture. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a schematic diagram showing an example of a cross section of a multilayer laminate including the metallic decorative laminate of the present embodiment. [Figure 2] 2 is a schematic diagram showing the relationship between the glittering resin layer of the present embodiment and external light and irradiated light. FIG. [Figure 3] FIG. 2 is a schematic diagram for explaining a design layer of the present embodiment. [Figure 4] FIG. 1 is a schematic diagram of an electromagnetic wave transmitting bright coated resin product (three layers laminated) described in Patent Document 2. [Figure 5] FIG. 2 is a schematic diagram of a glittering material in a glittering resin layer according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0008] The aforementioned Patent Document 1 describes an invention relating to a plated synthetic resin component for vehicles that 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 bumper uses aluminum flakes to create a metallic design, further improvements in the design are needed.

[0010] In contrast, the metallic decorative laminate of the present disclosure has a specific layer structure, making it possible to obtain an excellent metallic design.

[0011] Additionally, it is possible to provide a multilayer laminate, a metallic article, and a method for manufacturing the multilayer laminate, each of which includes the metallic decorative laminate as a component.

[0012] The metallic decorative laminate, the multilayer laminate, the metallic article, and the method for manufacturing the multilayer laminate according to the present invention will be described below. However, 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 Fig. 5, 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 an 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 can be arbitrarily combined.

[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 required to be a metallic decorative laminate that includes a resin component containing one or more fluorine-based resins and a photoluminescent resin layer containing one or more photoluminescent materials, as well as a base layer, and includes a design layer on at least one side of the base layer.

[0017] The metallic decorative laminate of this embodiment can be used to decorate plastic 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 bonding 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, and other vehicles that use lubricating oils.

[0018] 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.

[0019] The metallic decorative laminate can impart a metallic design to the surface of an article. Furthermore, by installing a light source, other designs can be imparted by light transmitted through the laminate. For illustrative purposes, FIG. 2 shows an example of a metallic decorative laminate. As shown in FIG. 2, external light 5 is reflected by the photoluminescent resin layer 11, and the metal layer reflected light 6 is visible to the observer 4, creating a metallic design. However, when external light 5 is absent or weak, such as at night, the metal layer reflected light 6 does not sufficiently reach the observer 4. This causes the observer 4 to perceive the metallic design as not being apparent.

[0020] In contrast, by placing the light source 7 on the side of the photoluminescent resin layer 11 opposite the observer 4, the irradiated light 8 passes through the metallic decorative laminate (including the photoluminescent resin layer) and reaches the observer 4 as light 9 transmitted through the laminate. By placing the light source 7, the observer 4 can see the design through the light 9 transmitted through the laminate even at night. By appropriately adjusting the pattern and transmittance of the design layer 14, the design layer 14 can be made to transmit or not transmit the light 9 transmitted through the laminate, making it possible to express a design similar to the design created by external light 5 or a completely different design.

[0021] It is also preferable to form the design layer 14 into a design including an area where the irradiated light 8 does not transmit (the black areas in the figure indicate the areas where light does not transmit), as shown in Figure 3, thereby creating a light-shielding area that blocks the irradiated light and creates a contrast with other areas. The light-shielding area adjusts the color tone and / or intensity of the light 9 transmitted through the laminate, which is derived from the irradiated light 8 from the light source 7.

[0022] By forming letters or patterns as in the light-shielding region 20, the letters or patterns can be expressed as areas where the laminate transmits weak or no light 9. It is also possible to significantly reduce the transmittance of the printed area, as in the light-shielding region 21, and mask areas where you do not want light to transmit. This creates a contrast between areas that transmit light and areas that do not. In the present disclosure, a design layer having a light-shielding region where the transmittance of the laminate transmitted light for the irradiated light 8 is 1% or less is specifically referred to as a light-shielding layer.

[0023] Furthermore, unlike plating, the metallic decorative laminate is permeable to radio waves classified as millimeter waves (hereinafter referred to as millimeter wave permeability). Sensors such as millimeter wave radar are used to detect obstacles around vehicles such as automobiles. Millimeter wave radar is a device that irradiates an obstacle with radio waves having a wavelength of 1 to 10 mm, measures the time it takes for the radio waves to reflect off the obstacle and return, and thereby measures the distance to the obstacle. Millimeter wave radar is less affected by weather conditions such as rain or fog, and can detect obstacles at a distance, so it has been introduced by many automobile manufacturers. Millimeter wave radar for automobiles uses a millimeter wave band in the 76 to 77 GHz range, and the millimeter wave radar device main unit is mounted, for example, behind the front and rear bumpers of the automobile body, and millimeter waves are irradiated from the device main unit to obstacles through the bumper.

[0024] Patent Document 2 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 reflect millimeter waves. A known method for suppressing this reflection and improving millimeter wave transmittance is to increase the distance between aluminum flakes (Patent Document 2). However, with the method described in Patent Document 2, 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.

[0025] Furthermore, in Patent Document 2, 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.

[0026] Although a certain film thickness is preferable for achieving a metallic design, the manufacturing method of the glossy resin layer described in Patent Document 2 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 2, the coating film formation process had to be performed at least twice, making the process complicated.

[0027] Furthermore, as described in Patent Document 2, when a glossy resin layer is manufactured using an acrylic urethane coating containing aluminum flakes, the aluminum flakes are insoluble in the acrylic urethane coating and have low dispersibility. Therefore, the aluminum flakes, which have a high specific gravity, settle during the manufacturing process due to differences in specific gravity. This results in a distribution of the content of the glossy resin layer, where the content increases from the upper surface to the lower surface in the thickness direction (e.g., in Figure 4, a region with a high content of the glossy material is formed, such as region 322 with a high content of the glossy material, in contrast to region 321 with a low content of the glossy material in the radio wave-transmitting glossy coating resin product 300). For example, when manufacturing a glossy resin layer by stacking three layers (see Figure 4), aluminum flakes (glossy material 320) settle due to differences in specific gravity on the resin substrate 330 side of each glossy coating film (glossy coating film (1) 310 to glossy coating film (3) 312), resulting in region 322 with a high content of aluminum flakes. In this way, in the region 322 with a high content of aluminum flakes, millimeter waves are reflected, resulting in a decrease in millimeter wave transmittance.

[0028] In contrast, the metallic decorative laminate of the present disclosure has excellent dispersibility of the luster material, resulting in uniform dispersion of the luster material. Furthermore, because of its excellent dispersibility, the luster resin layer can be thickened with a single layer. Furthermore, because a film thickness of 20 μm or more can be achieved without stacking multiple luster resin layers, no intermediate regions with a high luster material content (such as region 322 with a high luster material content in the luster coating film (2) 311 in FIG. 2) are formed. This allows for the production of a metallic decorative laminate that exhibits an excellent metallic design (hereinafter also referred to as excellent design) and has excellent millimeter wave transmittance.

[0029] In addition, in Patent Document 2, 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 stain resistance and chemical resistance. In contrast, the metallic decorative laminate of the present disclosure contains a fluorine-based resin in the glittering resin layer, so when the glittering resin layer is used as the outermost surface, it also has the properties of excellent stain resistance 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.

[0030] Even when the light-shielding layer is present, since general-purpose dyes have millimeter wave transparency, the influence on the millimeter wave transparency of the metallic decorative laminate is negligible.

[0031] It is preferable to include the glossy film layer, the base layer, and the design layer in this order, and it is preferable that the glossy film layer be the outermost surface facing the observer 4, as shown in Figure 2. When the design layer 14 is positioned closer to the article than the glossy resin layer 11 when viewed from the article side, the effect of the design layer 14 on the metal layer reflected light 6 is extremely small, which is preferable for the expression of a metallic design.

[0032] 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 200 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.

[0033] In order to balance design, weather resistance, and chemical resistance, the thickness is preferably 20 μm or more and 200 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.

[0034] 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 be able to express a required color tone, and further means the property that the required color tone can be expressed by light transmitted through the laminate.

[0035] In the present disclosure, "heat resistance" refers to whether or not there is little change in properties even when heated, and can be evaluated, for example, by the method described in the Examples.

[0036] 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 shiny 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 immersing the metallic decorative laminate in an organic solvent such as pentane and observing its appearance.

[0037] 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.

[0038] In the present disclosure, "moldability" refers to the property of ease of manufacturing a metallic article using the metallic decorative laminate of the present disclosure, and by increasing the layer thickness, breakage during molding can be suppressed, and by decreasing the layer thickness, even fine parts of the article can be decorated. For example, it can be evaluated by the method described in the examples.

[0039] The total light transmittance of the metallic decorative laminate of this embodiment can be adjusted as needed. The metallic decorative laminate may exhibit the same total light transmittance over the entire surface, or may have a light-shielding area as described above, with the light-shielding area having a total light transmittance of 1% or less, preferably approximately 0%. As will be described later, the metallic decorative laminate of this embodiment expresses the desired design through the photoluminescent material contained in the photoluminescent resin layer and the design layer.

[0040] The total light transmittance of the metallic decorative laminate of this embodiment can be adjusted by adjusting the content of the lustrous material, the shape of the lustrous material, the content of the pigment, etc., and by appropriately adjusting the total light transmittance of the design layer.

[0041] The total light transmittance of the metallic decorative laminate of this embodiment can be adjusted as needed, but the total light transmittance of the portion where the design is expressed by the light transmitted through the laminate 9 can be adjusted by the content of the luster material and / or pigment. If the content is increased to more strongly express the metallic design by the luster material, the total light transmittance will be lower. In addition, the total light transmittance will also be lowered by increasing the content of pigment to adjust the color tone. When the total light transmittance is reduced, the color of the article is masked, and in order to achieve this 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. There is no particular upper limit, but it is sufficient that the metallic design of the metallic decorative laminate of the present disclosure is expressed, and 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 arranged that the color of the article is substantially not recognizable from the metallic decorative laminate side.

[0042] The total light transmittance can be measured, for example, by the method described in the Examples.

[0043] The metallic decorative laminate of this embodiment may include only the glittering resin layer, base layer, and design layer described below, but may also include other resin layers described below.

[0044] <Glitter resin layer> The glittering resin layer is a layer that imparts metallic luster to the metallic decorative laminate, and is required to contain a resin component containing one or more fluororesins and one or more glittering materials. The glittering resin layer contains a resin component and one or more glittering materials, and the resin component contains one or more fluororesins.

[0045] The photoluminescent resin layer may contain only the fluorine-based resin as the resin component, but the resin component may further contain one or more thermoplastic resins described below, or may further contain other components described below.

[0046] In other words, the photoluminescent resin layer may contain only the fluororesin and the photoluminescent material, or may contain only the fluororesin, the thermoplastic resin, and the photoluminescent material, or may further contain other components described below.

[0047] Although details will be described later, it is preferable that the metallic article be laminated in the order of the article, the design layer, the base layer, and the glittering resin layer. In particular, it is preferable that the glittering resin layer be the outermost surface of the metallic article, and since the glittering resin layer comes into contact with the atmosphere, solvents, chemicals, etc., its chemical resistance and weather resistance play a major role in improving the chemical resistance and weather resistance of the metallic article.

[0048] The glittering resin layer contains a fluororesin and a glittering material, thereby improving the chemical resistance and weather resistance of the metallic article. Even those skilled in the art would not believe that using a combination of a fluororesin and a glittering material would improve chemical resistance and weather resistance compared to using a fluororesin alone. However, it has been found that the configuration of this embodiment significantly improves chemical resistance and weather resistance. While the reason for this is unclear, it is believed that when the glittering resin layer contains a fluororesin and a glittering material, aggregation of the fluororesin in the glittering resin layer is suppressed, resulting in a uniform dispersion of the fluororesin within the glittering resin layer, thereby allowing the chemical resistance and weather resistance characteristics of the fluororesin to be expressed on the layer surface. Furthermore, the fluororesin improves the dispersibility of the glittering material, and the glittering material is dispersed throughout the resin components, resulting in a synergistic effect of creating a uniform metallic design.

[0049] The thicker the layer thickness of the lustrous resin layer, the greater the amount of lustrous material, thereby improving the metallic design, and in order to achieve the above-mentioned effects, 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 formability, 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.

[0050] In order to balance millimeter wave transmittance, 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.

[0051] In order to balance millimeter wave transmittance, chemical resistance, weather resistance, designability, and moldability, the amount of the glittering material in the glittering resin layer is preferably 0.10 parts by mass or more and 20.00 parts by mass or less, more preferably 0.30 parts by mass or more and 15.00 parts by mass or less, even more preferably 0.50 parts by mass or more and 10.00 parts by mass or less, and even more preferably 0.80 parts by mass or more and 5.00 parts by mass or less, relative to 100 parts by mass of the total of the resin components.

[0052] The glittering resin layer contains, in addition to the resin component, 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 to 20.00 parts by mass relative to a total of 100 parts by mass of the resin component. By setting it to the lower limit or higher, the chemical resistance, weather resistance, and design of the metallic decorative laminate are improved, and by setting it to the upper limit or lower, the moldability is improved. It is more preferably 0.02 to 15.00 parts by mass, more preferably 0.03 to 10.00 parts by mass, even more preferably 0.05 to 5.00 parts by mass, even more preferably 0.07 to 3.00 parts by mass, and even more preferably 0.08 to 2.00 parts by mass.

[0053] In addition, the glittering resin layer may contain a pigment, which makes it possible to express colors with metallic luster, such as black, red, blue, white, navy blue, crimson, orange, and olive, which are difficult to express using glittering materials alone.

[0054] 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. 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, 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, 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.

[0055] 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. 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, 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, 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.

[0056] If necessary, the surface of the glittering resin layer may be embossed to have various patterns, or may be provided with fine irregularities to give it a matte finish.Furthermore, a hairline design may be provided by hairline processing.

[0057] <Resin component> The glittering resin layer contains one or more fluorine-based resins as resin components as described above, and may further contain one or more thermoplastic resins. These may be a mixture (polymer alloy) or a reaction product, but a mixture (polymer alloy) is more preferable in order to improve the dispersibility of the glittering material in the metallic decorative laminate.

[0058] 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.

[0059] Although the details of the thermoplastic resin will be described later, a single thermoplastic resin may be used alone or in combination of two or more. 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.

[0060] When the total amount of resin components contained in the glossy resin layer is taken as 100% by mass, the total amount 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. There is no particular upper limit, and it is preferably substantially 100% by mass. "Substantially" means excluding impurities and the like that are unintentionally contained.

[0061] The resin component 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 other than the glittering material contained in the glittering resin layer are referred to as resin components.

[0062] When the resin component contained in the glossy resin layer contains the fluorine-based resin and the thermoplastic resin, the ratio of the content of the fluorine-based resin to the content of the thermoplastic resin (content of the fluorine-based resin (% by mass) / content of the thermoplastic resin (% by mass)) 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. When an acrylic resin described below is used as the thermoplastic resin, the ratio is also 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.

[0063] By making the content of the fluororesin larger than the content of the thermoplastic resin (acrylic resin), the dispersibility of the fluororesin in the glittering resin layer is improved, and chemical resistance and weather resistance are improved, which is preferable.

[0064] <<Fluorine-based resin>> The fluororesin is generally added for the purpose of improving chemical resistance, weather resistance, etc. In this embodiment, the resin component contains the fluororesin, which improves the dispersibility of the luster material, and the metallic article using this has a uniform metallic luster, which is preferable, and also improves millimeter wave transmittance, which is preferable.

[0065] 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 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.

[0066] 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.

[0067] 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.

[0068] The content of the fluorine-based resin in the resin component of the glittering resin layer is preferably 30.00% by mass or more and 80.00% by mass or less, more preferably 35.00% by mass or more and 80.00% by mass or less, even more preferably 40.00% by mass or more and 75.00% by mass or less, even more preferably 50.00% by mass or more and 70.00% by mass or less, and even more preferably 55.00% by mass or more and 65.00% by mass or less.

[0069] <<Glitter material>> The lustrous material is not particularly limited as long as it is dispersed in the lustrous resin layer to reflect external light (incident light), impart a metallic luster to the lustrous resin layer, and is 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.

[0070] 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.

[0071] The lustrous material preferably 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 pulverized film.

[0072] The lustrous material may be any material that exhibits lustrous properties when contained in the resin composition; however, in order to improve ease of availability and design, 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; more preferably, scaly or flaky metal, scaly or flaky mica, or pulverized film; even more preferably, scaly or flaky metal or scaly or flaky mica; and even more preferably, scaly or flaky metal.

[0073] 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.

[0074] Examples of scaly or flake mica include white pearl pigments, interference pearl pigments, and colored pearl pigments.

[0075] 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.

[0076] 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.

[0077] The photoluminescent material is preferably uniformly dispersed in the resin component within the photoluminescent resin layer 11 in FIG. 5 and oriented so that the thickness direction 210 of the photoluminescent material is approximately parallel to the thickness direction 100. While FIG. 5 shows the photoluminescent material as a disk, the photoluminescent material is not limited to this. The longest length in the planar direction of the photoluminescent material 200 (the particle diameter direction 220 of the photoluminescent material) is defined 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 defined 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. The particle diameter of the photoluminescent material is 221 (D 50 In order to obtain the desired product and to achieve a metallic design, 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 order to improve the amount of transmitted light, improve millimeter wave transmittance, and improve chemical resistance and weather resistance, the volume average particle diameter (D) 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. 50 ) can be measured by a standard method.

[0078] In order to balance chemical resistance, weather resistance, millimeter wave transmittance, 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.

[0079] In order to achieve millimeter wave transparency, 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.

[0080] Photoluminescent material particle diameter 221 (D 50 The 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.

[0081] Fluorine-based resins generally have a tendency to aggregate. Aggregation tends to result in 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 an unevenly dispersed resin composition. When the resin component is applied, the aggregates tend to be unevenly distributed on the coating surface. This uneven state can prevent the fluororesin from fully exhibiting its properties. To prevent this growth, a nucleating agent, as 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.

[0082] The total content of the lustrous materials in the lustrous resin layer is preferably 5.00% by mass or more and 60.00% by mass or less, more preferably 8.00% by mass or more and 50.00% by mass or less, even more preferably 10.00% by mass or more and 45.00% by mass or less, even more preferably 15.00% by mass or more and 40.00% by mass or less, and even more preferably 20.00% by mass or more and 35.00% by mass or less.

[0083] <<Thermoplastic resin>> The glittering resin layer preferably further contains one or more thermoplastic resins.

[0084] The total content of thermoplastic resins in the resin components 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.

[0085] Examples of the thermoplastic resin include polyolefin resins, polyester resins, and polystyrene resins, with polyolefin resins being preferred due to their good moldability.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] The upper limit of Tg is not particularly limited, but from the viewpoint of formability, 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.

[0090] (acrylic resin) The polyolefin resin is preferably an acrylic resin. As the acrylic resin, any resin that is 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, can be used. More specifically, preferred examples include polyethyl methacrylate (PEMA), polybutyl methacrylate (PBMA), polycyclohexyl methacrylate (PCHMA), and polyethylhexyl methacrylate (PEHMA). Polymethyl methacrylate resin (PMMA) is particularly preferred as a resin component, because it has high transparency, excellent scratch resistance due to its high hardness, and can be processed into complex shapes due to its thermoplasticity.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] The acrylic resin preferably has an imide skeleton in its structure in order to achieve the above Tg range.

[0096] <<Other ingredients>> As the other components, nucleating agents, dyes, ultraviolet absorbers, antioxidants, antistatic agents, leveling agents, antifoaming agents, etc. may be used as necessary.

[0097] When the total amount of resin components contained in the glossy resin layer is 100% by mass, the total amount of the other components is preferably 0.05% by mass or more and 5.00% by mass or less, more preferably 0.10% by mass or more and 3.00% by mass or less, even more preferably 0.20% by mass or more and 2.00% by mass or less, and even more preferably 0.50% by mass or more and 1.00% by mass or less.

[0098] (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 formed, and the crystal size grows, the resin layer may become cloudy due to scattering by the crystals. The use of the nucleating agent is preferable because it can reduce the crystal 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 crystal size of the fluorine-based resin.

[0099] (dye) The pigment 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.

[0100] 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.

[0101] The pigment contained in the glittering resin layer is one commonly used in the technical field. It 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, 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.

[0102] As the ultraviolet absorber, antioxidant, antistatic agent, leveling agent and antifoaming agent, general-purpose compounds can be used, and as the ultraviolet absorber, benzotriazole-based compounds are preferred.

[0103] <Base layer> The base layer 13 is preferably located on the opposite side of the glittering resin layer 11 from the observer 4 in the metallic decorative laminate 1. The design layer 14, which will be described later, is preferably printed on the base layer 13. Having the base layer 13 is preferable because it makes it easier to form the design layer 14.

[0104] The base layer 13 is preferably transparent to the irradiated light 8 emitted from the light source 7, and preferably has a total light transmittance of 85% or more. The base layer 13 is preferably made of a general-purpose resin such as polycarbonate resin, urethane resin, polyester resin, acrylic resin, acrylic urethane resin, or vinyl chloride-vinyl acetate copolymer resin.

[0105] The base layer may be in direct contact with the glittering resin layer, or may be laminated via a design layer 14 or an adhesive layer, which will be described later.

[0106] Furthermore, the thickness of the base layer may be any thickness that is common for metallic decorative laminates, and is preferably 10 μm or more and 1000 μm or less, more preferably 50 μm or more and 700 μm or less, even more preferably 100 μm or more and 500 μm or less, and even more preferably 150 μm or more and 300 μm or less, in order to prevent defects such as wrinkles from occurring during film formation and to prevent breakage of the metallic decorative laminate during molding and processing of the metallic article.

[0107] The substrate layer preferably has millimeter wave transmittance, and more preferably has high transparency. The total light transmittance as a measure of transparency is preferably 85% or more, more preferably 88% or more, and even more preferably 90% or more. There is no particular upper limit as long as the design is exhibited, but the upper limit is preferably 100% or less, and is generally about 99%.

[0108] <Design layer> The design layer is a layer configuration for expressing designs that are difficult to express with the photoluminescent resin layer alone, together with the photoluminescent resin layer. It is particularly preferable that the design layer acts on the light 9 transmitted through the laminate. The design layer is preferably a layer printed on the base layer, and the design may be letters, figures, etc., but is preferably a light-shielding layer that blocks the irradiated light 8. By using a light-shielding layer, specific areas can be designated as areas where the light 9 transmitted through the laminate is blocked (light-shielding areas 20, 21). In particular, the light-shielding layer can be evaluated using the contrast ratio described in the examples.

[0109] The ink composition (coating liquid) used to form the design layer is, for example, a mixture of a solvent and solid components such as a colorant and a binder resin. The ink composition may also contain other components such as a stabilizer, plasticizer, catalyst, and curing agent. The explanation of the solvent is the same as above and will be omitted here. Because the solvent eventually evaporates, the design layer is formed primarily from solid components such as a colorant and a binder resin. While the above-mentioned pigments can be used as colorants, black carbon is preferred when the design layer is a light-shielding layer. The binder resin is not particularly limited, but is preferably a general-purpose resin such as a polycarbonate resin, a urethane resin, a polyester resin, an acrylic resin, an acrylic urethane resin, or a vinyl chloride-vinyl acetate copolymer resin.

[0110] The thickness of the design layer may be appropriately selected depending on the desired properties, but is preferably 0.1 μm to 100 μm, more preferably 0.5 μm to 50 μm, and even more preferably 1 μm to 30 μm.

[0111] <Other layer configurations> The metallic decorative laminate may further include other layers.

[0112] The other layers may include a base layer (release layer), an adhesive layer, a protective layer, etc., as needed, and it is preferable to further include at least one of a protective layer and an adhesive layer.

[0113] The adhesive layer is preferably a polyurethane adhesive layer in order to obtain sufficient transparency and adhesive strength.

[0114] <<Base material (release layer)>> The substrate is used to apply a coating liquid for forming a glittering resin layer to the metallic decorative laminate when manufacturing the metallic decorative laminate as described below, and is a layer for protecting the outermost surface on the glittering resin layer side when the multilayer laminate described below is transported or stored, etc. Since it is peeled off at any stage in the manufacturing process of the metallic article, it also serves as a release layer.

[0115] 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. PET is more preferred in view of requirements such as ease of handling during production and availability.

[0116] 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.

[0117] <<Protective layer>> For the protective layer, a material 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. The protective layer is a layer mainly for protecting the design layer.

[0118] The thickness of the protective layer can be, for example, 50 μm to 1000 μm, which is a typical thickness for a metallic decorative laminate. Having the protective layer thickness within 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 and processing of the metallic article. If the protective layer thickness exceeds 1000 μm, the moldability of the metallic article, as described below, may be reduced.

[0119] It is also preferable that the protective 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.

[0120] <Layer structure of metallic decorative laminate> Specific examples of the layer structure of the metallic decorative laminate include the following (1) to (6). Note that " / " indicates the boundary between layers. The right side of Fig. 2 is the side of the observer 4, and the left side is the side of the light source 7. (1) Design layer / base layer / glossy resin layer (2) Base layer / design layer / glossy resin layer (3) Design layer / base layer / adhesive layer / glossy resin layer (4) Base layer / design layer / adhesive layer / glossy resin layer (5) Design layer / adhesive layer / base layer / adhesive layer / glossy resin layer (6) Base layer / adhesive layer / design layer / adhesive layer / glossy resin layer

[0121] [Multilayer laminate] The multilayer laminate of this embodiment is required to further include a substrate layer on the side of the metallic decorative laminate opposite to the base layer of the glittering resin layer.

[0122] The multilayer 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 photoluminescent resin layer on a substrate (release layer) described later.

[0123] The multilayer laminate may include the metallic decorative laminate and the substrate, but may also include only the metallic decorative laminate and the substrate, or may further include the other layers described above.

[0124] The layer thickness of the multilayer 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.

[0125] [Decorative laminate] The decorative laminate includes a protective layer on the design layer side of the multilayer laminate, and is obtained by peeling off the base material (release layer).

[0126] <Layer structure of decorative laminate> Specific examples of the layer structure of the decorative laminate include the following (1) to (6). Note that " / " indicates the boundary between layers. The right side of Fig. 2 is the side of the observer 4, and the left side is the side of the light source 7. (1) Protective layer / design layer / base layer / glossy resin layer (2) Protective layer / Base layer / Design layer / Glossy resin layer (3) Protective layer / design layer / base layer / adhesive layer / glossy resin layer (4) Protective layer / Base layer / Design layer / Adhesive layer / Glossy resin layer (5) Protective layer / design layer / adhesive layer / base layer / adhesive layer / glossy resin layer (6) Protective layer / Base layer / Adhesive layer / Design layer / Adhesive layer / Photo-luminescent resin layer

[0127] [Metal-like articles] The metallic article of this embodiment is required to include the metallic decorative laminate.

[0128] 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 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 instead of plating or metal materials.

[0129] 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.

[0130] 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 glittering resin layer in order to keep the surfaces of the protective layer and the base layer clean and prevent them from becoming dirty.

[0131] [Methods for producing intermediate laminates, multilayer laminates, decorated laminates, and metallic articles] The metallic decorative laminate of this embodiment is a feature common to the multilayer laminate, the decorative laminate, and the metallic article, and is formed during the process of manufacturing the multilayer laminate.

[0132] The method for producing the multilayer laminate of this embodiment requires the steps of applying a coating liquid containing one or more fluorine-based resins and one or more lustrous materials to the substrate, heating the substrate, and providing a base layer including a design layer, in that order.

[0133] The fluororesin, the luster material, the thermoplastic resin, the other components, the metallic decorative laminate, the multi-layer laminate, the decorative laminate, and the metallic article have already been explained, so they will not be explained here. (Coating liquid containing one or more types of fluorine-based resin and one or more types of photoluminescent material) The coating liquid containing one or more fluorine-based resins and one or more photoluminescent materials is a coating liquid for forming a photoluminescent resin layer, and may further contain the thermoplastic resin and / or other components.

[0134] The coating liquid may further contain a solvent, and may be a homogeneous solvent or a slurry.

[0135] (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.

[0136] 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.

[0137] 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.

[0138] <Applying> The coating can be carried out 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.

[0139] <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.

[0140] 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 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.

[0141] The heating temperature can be selected appropriately 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.

[0142] 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.

[0143] The heating time can be selected appropriately depending on the size of the laminate to be produced, the heating temperature, the fluorine-based resin, thermoplastic resin, solvent, and substrate to be used, etc., but in order to obtain a metallic decorative laminate with excellent design and excellent millimeter wave transmittance, the heating time is preferably 30 seconds or more, more preferably 1 minute or more, and preferably 5 minutes or less, and more preferably 3 minutes or less.

[0144] <Providing a base layer including a design layer> A multilayer laminate can be obtained by applying an adhesive to the photoluminescent resin layer formed on the substrate and then adhering a base layer including a design layer to the base layer. The base layer including the design layer may have the design layer on the adhesive side, or the side of the base layer opposite the design layer may have the adhesive layer side.

[0145] In the above description, a base layer including a design layer is used, but the design layer may be formed on the base layer after the base layer is adhered.

[0146] <<Peeling the substrate>> The method for producing the decorative laminate of this embodiment may include peeling the substrate from the multilayer laminate.

[0147] The peeling method is not particularly limited as long as it is a method commonly used in the relevant field. <Metallic Product Manufacturing Method> The metallic article of this embodiment can be produced, for example, by the following method.

[0148] The method includes a molding step in which the surface temperature of the decorative laminate is set to 150°C to 200°C, the surface of the metallic decorative laminate opposite the glittering resin layer is brought into close contact with a mold so that the surface faces the article, and the metallic decorative laminate is molded onto the surface of the article to obtain a metallic article.

[0149] (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.

[0150] 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.

[0151] 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 decorative laminate and the mold is improved, allowing it to be processed into a more precise shape.

[0152] (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.

[0153] (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.

[0154] (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.

[0155] The metallic decorative laminate, the multilayer laminate including the metallic decorative laminate, the metallic article, and the method for producing the decorative laminate of the present embodiment preferably include the following [1] to [9]. [1] A metallic decorative laminate comprising a resin component containing one or more fluorine-based resins and a photoluminescent resin layer containing one or more photoluminescent materials, and a base layer, and a design layer on at least one side of the base layer. [2] The metallic decorative laminate according to [1], comprising the glittering film layer, the base layer, and the design layer in this order. [3] The metallic decorative laminate according to [1] or [2], wherein the glittering resin layer further contains one or more thermoplastic resins. [4] The metallic decorative laminate according to any one of [1] to [3], wherein the lustrous material contains at least one material selected from the group consisting of scaly or flaky metals, scaly or flaky alloy metals, scaly or flaky metal oxides, scaly or flaky mica, glass flakes, and pulverized film. [5] The metallic decorative laminate according to any one of [1] to [4], wherein the amount of the glittering material in the glittering resin layer is 0.10 parts by mass or more and 20.00 parts by mass or less per 100 parts by mass of the total of the resin components. [6] The metallic decorative laminate according to any one of [1] to [5], further comprising at least one of a protective layer and an adhesive layer. [7] A multilayer laminate comprising the metallic decorative laminate according to any one of [1] to [6], further comprising a substrate layer on the side of the glittering resin layer opposite to the base layer. [8] A metallic article comprising the metallic decorative laminate according to any one of [1] to [6]. [9] A method for producing the multilayer laminate described in [7], which comprises, in this order, applying a coating liquid containing one or more fluorine-based resins and one or more luster materials to a substrate, heating the coating liquid, and providing a base layer including a design layer. [Example]

[0156] The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples.

[0157] (Evaluation method) 1.Weather resistance evaluation A xenon weather meter SX75 7.5kW (manufactured by Suga Test Instruments) was used. The treatment conditions were a black panel temperature of 63±2°C, humidity of 50%RH, rainfall cycle (non-rainfall time / rainfall time) of 102 min / 18 min, and illuminance of 180 W / m 2 , tank temperature 25~35℃, 500MJ / m 2 The color difference between the sample surface on the glittering 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 follows: A to C. A and B were judged as pass, and C was judged as fail. A: When ΔE*=3.0 or less, the weather resistance was evaluated as very good. B: When ΔE* was greater than 3.0 and not greater than 5.0, the sample was evaluated as having weather resistance. C: When ΔE* was greater than 5.0, it was evaluated as not having weather resistance.

[0158] 2. Heat resistance evaluation The decorative laminates obtained in the examples and comparative examples were left in an environment of 100°C for 500 hours, and the color difference of the sample surface on the glittering 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 follows: A to C. A and B were judged as pass, and C was judged as fail. A: When Δb*=1.0 or less and there is no defect such as peeling of the decorative sheet, the heat resistance was evaluated as very good. B: When Δb* was greater than 1.0 and not greater than 3.0, and there was only slight trouble such as peeling of the decorative sheet, the product was evaluated as having heat resistance. C: When Δb* was greater than 5.0 and a major defect such as peeling of the decorative sheet was observed, the sample was evaluated as having no heat resistance.

[0159] 3.Design evaluation The decorative laminates obtained in the examples and comparative examples were visually observed from the glittering resin layer side and rated as follows: A to C. A was judged as pass, and B and C were judged as fail. A: It has a metallic design. B: It does not have a metallic design or has a matte finish. C: The design due to transmitted light through the laminate is poor.

[0160] 4. Contrast Ratio 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.

[0161] In a decorative laminate including the design layer (light-shielding layer) shown in Fig. 3, the difference between the total light transmittance (%) of the light-transmitting region 22 of the laminate and the total light transmittance (%) of the light-shielding region 21 (the difference between the total light transmittance of the light-transmitting region 22 of the laminate and the total light transmittance of the light-shielding region 21) was defined as the contrast ratio (points). The contrast ratio was evaluated according to the following A to C. A and B were judged as pass, and C was judged as fail. A: 20 points or more Excellent. B: 5 points or more but less than 20 points. A level that is not problematic for practical use. C: Less than 5 points Insufficient contrast.

[0162] 5. Millimeter wave transmittance The millimeter wave transmission attenuation of the metallic decorative laminate 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 the millimeter wave would transmit from the base layer side of the metal layer. The measurement was performed 250 times, and the average of the absolute values ​​of the 250 measurements was taken as the transmission attenuation (dB). The millimeter wave transmittance was evaluated according to the following A to C. A and B were judged as pass, and C was judged as fail. A: 2dB or less Excellent. B: Less than 5dB. A level that is not problematic for practical use. C: 5.00 dB or more Not having sufficient millimeter wave transmittance.

[0163] 6. Post-molding design evaluation The metallic articles produced using the decorative laminates obtained in the examples and comparative examples were visually observed and evaluated according to the following criteria A to C. A and B were judged as pass, and C was judged as fail. A: It has excellent design. B: It has a slightly matte feel, but is at a level that does not pose a problem in practical use. C: Poor design.

[0164] 7.Moldability evaluation For metallic articles made using the decorative laminates obtained in the Examples and Comparative Examples, the stretched portions of the laminate (stretched to 200% of the original stretching) at the corners of the mold after the molding process were visually observed for cloudiness, and were evaluated according to the following criteria A to C. A and B were judged as pass, and C was judged as fail. A: The metallic product exhibits excellent design. B: Slight cloudiness is observed, but at a level that does not pose a problem for practical use. C: Cloudy and cracks or breaks were observed.

[0165] (Materials used) (Fluorine-based resin (Arkema, Kyanr301)) Number average molecular weight (Mn) 1,200 Weight average molecular weight (Mw) 1,600 Z average molecular weight (Mz) 1,900 Polydispersity (Mw / Mn) 1.3 Peak area ratio 14% (Acrylic resin (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% (dye 1) carbon black #2650 (Mitsubishi Chemical Corporation, particle size 13 nm) (dye 2) White pigment MHI White #148 (Mikuni Pigment Co., Ltd.) (Glitter material 1) Aluminum flakes GX40A (manufactured by Asahi Kasei Corporation, volume average particle diameter (D 50 ):19μm) (Glitter material 2) pearl pigment TWINCLEPEARL SXC-SO (Nihon Koken Kogyo Co., Ltd., volume average particle diameter (D 50 ):22μm)

[0166] Example 1 <Production of decorative laminates including metallic decorative laminates> (Formation of photoluminescent resin layer) The coating liquid for the glittering resin layer, which will be described later, was applied to a substrate (PET film (G2000 (manufactured by Toyobo Co., Ltd.))). The amount of coating was adjusted so that the glittering resin layer would have a thickness of 30 μm after heating.

[0167] Immediately after coating, the substrate was heated at 180°C for 2 minutes to form a photoluminescent resin layer on the substrate, which was then cooled to room temperature.

[0168] ((Coating liquid for bright 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 form a uniform solution. Other components (0.57 g of ultraviolet absorber (Tinuvin 900, manufactured by BASF Japan Ltd.) and 0.06 g of nucleating agent (A-3000, manufactured by Mitsubishi Chemical Corporation) and 13.16 g of fluorine-based resin (Kyanr 301, manufactured by Arkema Inc.) were then added and stirred to form a solution containing resin components. 1.13 g of (Photoluminescent Material 1) was added to the resulting solution containing resin components and further stirred to form a coating liquid for the photoluminescent resin layer. Table 1 shows the contents (mass%) of fluororesin, acrylic resin and other components relative to 100 mass% of resin components excluding pigments (total of fluororesin, acrylic resin and other components (excluding pigments)), the amount of pigment used (parts by mass) relative to 100 mass parts of resin components excluding pigments, and the amount of lustrous material used (parts by mass) relative to 100 mass parts of resin components excluding pigments.

[0169] (Deposition of adhesive layer) (Deposition of adhesive layer and base layer) A urethane adhesive containing a base material consisting of a mixture of polyester diol (TM-K51, manufactured by Toyo-Morton Co., Ltd.), polycarbonate diol (Duranol T5652, manufactured by Asahi Kasei Corporation), carbodiimide (Carbodilite V-07, manufactured by Nisshinbo Chemical Co., Ltd.), epoxy-containing silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), and ethyl acetate, and a curing agent consisting of an aliphatic isocyanate (CAT-RT85, manufactured by Toyo-Morton Co., Ltd.) was applied to the surface of the photoluminescent resin layer using a bar coater to a dry film thickness of approximately 10 μm, and the coating was dried at 60°C for 1 minute. The side of the base layer opposite the design layer (described below) was then laminated to the urethane adhesive side. This produced a multilayer laminate including a metallic decorative laminate.

[0170] ((Base layer)) A PET film (average thickness 25 μm, Teflex FT3, manufactured by Toyobo) was used as the base layer, and a 6 μm thick black design layer (light-shielding layer) was formed on one side by screen printing using a urethane-based paint containing (Pigment 1). Table 1 shows the amount of pigment used (parts by mass) per 100 parts by mass of the urethane-based paint.

[0171] (Manufacturing of decorative laminates) The urethane adhesive was applied to the surface of a protective layer (PC-11FU (layer thickness: 500 μm) manufactured by Wavelock Advanced Technology Co., Ltd.), and the applied layer was dried at 60°C for 1 minute. The decorative layer side of the multilayer laminate was then placed on the urethane adhesive side and laminated. The substrate was then peeled off to produce a decorative laminate including a metallic decorative laminate.

[0172] The resulting decorative laminate was evaluated for weather resistance, heat resistance, design, and contrast ratio, and the results are shown in Tables 3 and 4 together with those of other examples and comparative examples.

[0173] <Manufacturing of metallic articles> 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.

[0174] The obtained metallic articles were evaluated for design after molding and moldability, and the results are shown in Tables 3 and 4 together with other examples and comparative examples. Examples 2 to 4 A decorative laminate and a metallic article were produced in the same manner as in Example 1, except that the materials and the amounts used were changed as shown in Table 1. (Comparative Examples 1 to 3) A decorated laminate and a metallic article were produced in the same manner as in Example 1, except that the materials and the amounts used were changed as shown in Table 2.

[0175] [Table 1]

[0176] [Table 2]

[0177] [Table 3]

[0178] [Table 4]

[0179] In the table, "-" indicates that the substance is not contained, could not be measured, or was not measured.

[0180] From the results of Examples 1 to 4 shown in Table 3, it was found that the metallic decorative laminate of this embodiment exhibits excellent design and has excellent properties in weather resistance, heat resistance, contrast ratio, and millimeter wave transmittance. It was also found that it was excellent in the post-molding design evaluation and moldability evaluation.

[0181] In contrast, the results of Comparative Example 1 shown in Table 4 confirmed that the absence of a photoluminescent material resulted in a poor design because the metallic design was not achieved. The results of Comparative Example 2 revealed that having a design layer containing a dye, as in this embodiment, resulted in excellent design due to the light transmitted through the laminate. The results of Comparative Example 3 revealed that the inclusion of a fluorine-based resin in the photoluminescent resin layer, as in this embodiment, not only improved weather resistance, but also improved design, contrast ratio, and millimeter wave transmittance due to the photoluminescent resin being uniformly dispersed throughout the layer. [Industrial Applicability]

[0182] 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. [Explanation of symbols]

[0183] 1: Metallic decorative laminate 2: Multi-layer laminate 3: Decorative laminate 4: Observer 5: External light 6: Light reflected from metal layer 7: Light source 8: Irradiated light 9: Light transmitted through laminate 10: Base material (peeling layer) 11: Photoluminescent resin layer 12: Adhesive layer 13: Base layer 14: Design layer 15: Protective layer 20: Light-shielding region 21: Light-shielding region 22: Light-transmitting region of laminate 31: Surface of photoluminescent resin layer on the side opposite to the article 32: Surface of photoluminescent resin layer on the side facing the article 100: Thickness direction 110: Width direction 120: Longitudinal direction 200: Photoluminescent material 210: Thickness direction of photoluminescent material 211: Thickness of photoluminescent material 220: Particle diameter direction of photoluminescent material 221: Particle size of photoluminescent material 300: Radio wave-transmitting photoluminescent coating resin product of Patent Document 1 310: Photoluminescent coating film (1) 311: Photoluminescent coating film (2) 312: Photoluminescent coating film (3) 320: Photoluminescent material 321: Region with low content of photoluminescent material 322: Region with high content of photoluminescent material 330: Resin substrate

Claims

1. a photoluminescent resin layer containing one or more fluorine-based resins and one or more photoluminescent materials, and a base layer; A metallic decorative laminate comprising a design layer on at least one side of the base layer.

2. The metallic decorative laminate according to claim 1 , comprising the glittering film layer, the base layer, and the design layer in this order.

3. The metallic decorative laminate according to claim 1, wherein the glittering resin layer further contains one or more thermoplastic resins.

4. 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.

5. The metallic decorative laminate according to claim 1, wherein the amount of the glittering material in the glittering resin layer is 0.10 parts by mass or more and 20.00 parts by mass or less with respect to a total of 100 parts by mass of the resin components.

6. The metallic decorative laminate according to claim 1 , further comprising at least one of a protective layer and an adhesive layer.

7. The metallic decorative laminate according to claim 1 , further comprising a substrate layer on the opposite side of the glittering resin layer from the base layer.

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

9. Applying a coating liquid containing one or more fluorine-based resins and one or more luster materials to a substrate; Heating, and providing a base layer including a design layer in this order.

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