Decorative laminate including metallic layer and adhesive layer

Abstract

To provide a decorative laminate comprising a metallic layer and an adhesive layer, which is excellent in metallic luster and can reduce or prevent appearance failures.SOLUTION: A decorative laminate according to one embodiment of the present invention comprises an adhesive layer, and a metallic layer comprising metallic pigment particles in the state order. An outermost surface of the metallic layer, which is opposite the adhesive layer, has clarity of about 0.5 or more.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a decorative laminate including a metallic layer and an adhesive layer.

Background Art

[0002] In recent years, for example, decorative sheets exhibiting a metallic design feeling have been developed and are used in a wide range of fields such as interior or exterior products.

[0003] Patent Document 1 (Japanese Patent Application Laid-Open No. 2010-100051) discloses a decorative sheet formed by sequentially laminating at least a concealment layer, a metallic layer, and a surface protection layer on a substrate, wherein the content ratio of the glitter pigment contained in the metallic layer is in the range of 15 to 45 parts by mass with respect to 100 parts by mass of the resin solid content of the metallic layer, the surface protection layer is formed by crosslinking and curing an ionizing radiation curable resin composition, and the coating amount of the ionizing radiation curable resin composition is 3 to 8 g / m 2 is described.

[0004] Patent Document 2 (Japanese Patent Application Laid-Open No. 05-111991) describes a decorative sheet provided with an acrylate emulsion layer containing aluminum particles having a scaly shape and a smooth surface on a base layer.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The decorative sheets described in Patent Documents 1 and 2 form a metallic layer using metal pigment particles such as aluminum particles. Conventional metallic layers formed on such decorative sheets typically exhibit a glittery, shimmering appearance, and do not exhibit the metallic luster that metal itself can possess (for example, the luster of metal plating).

[0007] Regarding metallic luster, for example, by forming a metal vapor-deposited layer on a substrate, it is possible to produce the metallic luster that the metal itself can exhibit. However, compared to metallic layers formed using luminous pigments, metal vapor-deposited layers are more prone to cracking and a decrease in metallic luster when stretched or bent, which could lead to defects in appearance.

[0008] For example, in the field of decorative films, a technique is known for bonding decorative films to a substrate via an adhesive layer. However, it has been difficult to apply a metallic layer containing metal pigment particles to such an adhesive layer to produce the metallic luster that the metal itself can exhibit.

[0009] This disclosure provides a decorative laminate comprising a metallic layer and an adhesive layer that exhibits excellent metallic luster and can reduce or prevent appearance defects. [Means for solving the problem]

[0010] According to one embodiment of the present disclosure, a decorative laminate is provided which sequentially comprises an adhesive layer and a metallic layer containing metal pigment particles, wherein the clarity of the outermost surface of the metallic layer, located opposite the adhesive layer side, is about 0.5 or higher.

[0011] Another embodiment of the present disclosure provides a method for manufacturing a decorative laminate, comprising applying a metallic coating composition containing metal pigment particles to a substantially smooth support to form a metallic layer, and then applying an adhesive layer to the metallic layer.

[0012] According to another embodiment of the present disclosure, an article is provided in which the above-described decorative laminate is adhered to a support member.

[0013] According to another embodiment of the present disclosure, a method for manufacturing an article having a three-dimensional shape is provided, which includes applying the above-described decorative laminate to a support member having a three-dimensional shape.

[0014] According to another embodiment of the present disclosure, a metallic coating composition containing metal pigment particles, a binder precursor, and a silane coupling agent, wherein the content of the metal pigment particles is about 20.0% by mass or more and about 40.0% by mass or less, the content of the binder precursor is about 0.1% by mass or more and about 10.0% by mass or less, and the content of the silane coupling agent is about 50.0% by mass or more and about 79.9% by mass or less in terms of solid content, is provided.

Advantages of the Invention

[0015] According to the present disclosure, it is possible to provide a decorative laminate including a metallic layer and an adhesive layer, which has excellent metallic luster and can reduce or prevent appearance defects.

[0016] The above description should not be regarded as disclosing all embodiments of the present invention and all advantages related to the present invention.

Brief Description of the Drawings

[0017] [Figure 1] FIG. 1 is a diagram simulating a cross-section of a decorative laminate according to an embodiment of the present disclosure. [Figure 2] FIG. 2 is a diagram related to a method for manufacturing a decorative laminate according to an embodiment of the present disclosure. [Figure 3] FIG. 3 is a diagram related to a method for manufacturing a decorative laminate according to another embodiment of the present disclosure. [Figure 4] FIG. 4 is an external appearance photograph of an article provided with a decorative laminate according to an embodiment of the present disclosure.

Modes for Carrying Out the Invention

[0018] Hereinafter, for the purpose of exemplifying representative embodiments of the present invention, a more detailed description will be given with reference to the drawings as necessary, but the present invention is not limited to these embodiments. Regarding the reference numbers in the drawings, elements with similar numbers in different drawings indicate similar or corresponding elements.

[0019] In the present disclosure, for example, in the "decorative laminate including an adhesive layer and a metallic layer containing metal pigment particles in this order", the "in this order" means that when focusing on the two components of the adhesive layer and the metallic layer, the decorative laminate contains these components in this order, and other layers such as a printing layer may be interposed between these components.

[0020] In the present disclosure, for example, in the "the metallic layer is disposed on the adhesive layer", the "on" means that the metallic layer is directly disposed on the upper side of the adhesive layer, or the metallic layer is indirectly disposed on the upper side of the substrate through another layer.

[0021] In the present disclosure, for example, in the "the bonding layer is disposed under the metallic layer", the "under" means that the bonding layer is directly disposed on the lower side of the metallic layer, or the bonding layer is indirectly disposed on the lower side of the metallic layer through another layer.

[0022] In the present disclosure, the "metal pigment particles" are intended to be particles that can impart a metallic design property to the metallic layer. Here, the "metallic design property" does not refer to a glittery design property like lame or a design property such as flip-flop property where the hue changes depending on the viewing angle, but is intended to be a design property such as the metallic luster that the metal itself can exhibit (for example, the specular luster like metal plating).

[0023] In the present disclosure, the "metallic layer" is intended to be a layer that can exhibit a metallic design property (for example, the specular luster like metal plating).

[0024] In this disclosure, "omitted" means that variations caused by manufacturing tolerances, etc., are included, and it is intended that variations of approximately ±20% are acceptable.

[0025] In this disclosure, "transparent" means that the average transmittance in the visible light region (wavelength 400 nm to 700 nm), measured in accordance with JIS K 7375, is approximately 80% or higher, preferably approximately 85% or higher, or approximately 90% or higher. There are no particular restrictions on the upper limit of the average transmittance, but for example, it may be less than approximately 100%, approximately 99% or lower, or approximately 98% or lower.

[0026] In this disclosure, "translucent" means that the average transmittance in the visible light region (wavelength 400nm to 700nm), measured in accordance with JIS K 7375, is less than approximately 80%, preferably less than approximately 75%, and is intended not to completely conceal the substrate.

[0027] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate.

[0028] In this disclosure, the term "film" also includes a component called a "sheet."

[0029] The decorative laminates of this disclosure will be described below, with reference to the drawings as necessary.

[0030] The decorative laminate 100 in Figure 1 includes a release liner 101, an adhesive layer 103, and a metallic layer 105. Here, the release liner is an optional component, and the decorative laminate of this disclosure may or may not include a release liner.

[0031] Hereinafter, for the purpose of illustrating typical embodiments of this disclosure, details of each component will be described, with some reference numerals omitted.

[0032] The decorative laminate (sometimes simply referred to as "laminated") of the present disclosure comprises, in order, an adhesive layer and a metallic layer containing metal pigment particles, wherein the clarity of the outermost surface of the metallic layer, located opposite the adhesive layer side, is approximately 0.5 or higher. Here, "the outermost surface of the metallic layer, located opposite the adhesive layer side," refers, for example, to the surface of the metallic layer 105 when the decorative laminate 100 is viewed from above (in the direction where reference numeral 100 is located) in Figure 1.

[0033] When applying a metallic layer to an adhesive layer, it is common practice to apply an adhesive to a release liner to form an adhesive layer, and then apply the metallic coating composition to this adhesive layer. However, when the metallic coating composition is applied to the adhesive layer in this manner, streaky defects occur in the metallic layer, or the haze of the metallic layer increases, resulting in a metallic layer that does not exhibit a good metallic luster. Although the principle is not clear, it is thought that this is because the adhesive layer is more flexible than the substrate used in release liners, etc. (e.g., PET substrate), and is therefore more susceptible to the influence of the Meyer bar used during the application of the coating composition. As a result, streaks occur, or the adhesive layer swells due to the solvent in the coating composition, or adhesive components migrate to the metallic layer, resulting in an increase in the haze of the metallic layer.

[0034] As described later, the inventors have found that when a metallic coating composition containing metal pigment particles is applied to a support with a substantially smooth surface to form a metallic layer, and then an adhesive layer is applied to this metallic layer, a metallic layer exhibiting good metallic luster (a mirror-like gloss similar to metal plating) is obtained, as shown in the photograph in Figure 4.

[0035] Furthermore, since the metallic layer of this disclosure is formed using metal pigment particles, it can reduce or prevent appearance defects associated with cracks compared to a metal vapor-deposited layer formed by vapor deposition.

[0036] The metallic luster of the metallic layer can be evaluated, for example, by a clarity test described later. Since this clarity is a parameter that reflects the metallic luster of the metallic layer, the metallic luster of the metallic layer can be evaluated by measuring the clarity at the outermost surface of the decorative laminate, not only when the metallic layer 105 is located on the outermost surface of the decorative laminate 100, as shown in Figure 1, but also when a transparent surface layer is applied on the metallic layer 105. The decorative laminate of this disclosure can achieve a clarity of about 0.5 or higher, about 0.6 or higher, or about 0.7 or higher. There is no particular upper limit to such clarity, and it can be, for example, about 2.0 or lower, about 1.8 or lower, or about 1.5 or lower.

[0037] The metallic layer of this disclosure comprises at least metallic pigment particles. The metallic layer may be a single layer or a multi-layer structure. The metallic layer may be formed over the entire surface of the decorative laminate or partially thereon.

[0038] There are no particular restrictions on the shape of the metal pigment particles; for example, they can be flaky, flattened, or plate-shaped. Among these, the flaky shape is preferred from the viewpoint of obtaining good metallic luster.

[0039] The size of the metallic pigment particles is not particularly limited as long as it can produce a metallic design in the metallic layer. The particle size of the metallic pigment particles can be evaluated, for example, by D50. From the viewpoint of obtaining good metallic luster, D50 is preferably about 1 micrometer or more, about 2 micrometers or more, about 3 micrometers or more, about 4 micrometers or more, or about 5 micrometers or more, and preferably about 20 micrometers or less, about 17 micrometers or less, about 15 micrometers or less, about 12 micrometers or less, or about 10 micrometers or less. The particle size (D50) of the metallic pigment particles can be measured using the Microtrac MT3300EX II series laser diffraction scattering particle size distribution analyzer manufactured by Microtrac-Bell, under measurement conditions compliant with JIS Z 8825:2013.

[0040] There are no particular restrictions on the material of the metal pigment particles, and examples include metals such as aluminum, chromium, nickel, tin, titanium, indium, copper, gold, silver, and brass, as well as alloys or compounds containing such metals. In particular, from the viewpoint of metallic luster, it is preferable that the metal pigment particles contain aluminum. The metal pigment particles incorporated into the metallic layer and metallic coating composition can be used individually or in combination of two or more types.

[0041] The metallic layer may consist solely of metal pigment particles, but may also contain optional components such as binders, as described later. When optional components (particularly binders and silane coupling agents) are included, the content of metal pigment particles can be, for example, approximately 20.0% by mass or more, approximately 22.0% by mass or more, approximately 25.0% by mass or more, approximately 27.0% by mass or more, or approximately 30.0% by mass or more, based on the total weight of the metallic layer, and approximately 40.0% by mass or less, approximately 38.0% by mass or less, or approximately 35.0% by mass or less. When the content of metal pigment particles is within this range, a metallic layer with excellent properties such as metallic luster can be obtained.

[0042] In some embodiments, the metallic layer of this disclosure includes a binder. The binder is not particularly limited and examples include resins having urethane bonds, phenoxy resins, (meth)acrylic resins, epoxy resins, phenolic resins, polyvinyl alcohol, and vinyl acetate resins. The binders can be used alone or in combination of two or more. In this disclosure, "resins having urethane bonds" can include not only urethane resins but also resins prepared using at least one selected from, for example, urethane (meth)acrylate and urethane (meth)acrylate oligomers, and urethane resins can also include (meth)acrylic urethane resins. Among these, resins having urethane bonds and phenoxy resins are preferred from the viewpoint of metallic luster and adhesion between metallic pigment particles.

[0043] The binder content can be, for example, based on the total weight of the metallic layer, approximately 0.1% by mass or more, approximately 0.3% by mass or more, approximately 0.6% by mass or more, approximately 0.8% by mass or more, approximately 1.0% by mass or more, approximately 1.5% by mass or more, approximately 2.0% by mass or more, approximately 2.5% by mass or more, or approximately 3.0% by mass or more, and approximately 10.0% by mass or less, approximately 9.0% by mass or less, approximately 8.0% by mass or less, approximately 7.0% by mass or less, approximately 6.0% by mass or less, or approximately 5.5% by mass or less. The binder can, for example, improve the adhesion between metal pigment particles, but in some cases it may increase the haze of the metallic layer. When the binder content is within this range, a metallic layer with excellent performance such as metallic luster can be obtained.

[0044] In some embodiments, the metallic layer of the present disclosure includes a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having an alkoxysilane at its terminus, but it is preferably one that simultaneously has at least one selected from the group consisting of vinyl groups, epoxy groups, (meth)acrylic groups, amine groups, mercapto groups, and isocyanate groups, more preferably one that has at least one selected from the group consisting of epoxy groups, amine groups, and isocyanate groups, and particularly preferably one that has at least one selected from the group consisting of epoxy groups and amine groups. The silane coupling agents can be used alone or in combination of two or more.

[0045] Examples of silane coupling agents having a vinyl group include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(β-methoxyethoxy)silane.

[0046] Examples of silane coupling agents having an epoxy group include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropyltriethoxysilane.

[0047] Examples of silane coupling agents having a (meth)acrylic group include γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, and γ-(meth)acryloxypropyltriethoxysilane. Here, "(meth)acryloxy" means acryloxy or metacloxy.

[0048] Examples of silane coupling agents having an amine group include N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane.

[0049] Examples of silane coupling agents having a mercapto group include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

[0050] Examples of silane coupling agents having an isocyanate group include γ-isocyanate-propyltrimethoxysilane and γ-isocyanate-propyltriethoxysilane.

[0051] The silane coupling agent content can be, for example, approximately 50.0% by mass or more, approximately 55.0% by mass or more, approximately 60.0% by mass or more, approximately 63.0% by mass or more, or approximately 65.0% by mass or more, based on the total weight of the metallic layer, and can be approximately 79.9% by mass or less, approximately 79.7% by mass or less, approximately 79.4% by mass or less, approximately 79.2% by mass or less, approximately 79.0% by mass or less, approximately 78.5% by mass or less, approximately 78.0% by mass or less, approximately 77.5% by mass or less, or approximately 77.0% by mass or less. The silane coupling agent can, for example, improve the adhesion between metal pigment particles. When the silane coupling agent content is within this range, a metallic layer with excellent properties such as metallic luster can be obtained. When the silane coupling agent is used in combination with the binder described above, the binder and the silane coupling agent can bond together, and at the same time, the metal pigment particles and the silane coupling agent can also bond together, thereby further improving the adhesion between metal pigment particles. As a result, even when decorative laminates are subjected to molding methods involving heating and / or pressure, such as vacuum forming or vacuum pressure forming, the reduction or suppression of the metallic luster of the metallic layer can be reduced. When using a silane coupling agent and a binder together, the respective contents can be those described above.

[0052] The metallic layer of this disclosure may optionally contain additives such as fillers other than metal pigment particles, ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, plasticizers, flow enhancers, leveling agents, pigments other than metal pigment particles, dyes, and fragrances. These optional components can be used individually or in combination of two or more. The individual and total amounts of these optional components can be determined within a range that does not impair the properties required for the metallic layer.

[0053] The metallic coating compositions of this disclosure for forming a metallic layer may contain various materials that can be used in the metallic layer described above, and may contain at least metal pigment particles. In particular, a metallic coating composition is preferred in which, in addition to metal pigment particles, it contains a binder precursor and a silane coupling agent, and in terms of solid content, the content of metal pigment particles is about 20.0% by mass or more and about 40.0% by mass or less, the content of binder precursor is about 0.1% by mass or more and about 10.0% by mass or less, and the content of silane coupling agent is about 50.0% by mass or more and about 79.9% by mass or less. The metallic layer formed by such a composition has excellent metallic luster as well as adhesion between metal pigment particles, so even when applied to a molding method that involves heating and / or pressure (e.g., vacuum forming, vacuum pressure forming), the decrease in the metallic luster of the metallic layer can be reduced or suppressed.

[0054] Here, "binder precursor" refers to the component that ultimately becomes the binder in the metallic layer, and examples include curable or crosslinkable monomers and / or curable or crosslinkable oligomers, resins that have been pre-cured or crosslinked, and non-curable or non-crosslinkable resins such as thermoplastic resins. Therefore, metallic coating compositions may contain additives such as crosslinking agents and curing agents as optional components. A metallic coating composition containing a crosslinking agent may be called a crosslinkable composition, and a metallic coating composition containing a curing agent may be called a curable composition.

[0055] The respective contents of metal pigment particles, binder precursors, and silane coupling agents in a metallic coating composition can be determined similarly to the contents of each component in the metallic layer described above. Here, "based on the total weight of the metallic layer" and "binder" can be read as "on a solid content basis" and "binder precursor," respectively.

[0056] The various additive components described above can be appropriately blended as long as they do not adversely affect the metallic layer obtained by the metallic coating composition. The metallic coating composition may optionally contain organic solvents such as toluene or aqueous dispersion media to improve workability and coating properties. As aqueous dispersion media, for example, water such as distilled water, purified water, deionized water, and tap water can be used. Water-soluble alcohols such as ethanol may also be used in combination with such water, as long as it does not affect the effects of the present invention.

[0057] The metallic layer of the decorative laminate disclosed herein is formed by applying the metallic coating composition to a substantially smooth surface support (sometimes simply referred to as the "support"), rather than by applying it to an adhesive layer. Here, "substance with a substantially smooth surface" does not include a support having an adhesive layer to which the metallic coating composition can be applied.

[0058] The metallic coating composition contains metal pigment particles (e.g., flake-shaped metal pigment particles), and as a result of these particles being oriented substantially uniformly in a direction substantially parallel to the support, the resulting metallic layer can obtain a good metallic luster. According to the method for manufacturing decorative laminates of this disclosure, the metal pigment particles are more likely to be oriented substantially uniformly when the thickness of the metallic layer is thin. Therefore, from the viewpoint of obtaining a good metallic luster, the thickness of the metallic layer is preferably, for example, about 0.07 micrometers or more, about 0.10 micrometers or more, about 0.15 micrometers or more, about 0.20 micrometers or more, about 0.25 micrometers or more, about 0.30 micrometers or more, about 0.35 micrometers or more, about 0.40 micrometers or more, about 0.45 micrometers or more, or about 0.50 micrometers or more, and preferably about 1.1 micrometers or less, about 1.0 micrometer or less, about 0.90 micrometers or less, about 0.85 micrometers or less, or about 0.80 micrometers or less. Here, the thickness of the metallic layer in this disclosure was measured in accordance with JIS K 5600-1-7 Section 7: Film Thickness, 5. Measurement of Dry Film Thickness, 5.2.1 b) Coating Method (Non-destructive Test Method). Specifically, the thickness of the substrate before application of the metallic layer was measured first, and then the overall thickness in the same measurement range was measured after applying and drying the metallic layer, and the difference was taken as the thickness of the metallic layer. This thickness is the average value of measurements taken at three arbitrary locations using a micrometer (model number: VL-50S) manufactured by Mitutoyo Corporation.

[0059] The decorative laminates of this disclosure include an adhesive layer. The adhesive layer is typically applied to an adherend, such as a support member of an article described later.

[0060] The adhesive layer may be applied directly to the metallic layer, or indirectly via another layer (e.g., a bonding layer).

[0061] There are no particular restrictions on the material of the adhesive layer; for example, commonly used solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing adhesives such as (meth)acrylic, polyolefin-based, polyurethane-based, polyester-based, and rubber-based adhesives can be used.

[0062] Among such materials, pressure-sensitive adhesives and heat-sensitive adhesives are preferred from the viewpoint of ease of bonding to the adherend, and heat-sensitive adhesives are more preferred from the viewpoint of being able to utilize heat such as an infrared heater during vacuum forming or vacuum pressure forming. In this disclosure, "pressure-sensitive adhesive" refers to an adhesive that is permanently tacky at room temperature (e.g., about 20°C), adheres to various surfaces with light pressure, and does not undergo a phase change (from liquid to solid). "Heat-sensitive adhesive" refers to an adhesive that can exhibit adhesion (tackiness) upon heating. The heat-sensitive adhesive layer in this disclosure does not exhibit adhesion at room temperature (e.g., about 20°C), but can exhibit adhesion during molding at temperatures of about 100°C or higher, about 120°C or higher, or about 140°C or higher. Pressure-sensitive adhesives and heat-sensitive adhesives may also be crosslinked by thermal crosslinking with a crosslinking agent or by radiation (e.g., electron beam or ultraviolet light).

[0063] There are no particular restrictions on the material of the pressure-sensitive adhesive; for example, (meth)acrylic polymers, natural rubber, synthetic rubber, polyester polymers, polyether polymers, polyurethane polymers, silicone polymers, or other polymers can be used. Among these, pressure-sensitive adhesives made of (meth)acrylic polymers are preferred because they have excellent transparency, weather resistance, and adhesion.

[0064] There are no particular restrictions on the materials used for the heat-sensitive adhesive. For example, a material can be provided that includes the following components: (A) a carboxyl group-containing (meth)acrylic polymer having a glass transition temperature (Tg) of approximately 25°C or lower, in which the ratio of repeating units containing carboxyl groups to the total number of repeating units of the polymer is approximately 4.0 to approximately 25%, and (B) an amino group-containing (meth)acrylic polymer having a glass transition temperature (Tg) of approximately 75°C or higher, in which the ratio of repeating units containing amino groups to the total number of repeating units of the polymer is approximately 3.5 to approximately 15%, and the mixing ratio of component (A) to component (B) is approximately 62:approximately 38 to approximately 75:approximately 25 by mass ratio. Here, the (meth)acrylic polymer may be a copolymer arbitrarily combined with other non-(meth)acrylate monomers other than (meth)acrylic monomers, such as vinyl unsaturated monomers.

[0065] The monoethylenically unsaturated monomers that make up (meth)acrylic polymers are generally of the formula CH2=CR 1 COOR 2 (In the formula, R 1 R is a hydrogen or methyl group, 2The main component is a linear, branched, or cyclic alkyl group, phenyl group, alkoxyalkyl group, or phenoxyalkyl group. Other components may include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene, and vinyl esters such as vinyl acetate. Examples of such monomers include alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate, isoamyl(meth)acrylate, n-hexyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isooctyl(meth)acrylate, isononyl(meth)acrylate, isobornyl(meth)acrylate, dicyclopentanyl(meth)acrylate, decyl(meth)acrylate, and dodecyl(meth)acrylate; phenoxyalkyl(meth)acrylates such as phenoxyethyl(meth)acrylate; and alkoxyalkyl(meth)acrylates such as methoxypropyl(meth)acrylate and 2-methoxybutyl(meth)acrylate. For example, to obtain a desired glass transition temperature, adhesion, and hot adhesion / hot holding power, one or more of these monomers can be used as appropriate, depending on the purpose. The monoethylene unsaturated monomer is preferably an alkyl (meth)acrylate, where the number of carbon atoms in the alkyl group is preferably 1 to 12.

[0066] Component (A) is a (meth)acrylic polymer having a glass transition temperature (Tg) of approximately 25°C or lower, and is a soft component. While this soft component (A) itself is tacky at room temperature, the composition mixed with component (B) in the above amounts exhibits almost no tackiness at room temperature. However, the adhesive made by mixing component (A) and component (B) in the above amounts can exhibit good adhesion when heated and pressed onto the adherend.

[0067] (Meth)acrylic polymers with a glass transition temperature (Tg) of approximately 25°C or lower can be easily provided by using monomers as the main component, such that the glass transition temperature (Tg) of the homopolymer is approximately 25°C or lower. Examples of such monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isoamyl acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and dodecyl (meth)acrylate. Considering the adhesion at room temperature and the cohesive force at high temperatures, the Tg of the (meth)acrylic polymer is preferably approximately 0°C to approximately -50°C.

[0068] Here, the glass transition temperature (°C) of the polymer in this disclosure is the value obtained by measuring it as follows: <Measurement of Tg (glass transition temperature) (below 30°C)> Using an ARES system manufactured by Rheometric Scientific, the peak temperature of the loss tangent (tanδ) (loss modulus G'' / storage modulus G') was measured under Mode: Shear, Frequency: 1.0 Hz, and Temperature: -60°C to 30°C (5.0°C / min). <Measurement of Tg (glass transition temperature) (above 30°C)> Using an RSA-III measuring device from Rheometric Scientific, the peak temperature of the loss tangent (tanδ) (loss modulus E'' / storage modulus E') was measured in Mode: Tension, Frequency: 10.0 Hz, and Temperature: 30°C to 150°C (5.0°C / min).

[0069] Component (A) is a (meth)acrylic polymer containing carboxyl groups. The presence of carboxyl groups in component (A) and amino groups in component (B) improves the compatibility between component (A) and component (B), preventing phase separation between component (A) and component (B) in the adhesive composition and enabling the composition to exhibit good performance (e.g., heat adhesion, hot adhesion, hot holding power). From the viewpoint of achieving good compatibility, it is preferable that the carboxyl groups contained in the (meth)acrylic polymer of component (A) are present in an amount such that the ratio of repeating units containing carboxyl groups to the total number of repeating units of the polymer is approximately 4.0 to approximately 25% (also expressed as carboxyl group amount mol%).

[0070] By copolymerizing an unsaturated monomer containing a carboxyl group with the above-mentioned monoethylenically unsaturated monomer, a carboxyl group can be incorporated into the (meth)acrylic polymer. Examples of such monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, ω-carboxypolycaprolactone mono(meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, β-carboxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, and 2-(meth)acryloyloxyethyl hexahydrophthalic acid. When considering resistance to yellowing, (meth)acrylic acid, ω-carboxypolycaprolactone mono(meth)acrylate, and β-carboxyethyl (meth)acrylate are preferred as the carboxyl group-containing unsaturated monomer.

[0071] The molecular weight of the carboxyl group-containing (meth)acrylic polymer of component (A) is not particularly limited, but generally, a weight-average molecular weight of about 100,000 to about 1,000,000 is preferred, and about 200,000 to about 800,000 is more preferred. A smaller weight-average molecular weight tends to reduce cohesiveness, and a larger weight-average molecular weight tends to reduce compatibility, but the polymer is not particularly limited as long as it satisfies the conditions of component (A). Herein, "weight-average molecular weight" in this disclosure refers to the weight-average molecular weight in terms of polystyrene as measured by gel permeation chromatography.

[0072] Component (B) is a (meth)acrylic polymer having a glass transition temperature (Tg) of approximately 75°C or higher, and is a hard component. If this hard component (B) is not present or present in small amounts, the adhesive will only be a tack at room temperature if component (A) is present. By including component (B), which has a glass transition temperature (Tg) of approximately 75°C or higher, the adhesive develops tackiness during heat bonding. As a result, for example, even if a decorative laminate stretched and attached to a three-dimensional substrate is exposed to high temperatures and expands and contracts due to residual stress, the adhesive layer can withstand the expansion and contraction force, thus preventing slippage or peeling from the edges of the decorative laminate. The glass transition temperature (Tg) of component (B) is preferably approximately 75°C or higher. As an upper limit for the Tg of component (B), for example, from the viewpoint of the balance between high-temperature adhesive strength and room-temperature adhesive strength, and the applicable temperature during heat bonding, it is preferable to have a Tg of approximately 250°C or lower. The Tg of component (B) is more preferably in the range of approximately 80 to approximately 120°C.

[0073] (Meth)acrylic polymers with a glass transition temperature (Tg) of approximately 75°C or higher can be easily provided by using monomers whose homopolymer Tg is approximately 75°C or higher as the main component. Examples of such monomers include methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0074] Component (B) is a (meth)acrylic polymer containing amino groups. The presence of carboxyl groups in component (A) and amino groups in component (B) improves the compatibility between components (A) and (B). This prevents phase separation between components (A) and (B) in the adhesive composition, resulting in good performance (e.g., heat adhesion, hot adhesion, hot holding power). From the viewpoint of achieving good compatibility, it is preferable that the amino groups contained in the (meth)acrylic polymer of component (B) are present in an amount such that the ratio of repeating units containing amino groups to the total number of repeating units of the polymer is approximately 3.5 to approximately 15% (also expressed as amino group amount mol%).

[0075] Examples of unsaturated monomers containing amino groups that copolymerize with the above-mentioned monoethylene unsaturated monomers to form amino group-containing (meth)acrylic polymers include dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl acrylate (DMAEA) and N,N-dimethylaminoethyl methacrylate (DM), dialkylaminoalkyl (meth)acrylamides such as N,N-dimethylaminopropyl acrylamide (DMAPAA) and N,N-dimethylaminopropyl methacrylamide, and monomers having tertiary amino groups, such as vinyl monomers having nitrogen-containing heterocycles, including vinylimidazole.

[0076] The molecular weight of the amino group-containing (meth)acrylic polymer of component (B) is not particularly limited, but generally, from the viewpoint of hot adhesion, hot holding power, compatibility, etc., a weight-average molecular weight of about 10,000 to about 200,000 is preferred, and about 40,000 to about 150,000 is more preferred.

[0077] From the viewpoint of room temperature adhesion, heat adhesion, hot adhesion, and hot holding power, it is preferable that components (A) and (B) are included in amounts such that the mixing ratio of components (A) and (B) is approximately 62:38 to approximately 75:25 by mass, and more preferably approximately 65:35 to approximately 70:30.

[0078] (Meth)acrylic polymers can be produced by radical polymerization, and known methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization can be used as manufacturing methods.

[0079] For polymerization initiators, organic peroxides such as benzoyl peroxide, lauroyl peroxide, and bis(4-tert-butylcyclohexyl) peroxydicarbonate; and azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis(2-methylpropionic acid)dimethyl, and azobis-2,4-dimethylvaleronitrile (AVN) can be used. The amount of initiator used can be about 0.05 to about 5 parts by mass per 100 parts by mass of the monomer mixture.

[0080] The adhesives of this disclosure and the adhesive layers obtained from these adhesives may contain, as optional components, fillers such as tackifying resins, crosslinking agents, conductive fillers, and thermally conductive fillers, silane coupling agents, plasticizers, thickeners, pigments, dyes, flame retardants, antioxidants, ultraviolet absorbers, stabilizers, and the like. These optional components may be used individually or in combination of two or more.

[0081] In one embodiment, the adhesive includes a tackifying resin for the purpose of adjusting its tackiness. Examples of tackifying resins that can be incorporated include rosin-based tackifying resins, terpene-based tackifying resins, petroleum-based tackifying resins, coal-based tackifying resins, and other known tackifying resins. The tackifying resin can be used alone or in combination with other tackifying resins. The tackifying resin can be used in an amount of about 0.5 parts by mass or more, or about 1 part by mass or more, or about 100 parts by mass or less, or about 50 parts by mass or less, per 100 parts by mass of rubber and / or polymer.

[0082] In one embodiment, the adhesive contains a polyfunctional compound as a crosslinking agent. Generally, polyfunctional compounds have at least two, preferably two to four, functional groups in a single molecule. Examples of such polyfunctional compounds include isocyanate compounds, epoxy compounds, amine compounds, metal chelate compounds, and aziridine compounds. When a polymer, such as a (meth)acrylic polymer, contains carboxyl groups, using an epoxy compound among these crosslinking agents can particularly improve heat resistance.

[0083] The crosslinking agent is used in an amount ranging from approximately 0.05 parts by mass to approximately 10 parts by mass per 100 parts by mass of polymer. By using the crosslinking agent in this amount, suitable three-dimensional crosslinks are formed in the polymer (e.g., (meth)acrylic polymer), and excellent heat resistance can be achieved. The above crosslinking agents can be used alone or in combination.

[0084] In one embodiment, the adhesive layer contains a white pigment. The white pigment can be used alone or in a mixture of two or more. Titanium dioxide is advantageous as the white pigment due to its high whiteness. Talc, kaolin, aluminum paste, carbon black, or calcium carbonate may be used as additives in combination with the white pigment. The white pigment may be particles of various shapes, such as spherical, needle-shaped, plate-shaped, or flake-shaped, and spherical particles are preferable due to their good dispersibility. The white pigment may be surface-treated with a coupling agent such as silane or titanate to further improve dispersibility. The amount of white pigment can be about 1 part by mass or more, about 3 parts by mass or more, about 5 parts by mass or more, or about 8 parts by mass or more, about 60 parts by mass or less, about 50 parts by mass or less, about 40 parts by mass or less, about 30 parts by mass or less, about 20 parts by mass or less, or about 10 parts by mass or less per 100 parts by mass of the rubber and / or polymer constituting the adhesive.

[0085] There are no particular limitations on the thickness of the adhesive layer of this disclosure; for example, it can be about 5 micrometers or more, about 10 micrometers or more, or about 20 micrometers or more, and it can be about 100 micrometers or less, about 80 micrometers or less, or about 50 micrometers or less.

[0086] In some embodiments, the decorative laminates of the present disclosure optionally include additional layers. Such additional layers may include, for example, at least one selected from the group consisting of surface layers, decorative layers (e.g., color layers, pattern layers, relief layers), bonding layers, and release liners. The additional layers may be applied, for example, on the metallic layer, between the metallic layer and the adhesive layer, or on the adhesive layer surface opposite to the surface on which the metallic layer is located. The additional layers may be applied to the entire surface or to a portion of the laminate, to the extent that they do not completely conceal the metallic luster of the metallic layer. The additional layers may have a three-dimensional shape, such as an embossed pattern, on their surface.

[0087] There are no particular restrictions on the material of the surface layer. For example, (meth)acrylic resins containing polymethyl methacrylate (PMMA) and (meth)acrylic copolymers, resins having urethane bonds (e.g., polyurethane), fluororesins such as ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), and methyl methacrylate-vinylidene fluoride copolymer (PMMA / PVDF), silicone resins, polyolefins such as polyvinyl chloride (PVC), polycarbonate (PC), polyethylene (PE), and polypropylene (PP), polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamides such as nylon, ethylene / acrylic acid copolymer (EAA) and its ionomers, copolymers such as ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer (EVOH) can be used individually or in blends of two or more. The surface layer may have a multilayer structure. For example, the surface layer may be a laminate of films formed from the above resins, or a multilayer coating of the above resins. The surface layer may have a three-dimensional uneven shape, such as an embossed pattern, on all or part of its surface.

[0088] The surface layer can be formed by coating the metallic layer with a resin composition directly or via a bonding layer. The coating of the surface layer can be performed before or after applying the decorative laminate to the adherend (e.g., the support member described later). Alternatively, a surface layer film can be formed by coating a release liner with a resin composition, and this film can be laminated to the metallic layer via a bonding layer. For example, if the metallic layer is adhesive to the surface layer film, the surface layer film can be laminated directly to the metallic layer without a bonding layer. The surface layer film can be formed by coating a release liner with a resin material such as a curable (meth)acrylic resin composition or a reactive polyurethane composition using a knife coat, bar coat, blade coat, doctor coat, roll coat, cast coat, etc., and curing it with light or heat as needed.

[0089] As the surface layer, a film pre-formed by extrusion, stretching, etc., may be used. Such a film can be laminated to the metallic layer via a bonding layer. Alternatively, if the metallic layer is adhesive to such a film, the film can be directly laminated to the metallic layer without a bonding layer. By using a film with high flatness as such, an appearance with higher surface flatness can be given to the article (structure). The surface layer can also be formed by multilayer extrusion with other layers. As other layers, for example, a (meth)acrylic film can be used. As a (meth)acrylic film, for example, a resin containing polymethyl methacrylate (PMMA), butyl polyacrylate, (meth)acrylic copolymer, ethylene / acrylic copolymer, ethylene vinyl acetate / acrylic copolymer, etc., can be used in film form. (Meth)acrylic films have excellent transparency and / or scratch resistance, are resistant to heat and / or light, and are less prone to fading and / or gloss changes. In addition, they have excellent moldability even without the use of plasticizers, and because plasticizers do not need to be used, they also have excellent stain resistance. Among these, those with PMMA as the main component are preferred. For example, if a (meth)acrylic resin with excellent scratch resistance is used as another layer, and a fluororesin such as ETFE, PVDF, or PMMA / PVDF with excellent chemical resistance is used as the surface layer, the resulting surface layer can combine the properties of both layers.

[0090] The surface layer of this disclosure may contain optional components such as fillers, antioxidants, UV absorbers, light stabilizers, heat stabilizers, hard coat materials, gloss enhancers, dispersants, plasticizers, flow enhancers, surfactants, leveling agents, silane coupling agents, catalysts, pigments, and dyes, to the extent that they do not impair the performance (e.g., protective performance, metallic luster) according to the application. In particular, by using UV absorbers such as benzotriazole and Tinuvin® 400 (manufactured by BASF), and hindered amine light stabilizers (HALS) such as Tinuvin® 292 (manufactured by BASF), discoloration, fading, and deterioration of the underlying metallic layer can be effectively prevented. The hard coat material may be included in the surface layer, or it may be applied as a hard coat layer by being separately coated on the surface layer.

[0091] The surface layer may be partially translucent or opaque, but it is preferable that it be transparent from the viewpoint of visibility of metallic luster, etc. From the viewpoint of transparency of the surface layer and protective performance such as chemical resistance, it is preferable that pigments, fillers, or the above-mentioned light-diffusing particles, etc., that are of a size that contributes to light scattering are not included in the surface layer.

[0092] The thickness of the surface layer can vary, but for example, it may be about 1 micrometer or more, about 5 micrometers or more, or about 10 micrometers or more, or it may be about 200 micrometers or less, about 100 micrometers or less, or about 80 micrometers or less. When applying a decorative laminate to a support member with a complex shape, a thinner surface layer is advantageous from the viewpoint of shape conformability, and for example, it is preferable to have a surface layer of about 100 micrometers or less, or about 80 micrometers or less. On the other hand, when imparting high chemical resistance, weather resistance, scratch resistance, etc., to an article, a thicker surface layer is advantageous, and for example, it is preferable to have a surface layer of about 5 micrometers or more, or about 10 micrometers or more.

[0093] The decorative layer as an additional layer is intended to be a layer that can provide decoration other than that of the metallic layer. Such decorative layers include, but are not limited to, the following, color layers exhibiting paint colors, such as light colors like white and yellow, or dark colors like red, brown, green, blue, gray, and black; pattern layers that impart patterns such as wood grain, stone patterns, geometric patterns, and leather patterns to an item, logos, and illustrations; relief layers with raised or recessed shapes on the surface; and combinations thereof.

[0094] The decorative layer can be applied directly or via a bonding layer to all or part of the layers constituting the decorative laminate, such as a surface layer, metallic layer, adhesive layer, etc., although this is not limited to the following.

[0095] The material for the color layer is not limited to the following, but for example, materials can be used in which pigments such as inorganic pigments such as carbon black, lead yellow, yellow iron oxide, red iron oxide, etc., phthalocyanine pigments such as phthalocyanine blue, phthalocyanine green, etc., organic pigments such as azolake pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments such as quinacridone red, etc. are dispersed in a binder resin such as a (meth)acrylic resin or a resin having urethane bonds. Among these, resins having urethane bonds are preferred from the viewpoint of impact resistance, etc.

[0096] The color layer can be formed using such materials by coating methods such as gravure coating, roll coating, die coating, bar coating, and knife coating.

[0097] The pattern layer is not limited to the following, but for example, patterns such as designs, logos, and illustrations may be directly applied to the surface layer, metallic layer, adhesive layer, etc., using printing methods such as gravure direct printing, gravure offset printing, inkjet printing, laser printing, and screen printing. Alternatively, films, sheets, etc., having designs, logos, and illustrations formed by coatings such as gravure coating, roll coating, die coating, bar coating, and knife coating, as well as by die-cutting and etching, may be used. As for the material of the pattern layer, for example, the same material used for the color layer may be used.

[0098] As the relief layer, a thermoplastic resin film having an uneven surface shape achieved by conventionally known methods, such as embossing, scratching, laser processing, dry etching, or hot pressing, can be used. Alternatively, a thermosetting or radiation-curable resin, such as a curable (meth)acrylic resin, can be applied to a release liner having an uneven surface shape, cured by heating or radiation, and then the release liner can be removed to form the relief layer.

[0099] The thermoplastic resin, thermosetting resin, and radiation-curable resin used in the relief layer are not particularly limited, but for example, fluororesins, polyester resins such as PET and PEN, (meth)acrylic resins, polyolefin resins such as polyethylene and polypropylene, thermoplastic elastomers, polycarbonate, polyamide, ABS resin, acrylonitrile-styrene resin, polystyrene, vinyl chloride, and resins having urethane bonds can be used. Among these, resins having urethane bonds are preferred from the viewpoint of impact resistance, etc. The relief layer may also contain at least one of the pigments used in the color layer.

[0100] The decorative layer of the present disclosure may include, to the extent that it does not adversely affect the effects of the present disclosure, optional components such as fillers, reinforcing agents, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, plasticizers, flow enhancers, surfactants, leveling agents, silane coupling agents, catalysts, and the like.

[0101] The thickness of the decorative layer is not particularly limited and can be adjusted as appropriate according to the required level of decoration, but for example, it can be about 1.0 micrometer or more, about 3.0 micrometers or more, or about 5.0 micrometers or more, and can be about 50 micrometers or less, about 40 micrometers or less, or about 30 micrometers or less.

[0102] The decorative laminates disclosed herein may utilize a bonding layer (sometimes referred to as a "primer layer," etc.) to bond additional layers within the laminate. Commonly used adhesives such as (meth)acrylic, polyolefin, polyurethane, polyester, and rubber-based solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing adhesives can be used as the bonding layer. The bonding layer can be applied by known coating methods, etc. To distinguish it from the adhesive layer described above, the adhesive layer described above may be referred to as the first adhesive layer, the bonding layer as the second adhesive layer, etc.

[0103] The decorative laminates of the present disclosure typically have a release liner applied to the adhesive layer. Examples of release liners include paper; plastic materials such as polyethylene, polypropylene, polyester (e.g., PET), and cellulose acetate; and paper coated with such plastic materials. These liners may have a surface that has been released with a release agent such as silicone. The thickness of the release liner can generally be about 5 micrometers or more, about 15 micrometers or more, or about 25 micrometers or more, and about 500 micrometers or less, about 300 micrometers or less, or about 250 micrometers or less.

[0104] The decorative laminates disclosed herein may be, for example, single sheets, rolls wound into a roll, or three-dimensional objects.

[0105] The decorative laminates of this disclosure are formed by applying a metallic coating composition containing metal pigment particles to a substantially smooth support to form a metallic layer, and then applying an adhesive layer to this metallic layer. The manufacturing methods of the decorative laminates of this disclosure will be described below with reference to Figures 2 and 3, but the manufacturing methods of the decorative laminates are not limited to these.

[0106] Figure 2 shows a method for manufacturing a decorative laminate by laminating and bonding an adhesive layer to a metallic layer. This method involves preparing a support 207 with a substantially smooth surface (step (a)), and applying a metallic coating composition to the substantially smooth surface of the support 207 to form a metallic layer 205 (step (b)). Here, known methods such as knife coaters, die coaters, roll coaters, bar coaters, cast coaters, notch bar coaters, gravure coaters, and rod coaters can be used as means for applying the metallic coating composition in step (b). These methods can be used individually or in combination of two or more. In forming the metallic layer, additional steps such as a drying step, a heat curing step, and an ionizing radiation curing step can be applied as needed. Such additional steps can be employed individually or in combination of two or more.

[0107] The viscosity of the metallic coating composition is preferably, for example, about 140 mPa·s or less, about 130 mPa·s or less, or about 120 mPa·s or less at 25°C. When the viscosity is within this range, the metallic pigment particles tend to orient almost uniformly on the support surface, and as a result, a good metallic luster can be obtained. There is no particular limit to the lower limit of viscosity, and for example, it can be about 4 mPa·s or more, about 5 mPa·s or more, or about 6 mPa·s or more. The viscosity specified herein is the value measured using a Type B viscometer (TVB-15 model) manufactured by Toki Sangyo Co., Ltd. (Minato-ku, Tokyo, Japan). The measurement is performed at 25°C using an M2 or M3 rotor (rotation speed: 100 rpm), and the value at 1 minute after the start of measurement is taken as the measured value.

[0108] Following step (b), the adhesive film prepared by applying the adhesive layer 203 to the release liner 201 is applied to the metallic layer 205 via the adhesive layer 203 (step (c)) to obtain a decorative laminate (step (d)). Here, the support 207 can constitute the surface layer of the decorative laminate or the release liner. When the support constitutes the release liner, the decorative laminate in step (d) can be referred to as an intermediate of the decorative laminate. To distinguish it from the release liner of the adhesive film, the release liner that is the support can be referred to as the first release liner, and the release liner that is the adhesive film can be referred to as the second release liner. These release liners can be used in the same way as the release liners described above. When the support constitutes the surface layer, the film-type surface layer among the surface layers described above can be used in the same way.

[0109] In Figure 2, the support constitutes a release liner. In this case, the support 207 of the release liner is peeled off from the intermediate (step (e)) to obtain a decorative laminate (step (f)).

[0110] Following step (f), additional layers, such as a surface layer, may be applied to the metallic layer 205 directly or indirectly via a bonding layer.

[0111] Figure 3 shows a method for manufacturing a decorative laminate by coating a metallic layer with an adhesive. This method involves preparing a support 307 with a substantially smooth surface (step (a)), applying a metallic coating composition to the substantially smooth surface of the support 307 to form a metallic layer 305, and then applying an adhesive to the metallic layer 305 to form an adhesive layer 303 (step (b)). Here, the known methods described above can be used as means for applying the metallic coating composition and adhesive in step (b). Additional steps such as a drying step, a thermosetting step, and an ionizing radiation curing step can be applied as needed in the formation of the metallic layer and the adhesive layer. One or more of these additional steps can be used, or a combination of two or more.

[0112] Following step (b), a release liner 301 is applied to the adhesive layer 303 (step (c)) to obtain a decorative laminate (step (d)). Here, the support 307 can constitute the surface layer of the decorative laminate or the release liner. When the support constitutes the release liner, the decorative laminate in step (d) can be referred to as an intermediate of the decorative laminate. To distinguish it from the release liner applied to the adhesive layer, the release liner that is the support can be referred to as the first release liner, and the release liner applied to the adhesive layer can be referred to as the second release liner. These release liners can be used in the same way as the release liners described above. When the support constitutes the surface layer, the surface layer in the form of a film among the surface layers described above can be used in the same way.

[0113] In Figure 3, the support constitutes a release liner. In this case, the support 307 of the release liner is peeled off from the intermediate (step (e)) to obtain a decorative laminate (step (f)).

[0114] Following step (f), additional layers, such as a surface layer, may be applied to the metallic layer 305 directly or indirectly via a bonding layer.

[0115] The support used in the manufacturing method of the decorative laminate of this disclosure is composed of a substantially smooth surface on which the metallic coating composition is applied. The smoothness of the substantially smooth surface of the support can be evaluated by a surface roughness test described later. Such roughness (Sa) can be about 3.0 micrometers or less, about 0.5 micrometers or less, about 0.3 micrometers or less, about 0.2 micrometers or less, about 0.15 micrometers or less, about 0.1 micrometers or less, or about 0.08 micrometers or less. There is no particular limit to the lower limit of roughness; for example, it can be about 0.01 micrometers or more, about 0.03 micrometers or more, about 0.05 micrometers or more, or about 0.07 micrometers or more. When a support exhibiting such roughness is used, the metallic pigment particles tend to orient substantially uniformly on the surface of the support, and as a result, a good metallic luster can be obtained.

[0116] The surface of a metallic layer prepared by the manufacturing method of this disclosure may typically exhibit the same roughness (Sa) as described above, as a result of the transfer of the smooth surface of the support. The surface roughness of the metallic layer can also be measured and calculated in the same manner as described above.

[0117] According to one embodiment of the present disclosure, an article is provided in which the above-mentioned decorative laminate is bonded to a support member. Examples of such articles include a substantially flat article before molding, in which the decorative laminate is bonded to a support member such as a polycarbonate sheet, or an article having a three-dimensional shape obtained by further molding such a substantially flat article, or an article having a three-dimensional shape obtained by bonding the decorative laminate to a support member having a curved surface or the like. In the present disclosure, "three-dimensional shape" typically refers to a three-dimensional shape in which the Z axis is added to a two-dimensional shape (a planar shape with only the X and Y axes).

[0118] Articles having a three-dimensional shape are preferably manufactured by applying the above-described decorative laminate to a support member having a three-dimensional shape, from the viewpoint of productivity and other factors. The application of this decorative laminate to the support member is preferably carried out by vacuum forming or vacuum pressure forming, from the viewpoint of obtaining a highly accurate article. The decorative laminate disclosed herein can be used for vacuum forming or vacuum pressure forming with stretching. In particular, a decorative laminate comprising a metallic layer prepared using a metallic coating composition containing metal pigment particles, a binder precursor, and a silane coupling agent is more preferably used for vacuum forming or vacuum pressure forming because it exhibits excellent adhesion between metal pigment particles and can maintain excellent metallic luster even after stretching.

[0119] In vacuum forming and vacuum pressure forming, decorative laminates are generally subjected to heating and vacuum. The heating temperature can generally be about 50°C or higher, about 80°C or higher, about 100°C or higher, about 120°C or higher, or about 130°C or higher, and can be about 180°C or lower, about 170°C or lower, or about 160°C or lower. The vacuum level in the reduced pressure atmosphere can be about 0.10 atm or lower, about 0.05 atm or lower, or about 0.01 atm or lower, with atmospheric pressure being 1 atm. There are no particular restrictions on the lower limit of the vacuum level; for example, it can be about 0.0001 atm or higher, about 0.0005 atm or higher, about 0.001 atm or higher, or about 0.005 atm or higher. In vacuum pressure forming, decorative laminates are further subjected to pressure. The pressure can be, for example, greater than approximately 3 atm, approximately 4 atm or more, or approximately 5 atm or more, with atmospheric pressure being 1 atm. There is no particular upper limit on the pressure, but for example, it can be approximately 20 atm or less, approximately 15 atm or less, or approximately 10 atm or less.

[0120] The maximum area elongation of the decorative laminate after molding may be approximately 0% or more, approximately 5% or more, approximately 10% or more, approximately 30% or more, approximately 50% or more, approximately 100% or more, approximately 200% or more, or approximately 300% or more, approximately 1,000% or less, approximately 700% or less, approximately 500% or less, or approximately 450% or less.

[0121] The area growth rate is defined as: Area growth rate (%) = (BA) × 100 / A (A: area of ​​a part of the decorative laminate before molding, B: area of ​​the part of the decorative laminate corresponding to A after molding). For example, if the area of ​​a part of the decorative laminate is 100 cm² before molding... 2 And that part, after molding, is 250 cm on the surface of the support member. 2 In that case, it is 150%. The maximum area elongation rate refers to the value of the location with the highest area elongation rate among all decorative laminates on the surface of the article.

[0122] For example, when a flat decorative laminate is attached to a three-dimensional support member using vacuum forming, the initial contact point of the film with the support member is hardly stretched, resulting in an area elongation rate of almost 0%. However, the edges, which are attached last, are greatly stretched, resulting in an area elongation rate of over 200%. Thus, the area elongation rate of the decorative laminate varies significantly depending on where it is attached. Whether or not defects such as failure to conform to the support member or tearing of the film occur in the area where the film is stretched the most determines the success or failure of the molding. Therefore, rather than the average area elongation rate of the entire article, the area elongation rate of the most stretched part, i.e., the maximum area elongation rate, becomes the practical indicator of the success or failure of the final product.

[0123] The maximum area elongation rate can be determined, for example, by printing a 1mm square grid across the entire surface of the decorative laminate before molding and measuring the change in area after molding, or by measuring the thickness of the decorative laminate before and after molding.

[0124] There are no particular restrictions on the material of the support member, and examples include resins having urethane bonds (e.g., polyurethane resin), polyolefin resins (e.g., polyethylene and polypropylene), glycol-modified polyethylene terephthalate resin (PET-G), (meth)acrylic resin (e.g., polymethyl methacrylate resin), polycarbonate resin, and acrylonitrile-butadiene-styrene copolymer (ABS). These can be used individually or in combination of two or more.

[0125] The support member may be transparent, translucent, or opaque in whole or in part in the visible range in order to provide the desired appearance.

[0126] There are no particular restrictions on the thickness of the support member; for example, it can be approximately 0.2 mm or more, approximately 0.5 mm or more, approximately 1.0 mm or more, or approximately 1.5 mm or more, and it can be approximately 3.0 mm or less, approximately 2.5 mm or less, or approximately 2.0 mm or less.

[0127] Articles to which the decorative laminates of the present disclosure are applied can be used in a variety of applications. Such applications include, for example, signs (e.g., internally illuminated signs and externally illuminated signs); signs (e.g., internally illuminated signs and externally illuminated signs); various interior or exterior parts, such as interior or exterior parts for vehicles such as automobiles, trains, aircraft, and ships (e.g., roof members, pillar members, door trim members, instrument panel members, front members such as hoods, bumper members, fender members, side sill members, and interior panel members); building components (e.g., doors); electrical appliances such as personal computers, smartphones, mobile phones, refrigerators, and air conditioners; stationery; furniture; desks; and various containers such as cans. Among these, articles to which the decorative laminates of the present disclosure are applied are particularly suitable for use as interior or exterior parts for vehicles. [Examples]

[0128] The following examples illustrate specific embodiments of the present disclosure, but the present invention is not limited thereto. All parts and percentages are by mass unless otherwise specified. Numerical values ​​include errors inherent to the measurement principle and measuring device. Numerical values ​​are shown with significant figures after normal rounding.

[0129] The products used in this example are shown in Table 1 below.

[0130] [Table 1]

[0131] 《Example Test 1》 In Test Example 1, the metallic luster of the metallic layer was evaluated with and without the use of a support having a substantially smooth surface.

[0132] (Preparation of metallic coating composition 1) Metallic coating composition 1 was prepared by uniformly mixing 20 parts by mass of Toyal Shine™ TS-408PM, which is a metal pigment particle, and 80 parts by mass of MEK.

[0133] (Preparation of metallic coating composition 2) Metallic coating composition 2 was prepared by uniformly mixing 20 parts by mass of Toyal Shine™ TS-710PM, which is a metal pigment particle, and 80 parts by mass of MEK.

[0134] (Preparation of metallic coating composition 3) Metallic coating composition 3 was prepared by uniformly mixing 20 parts by mass of Toyal Shine™ EMRS-710, which is a metal pigment particle, and 80 parts by mass of MEK.

[0135] (Preparation of adhesive 1) 94 parts by mass of butyl acrylate (BA) and 6 parts by mass of acrylic acid (AA) were dissolved in a mixed solution of 100 parts by mass of toluene and 100 parts by mass of ethyl acetate. 0.2 parts by mass of azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-65) was added as a polymerization initiator, and the mixture was reacted under a nitrogen atmosphere at 50°C for 24 hours to prepare a toluene / ethyl acetate mixed solution of acrylic resin 1 (solid content 33%). The weight-average molecular weight of acrylic resin 1 was 760,000, and the glass transition temperature (Tg) was -20°C.

[0136] 60 parts by mass of methyl methacrylate (MMA), 34 parts by mass of n-butyl methacrylate (BMA), and 6 parts by mass of dimethylaminoethyl methacrylate (DMAEMA) were dissolved in 150 parts by mass of ethyl acetate. 0.6 parts by mass of dimethyl-2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-601) was added as a polymerization initiator, and the mixture was reacted under a nitrogen atmosphere at 65°C for 24 hours to prepare an ethyl acetate solution of acrylic resin 2 (solid content 39%). The weight-average molecular weight of acrylic resin 2 was 68,000, and the glass transition temperature (Tg) was 104°C.

[0137] A white adhesive 1 was prepared by uniformly mixing 49.16 parts by mass of acrylic resin 1, 17.85 parts by mass of acrylic resin 2, 0.23 parts by mass of SONGNOX (trademark) 1010, 1.08 parts by mass of Ti-Pure (trademark) R-960, 0.46 parts by mass of E-5XM, and 31.22 parts by mass of MIBK.

[0138] (Preparation of adhesive 2) White adhesive 2 was prepared by uniformly mixing 16 parts by mass of Desmocoll (trademark) 530 and 84 parts by mass of MEK.

[0139] (Preparation of adhesive 3) A white adhesive 3 was prepared by uniformly mixing 75.05 parts by mass of pressure-sensitive adhesive 1, 0.94 parts by mass of crosslinking agent, 0.41 parts by mass of acrylic resin 2, 0.83 parts by mass of Ti-Pure® R-960, 0.26 parts by mass of MIBK, and 22.51 parts by mass of MEK.

[0140] (Example 1) A metallic coating composition 1 was coated onto the nearly smooth surface of the release liner 1 using a Meyer bar coater with a No. 8 Meyer bar, and then dried in an oven at approximately 100°C for approximately 1 minute to produce a laminate having a metallic layer approximately 0.4 micrometers thick.

[0141] After coating another release liner 1 with adhesive 1, an adhesive layer approximately 40 micrometers thick was prepared by drying it in an oven at approximately 80°C for approximately 3 minutes and then in an oven at approximately 120°C for approximately 5 minutes. Subsequently, an adhesive transfer film was fabricated by laminating the release liner 2 onto this adhesive layer using a heat lamination method.

[0142] After removing the separator from the adhesive transfer film, the adhesive transfer film was bonded to the metallic layer of the laminate via the adhesive layer using a heat lamination method. Subsequently, the release liner 1 on the metallic layer side was removed to obtain the decorative laminate of Example 1.

[0143] (Example 2) A laminate comprising a metallic layer was prepared in the same manner as in Example 1. Adhesive 2 was coated onto this metallic layer, and then dried in an oven at approximately 80°C for approximately 3 minutes and in an oven at approximately 120°C for approximately 5 minutes to prepare an adhesive layer with a thickness of approximately 40 micrometers. Subsequently, a release liner 1 was separately laminated onto this adhesive layer by a heat lamination method. Then, the release liner 1 on the metallic layer side was removed to obtain the decorative laminate of Example 2.

[0144] (Example 3) A metallic coating composition 1 was coated onto the nearly smooth surface of the release liner 2 using a Meyer bar coater with a No. 5 Meyer bar, and then dried in an oven at approximately 100°C for approximately 1 minute to produce a laminate having a metallic layer approximately 0.2 micrometers thick.

[0145] After coating the metallic layer with adhesive 1, an adhesive layer approximately 40 micrometers thick was prepared by drying it in an oven at approximately 80°C for approximately 3 minutes and then in an oven at approximately 120°C for approximately 5 minutes. Subsequently, a release liner 1 was laminated onto this adhesive layer by a heat lamination method at 60°C. Then, the release liner 2 on the metallic layer side was removed to obtain the decorative laminate of Example 3.

[0146] (Example 4) The decorative laminate of Example 4 was obtained in the same manner as in Example 3, except that the metallic layer was prepared using metallic coating composition 2.

[0147] (Example 5) The decorative laminate of Example 5 was obtained in the same manner as in Example 3, except that the metallic layer was prepared using metallic coating composition 3, and the adhesive layer was prepared using adhesive 3, and the drying conditions during the preparation of the adhesive layer were changed to approximately 3 minutes in an oven at approximately 65°C and approximately 5 minutes in an oven at approximately 95°C.

[0148] (Comparative Example 1) Adhesive 1 was coated onto the substantially smooth surface of the release liner 1, and then dried in an oven at approximately 80°C for approximately 3 minutes and in an oven at approximately 120°C for approximately 5 minutes to prepare an adhesive layer with a thickness of approximately 40 micrometers. Next, metallic coating composition 1 was coated onto the adhesive layer using a Meyer bar coater with a Meyer bar No. 8, and then dried in an oven at approximately 100°C for approximately 1 minute to produce a decorative laminate of Comparative Example 1, which had a metallic layer with a thickness of approximately 0.4 micrometers.

[0149] (Comparative Example 2) A decorative laminate for Comparative Example 2 was prepared by preparing an adhesive layer in the same manner as in Comparative Example 1, and then coating the adhesive layer with Leaf Powder (trademark) 49CJ-1120 containing propylene glycol monomethyl ether as a solvent using a Meyer bar coater with a No. 5 Meyer bar. The laminate was then dried in an oven at approximately 100°C for approximately 1 minute to produce a metallic layer with a thickness of approximately 2.3 micrometers.

[0150] <Physical Property Evaluation Test 1> The characteristics of each decorative laminate were evaluated by conducting the following tests. The results are shown in Table 2.

[0151] (Metallic luster test: clarity) Three locations were arbitrarily selected from the metallic layer of the laminate, and the sharpness (Gd value) was measured for each selected area. The average value was then calculated. A sharpness and gloss meter (PGD-IV) manufactured by the Japan Color Research Institute was used to measure the sharpness.

[0152] (Visual inspection) The surface of the metallic layer was visually observed under a 400 lux white fluorescent light, focusing on the reflection of the subject's face. The distance between the metallic layer and the face was approximately 50 cm. A metallic luster was observed, and the face's outline was clearly defined, resulting in a rating of "Good." A good metallic luster was observed, but the outline was unclear, resulting in a rating of "Poor." A poor metallic luster was not observed, and areas with visible defects were rated as "Poor." Here, "defective areas" refer to areas where the metallic luster is clearly reduced, such as areas that appear streaky or where haze is elevated.

[0153] (Surface roughness test: Sa value) The object to be measured (e.g., a support or decorative laminate) was fixed onto a roughly smooth aluminum plate with the surface to be measured facing upwards. Using a 3D measuring laser microscope (LEXT® OLS4100, manufactured by Olympus Corporation), the surface roughness (Sa) of the metallic layer was measured at five arbitrary locations with a 20x objective lens, and the average value was calculated. Table 2 shows the surface roughness of the outermost surface of the metallic layer.

[0154] [Table 2]

[0155] 《Example Test 2》 In Test Example 2, the effects of the binder and silane coupling agent on the metallic layer were evaluated.

[0156] (Preparation of metallic coating compositions (MC1-12)) Metallic coating compositions (MC1-MC12) were prepared by mixing each component in the proportions shown in Table 3. Here, the numerical values ​​for each component shown in Table 3 represent the content (mass%) based on the solid content of each component.

[0157] [Table 3]

[0158] (Example 6) A metallic coating composition MC1 was coated onto the nearly smooth surface of the release liner 2 using a Meyer bar coater with a No. 5 Meyer bar. The coated surface was then dried in an oven at approximately 100°C for approximately 1 minute to produce a laminate with a metallic layer approximately 0.2 micrometers thick. Subsequently, adhesive 1 was coated onto this metallic layer, and then dried in an oven at approximately 80°C for approximately 3 minutes and in an oven at approximately 120°C for approximately 5 minutes to prepare an adhesive layer approximately 40 micrometers thick. The release liner 1 was then laminated onto this adhesive layer by a heat lamination method. The release liner 2 on the metallic layer side was then removed to obtain a laminate comprising the metallic layer and the adhesive layer.

[0159] A multilayer film (surface layer) was prepared by laminating DX14S, S014G, a bonding layer made of phenoxy resin with a thickness of approximately 0.5 micrometers, and a transfer sheet in this order. The metallic layer of the laminate and the transfer sheet of the multilayer film were then placed in contact, and the laminate was bonded by heat lamination to obtain the decorative laminate of Example 6.

[0160] The release liner 1 was removed from the decorative laminate, and the laminate was bonded to a support member (PC / ABS plate (CK43 black, manufactured by Technopolymer Co., Ltd., Minato-ku, Tokyo, Japan)) at a molding temperature of 145°C using the vacuum pressure molding method (TOM molding method) to form an article.

[0161] (Examples 7-17) Articles of Examples 7 to 17 were prepared in the same manner as in Example 6, except that the metallic coating composition was changed to the one shown in Table 4.

[0162] <Physical Property Evaluation Test 2> The characteristics of each article were evaluated by conducting the clarity and appearance tests described above, as well as the adhesion tests described below. The results are shown in Table 4. Note that the decorative laminates disclosed herein may also be used without heating and / or pressure, as is done in vacuum pressure molding. In such cases, the adhesion requirements described below are not necessarily required. In other words, if good metallic luster is obtained, it falls under the examples. Furthermore, if it also exhibits excellent adhesion, it can be said to be suitable for use in molding with heating and / or pressure.

[0163] (Adhesion test) The adhesion performance of decorative laminates in articles was evaluated using the cross-cut method in accordance with JIS K 5600, according to the following criteria. A 10x10 grid with a grid spacing of 2 mm and Scotch™ filament tape 898 (manufactured by 3M Japan Ltd.) were used. The number of remaining squares in the metallic layer after tape removal was visually confirmed.

[0164] [Table 4]

[0165] It will be apparent to those skilled in the art that the above embodiments and examples can be modified in various ways without departing from the basic principles of the present invention. Furthermore, it will be apparent to those skilled in the art that various improvements and modifications of the present invention can be implemented without departing from the spirit and scope of the invention. [Explanation of symbols]

[0166] 100 decorative laminates 101, 201, 301 Release Liner 103, 203, 303 adhesive layer 105, 205, 305 metallic layer 207, 307 Support Some embodiments of this disclosure are described in the following sections [1]-

[20] . [Item 1] Adhesive layer, and Metallic layer containing metal pigment particles It includes in order, The clarity of the outermost surface of the metallic layer, located on the side opposite to the adhesive layer, is 0.5 or higher. Decorative laminate. [Item 2] The decorative laminate according to item 1, wherein the shape of the metal pigment particles is flaky. [Item 3] The decorative laminate according to item 1 or 2, wherein the thickness of the metallic layer is 0.07 micrometers or more and 1.1 micrometers or less. [Item 4] A decorative laminate according to any one of items 1 to 3, wherein the content of the metal pigment particles in the metallic layer is 20.0% by mass or more and 40.0% by mass or less. [Item 5] The decorative laminate according to any one of items 1 to 4, wherein the metallic layer comprises a binder and a silane coupling agent. [Item 6] The decorative laminate according to item 5, wherein the content of the binder in the metallic layer is 0.1% by mass or more and 10.0% by mass or less, and the content of the silane coupling agent in the metallic layer is 50.0% by mass or more and 79.9% by mass or less. [Item 7] The decorative laminate according to item 5 or 6, wherein the silane coupling agent comprises at least one selected from the group consisting of epoxy groups and amine groups. [Item 8] The decorative laminate according to any one of items 5 to 7, wherein the binder comprises at least one selected from the group consisting of a resin having a urethane bond and a phenoxy resin. [Item 9] The decorative laminate according to any one of items 1 to 8, wherein the adhesive layer contains a white pigment. [Item 10] A decorative laminate according to any one of items 1 to 9, comprising at least one selected from the group consisting of a surface layer, a decorative layer, a bonding layer, and a release liner. [Item 11] A decorative laminate as described in any one of items 1 to 10, used for vacuum forming or vacuum pressure forming. [Item 12] A metallic coating composition containing metal pigment particles is applied to a support with a substantially smooth surface to form a metallic layer. Applying an adhesive layer to the metallic layer, A method for manufacturing decorative laminates, including [the specified element]. [Item 13] The manufacturing method according to item 12, wherein the support constitutes the surface layer or release liner of the decorative laminate. [Item 14] The manufacturing method according to item 12 or 13, wherein the surface roughness (Sa) of the support is 0.5 micrometers or less. [Item 15] An article in which a decorative laminate described in any one of items 1 to 11 is bonded to a support member. [Item 16] Articles having a three-dimensional shape, as described in item 15. [Item 17] Articles that are interior or exterior parts of a vehicle, as described in item 15 or 16. [Item 18] A method for manufacturing an article having a three-dimensional shape, comprising applying a decorative laminate described in any one of items 1 to 11 to a support member having a three-dimensional shape. [Item 19] The manufacturing method according to item 18, wherein the application of the film to the support member is performed by vacuum forming or vacuum pressure forming. [Item 20] A metallic coating composition comprising metal pigment particles, a binder precursor, and a silane coupling agent, In terms of solid content, the content of the metal pigment particles is 20.0% by mass or more and 40.0% by mass or less, the content of the binder precursor is 0.1% by mass or more and 10.0% by mass or less, and the content of the silane coupling agent is 50.0% by mass or more and 79.9% by mass or less. Metallic coating composition.

Claims

1. Adhesive layer, and A metallic layer containing metal pigment particles, a binder, and a silane coupling agent. It includes in order, The content of the binder in the metallic layer is 0.1% by mass or more and 10.0% by mass or less, and the content of the silane coupling agent in the metallic layer is 50.0% by mass or more and 79.9% by mass or less. The clarity of the outermost surface of the metallic layer, located on the side opposite to the adhesive layer, is 0.5 or higher. Decorative laminate.

2. Adhesive layer, and Metallic layer containing metal pigment particles It includes in order, The thickness of the metallic layer is 0.07 micrometers or more and 0.9 micrometers or less. The clarity of the outermost surface of the metallic layer, located on the side opposite to the adhesive layer, is 0.5 or higher. Decorative laminate.

3. The decorative laminate according to claim 1 or 2, wherein the shape of the metal pigment particles is flaky.

4. The decorative laminate according to claim 1, wherein the thickness of the metallic layer is 0.07 micrometers or more and 1.1 micrometers or less.

5. The decorative laminate according to any one of claims 1 to 4, wherein the content of the metal pigment particles in the metallic layer is 20.0% by mass or more and 40.0% by mass or less.

6. The decorative laminate according to claim 2, wherein the metallic layer comprises a binder and a silane coupling agent.

7. The decorative laminate according to claim 6, wherein the content of the binder in the metallic layer is 0.1% by mass or more and 10.0% by mass or less, and the content of the silane coupling agent in the metallic layer is 50.0% by mass or more and 79.9% by mass or less.

8. The decorative laminate according to claim 1 or 6, wherein the silane coupling agent comprises at least one selected from the group consisting of epoxy groups and amine groups.

9. A decorative laminate according to any one of claims 1 to 8, comprising at least one selected from the group consisting of a surface layer, a decorative layer, a bonding layer, and a release liner.

10. A decorative laminate according to any one of claims 1 to 9, used for vacuum forming or vacuum pressure forming.

11. A metallic coating composition containing metal pigment particles, a binder precursor, and a silane coupling agent is applied to a support with a substantially smooth surface to form a metallic layer. Applying an adhesive layer to the metallic layer, Includes, In terms of solid content, the content of the binder precursor is 0.1% by mass or more and 10.0% by mass or less, and the content of the silane coupling agent is 50.0% by mass or more and 79.9% by mass or less. The surface roughness (Sa) of the support is 0.5 micrometers or less. A method for manufacturing decorative laminates.

12. A metallic coating composition containing metal pigment particles is applied to a support with a substantially smooth surface to form a metallic layer, Applying an adhesive layer to the metallic layer, Includes, The surface roughness (Sa) of the support is 0.5 micrometers or less. The thickness of the metallic layer is 0.07 micrometers or more and 0.9 micrometers or less. A method for manufacturing decorative laminates.

13. The manufacturing method according to claim 11 or 12, wherein the support constitutes the surface layer or release liner of the decorative laminate.

14. An article in which a decorative laminate according to any one of claims 1 to 10 is bonded to a support member.

15. The article according to claim 14, having a three-dimensional shape.

16. A method for manufacturing an article having a three-dimensional shape, comprising applying a decorative laminate according to any one of claims 1 to 10 to a support member having a three-dimensional shape.

17. The manufacturing method according to claim 16, wherein the decorative laminate is applied to the support member by vacuum forming or vacuum pressure forming.

18. A metallic coating composition comprising metal pigment particles, a binder precursor, and a silane coupling agent, In terms of solid content, the content of the metal pigment particles is 20.0% by mass or more and 40.0% by mass or less, the content of the binder precursor is 0.1% by mass or more and 10.0% by mass or less, and the content of the silane coupling agent is 50.0% by mass or more and 79.9% by mass or less. Metallic coating composition.

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