Metal-like decorative member and metal-like decorative molded body using the same

Abstract

To provide a metal-like decorative member capable of improving a metallic sheen after molding when using a transparent substrate containing a rubber particle.SOLUTION: A metal-like decorative member includes a metal vapor deposition film having a metal deposition film arranged on a transparent substrate in a manner in which the transparent substrate faces an outer layer. The transparent substrate is a transparent resin substrate containing a rubber particle and a binder resin. The metal deposition film includes island parts made of metal and a sea part positioned between the island parts. An area A for a piece of the island parts is 4,400 to 56,000nm2.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a metallic decorative member and a metallic decorative molded article using the same. [Background technology]

[0002] Conventionally, in order to improve the design of molded articles, metallic luster has been imparted to the surface of the molded article. Metal plating has long been used as a means of imparting metallic luster. However, metal plating has problems such as a complicated process, high manufacturing costs, and the generation of waste liquid, which places a burden on the environment. In addition, when the surface of a molded article has an uneven shape, it is difficult to apply a uniform and beautiful plating film.

[0003] As an alternative to metal plating, a method has been proposed in which the surface of an adherend, such as a resin molded body, is decorated using a decorative sheet having a metal vapor deposition film formed by physical vapor deposition (PVD) (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5809768 Summary of the Invention [Problem to be solved by the invention]

[0005] The basic structure of a decorative sheet having a metal deposition film is a metal deposition film having a metal deposition film on a transparent substrate. However, since a metal deposition film alone has problems such as insufficient strength, a laminate is usually produced by laminating a resin substrate on the inner layer side of the metal deposition film, and the laminate is then molded to obtain a metallic decorated molded product.

[0006] However, when such a laminate is obtained from a conventional metal-deposited film and then molded, it frequently occurs that the desired metallic luster is not obtained. [Means for solving the problem]

[0007] As a result of intensive research, the inventors first focused on the drying process of the resin substrate. The drying process is a process carried out before forming a laminate for the purpose of removing moisture from the resin substrate. The inventors hypothesized that the transparent base material of the metallized film shrinks during the drying process, causing wrinkles on the metallized surface, thereby reducing the metallic luster. However, even when a transparent substrate having a low shrinkage rate is used for the metal-deposited film, it is often the case that the expected metallic luster cannot be obtained after molding.

[0008] After further intensive investigation, the inventors found that the above problems are more likely to occur when using a specific transparent substrate (specifically, a "transparent substrate containing rubber particles" used to improve moldability), and further found that even when such a specific transparent substrate is used, it is possible to improve the metallic luster of the metallic-toned decorated molded body obtained by molding by giving the metal vapor deposition film a specific composition, and thus completed the present invention.

[0009] The present invention provides the following [1] and [2]. [1] A metallic decorative member comprising a transparent substrate and a metal deposition film having a metal deposition film on the transparent substrate, the transparent substrate being arranged to face the outer layer side, the transparent substrate being a transparent resin substrate containing rubber particles and a binder resin, the metal deposition film having islands and sea portions located between the islands, each of the islands having an area A of 4,400 to 56,000 nm 2 This is a metallic decorative component. [2] A metallic decorative molding formed from the metallic decorative member described in [1] above. Effect of the Invention

[0010] According to the present invention, when a transparent substrate containing rubber particles is used, it is possible to provide a metallic decorative component that can have excellent metallic luster after molding, and a metallic decorative molded body using the same. [Brief description of the drawings]

[0011] [Figure 1] 1 is a cross-sectional view showing one embodiment of a metallic decorative member of the present invention. [Diagram 2] FIG. 2 is a cross-sectional view showing another embodiment of the metallic decorative member of the present invention. [Diagram 3] 1A to 1C are schematic diagrams illustrating an example of behavior of islands of a metal vapor-deposited film when heated. [Figure 4] 11A to 11C are schematic diagrams illustrating another example of the behavior of the island portions of the metal vapor deposition film when heated. [Diagram 5] 2 is a SEM photograph of a metal vapor deposition film of the metallic decorative member of Example 1. [Figure 6] 1 is a SEM photograph of a metal vapor deposition film of a metallic decorative member of Comparative Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] [Metallic decorative materials] The metallic decorative member of the present invention is formed by arranging a metal deposition film having a metal deposition film on a transparent substrate so that the transparent substrate faces the outer layer side, the transparent substrate being a transparent resin substrate containing rubber particles and a binder resin, the metal deposition film having islands made of metal and sea portions located between the islands, and an area A per island being 4,400 to 56,000 nm 2 It is what it is.

[0013] 1 and 2 are cross-sectional views showing an embodiment of a metallic decorative member of the present invention. 1 and 2, a metal-deposited film 10 having a metal-deposited film 12 on a transparent substrate 11 is disposed so that the transparent substrate 11 faces the outer layer side. The metal-deposited film 10 of the metal-deposited film 10 of the metal-deposited film 10 of Fig. 2 has a primer layer 13 between the transparent substrate 11 and the metal-deposited film 12. The metal-deposited film 10 of the metal-deposited film 100 of Fig. 2 has an adhesive layer 20 and a resin substrate 30 on the inner layer side of the metal-deposited film 10.

[0014] <Metal deposition film> A metal vapor-deposited film has a metal vapor-deposited film on a transparent substrate. A primer layer may be provided between the transparent substrate and the metal vapor deposition film in order to improve adhesion.

[0015] <<Transparent base material>> The transparent substrate serves as a support for the metal vapor deposition film, and is disposed on the outer layer side, and serves to impart scratch resistance to the metallic decorative member.

[0016] In the present invention, a transparent resin substrate containing rubber particles and a binder resin is used as the transparent substrate. By containing rubber particles in the transparent substrate, the transparent substrate is less likely to crack during molding, and moldability can be improved. On the other hand, when the transparent substrate contains rubber particles, the metallic luster may be reduced by heat treatment. The reason for this is thought to be as follows (1).

[0017] (1) Metallic decorative members may be heat-treated before molding in order to remove moisture from the resin substrate laminated on the inner layer side of the metallized film. During the heat treatment before molding for the purpose of removing moisture, it is believed that minute dimensional changes occur near the surface of the transparent substrate of the metallized film. Specifically, it is believed that the thermal behavior of a transparent substrate containing rubber particles is subtly different between the area where the rubber particles are present near the surface and the area where the rubber particles are not present near the surface. Due to the difference in thermal behavior of this microscopic region, the islands of the metallized film, which are usually arranged in an orderly manner as shown in Figures 3(a) and 4(a), may become disordered as shown in Figures 3(b) or 4(b), and in such a case, it is believed that the metallic luster is reduced. In addition, when the metallic decorative member has another layer such as a resin substrate on the inner layer side of the metallized film, and high heat is applied to the transparent base material of the metallized film in the process of forming the other layer, the heat at this time may also cause a decrease in metallic gloss as described above. For example, when the metallic decorative member has a resin substrate described later, if the metal adhesive film and the resin substrate are laminated in a state where high heat is applied to the transparent base material of the metallized film, the heat at this time may cause a decrease in metallic gloss as described above.

[0018] If molding and heat treatment are performed in a state where the island portions are disordered as described above, it is believed that the following (2) will occur. (2) As shown in Figure 3(b), when a metallic decorative component is molded with overlapping island portions of the metal deposition film, the metal of the overlapping island portions is damaged as it stretches and peels off, further reducing the metallic luster. And because the island portions are damaged in this way, it is difficult to restore the metallic luster even with heat treatment after molding. On the other hand, if the metallic decorative component is molded without overlapping islands of the metal vapor deposition film as shown in Fig. 4(b), the loss of metallic luster during molding can be suppressed. Furthermore, it is considered that the heat applied to the metallic decorative component during molding (for example, the heat when drawing down the metallic decorative component in vacuum molding) makes the disordered island parts closer to their original state, and the metallic luster is easily restored.

[0019] In some cases, the arrangement of the islands in the metal-deposited film is not significantly disturbed during the heat treatment before molding. As will be described in detail later, by using a metal-deposited film in which the area A per island is within a specific range, the metal-deposited film is more likely to be smoothed by the heat and pressure during molding, making it easier to achieve excellent metallic luster after molding.

[0020] The above-mentioned fluctuation in metallic gloss caused by the movement of the island in a micro-area is difficult to distinguish clearly by the specular gloss, which is a general-purpose measurement, but it can be clearly distinguished by the human eye by the clarity of the reflected background. Specifically, the background reflected in the metal-deposited film in the state of FIG. 4(b) is more clearly visible with a clearer outline than the background reflected in the metal-deposited film in the state of FIG. 3(b). In addition, as a method for objectively measuring the above-mentioned fluctuation in metallic gloss caused by the movement of the island in a micro-area, there is a method for measuring the distinctness of image (DOI) using a wavescan device (manufactured by BYK Japan, product name: Wavescan Dual AW-4840) or the like. It is considered that the fluctuation in metallic gloss caused by the movement of the island in a micro-area can also be measured by the ratio of the 20-degree specular gloss (G20) to the peak reflectance (Rspec). Peak reflectance (Rspec) is the gloss over a narrow angular range of 20 degrees ±0.09905 degrees.

[0021] Examples of binder resins for transparent substrates include polyolefin resins such as polyethylene and polypropylene; vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; acrylic resins such as polymethyl(meth)acrylate and polyethyl(meth)acrylate; styrene resins such as polystyrene; and polyamide resins represented by nylon 6 or nylon 66. Among these resins, acrylic resins are preferred because they have excellent light resistance, high hardness, and scratch resistance, and further have a low refractive index, which means that they are excellent in transparency and scratches are less noticeable. The content of the acrylic resin is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more of the total binder resin in the transparent substrate.

[0022] The acrylic resin as the binder resin is preferably a homopolymer of a methacrylic acid ester or a copolymer mainly composed of a methacrylic acid ester. As the methacrylic acid ester, an alkyl ester of methacrylic acid is usually used, and the alkyl group may have about 1 to 4 carbon atoms. When a copolymer is used, an acrylic acid ester, an aromatic vinyl compound, a vinyl cyan compound, or the like is used. Such an acrylic resin can be obtained, for example, by polymerization of 50-100% by weight of an alkyl methacrylate having an alkyl group having 1-4 carbon atoms, 0-50% by weight of an acrylic ester, and 0-49% by weight of another vinyl monomer copolymerizable therewith. Here, the acrylic ester is preferably used in an amount of 0.1-50% by weight, more preferably 1-50% by weight, and the copolymerization ratio of the alkyl methacrylate is preferably 50-99% by weight, more preferably 50-99.9% by weight.

[0023] The rubber particles are particles having an elastic layer. From the viewpoint of transparency, the rubber particles preferably have a layer containing the same type of resin as the binder resin in the outer shell of the elastic layer. In other words, from the viewpoint of transparency, the rubber particles preferably contain the same type of resin as the binder resin in the outer shell. For example, it is preferable that the rubber particles contain an acrylic resin as the binder resin, and the rubber particles contain an acrylic resin in the outer shell. From the viewpoint of improving transparency, it is preferable that the elastic layer of the rubber particle, the outer shell of the rubber particle, and the binder resin contain the same type of component.

[0024] Furthermore, from the viewpoint of transparency, when the refractive index of the elastomer layer of the rubber particle is n0, the refractive index of the outer shell of the rubber particle is n1, and the refractive index of the binder resin is n2, it is preferable that the following formula (A) is satisfied, and it is more preferable that the following formulas (A) and (B) are satisfied. 0.98≦n1 / n2≦1.02 (A) 0.98≦n0 / n1≦1.02 (B)

[0025] The rubber particles can be obtained, for example, by obtaining an elastic polymer and then polymerizing the components constituting the outer shell in the presence of the elastic polymer. For example, in the presence of 100 parts by weight of an elastic copolymer having a layer obtained by polymerizing 50 to 99.9% by weight of an alkyl acrylate, 0 to 49.9% by weight of another vinyl monomer copolymerizable therewith, and 0.1 to 10% by weight of a copolymerizable crosslinking monomer, 10 to 400 parts by weight of a monomer composition consisting of 50 to 100% by weight of a methacrylic acid ester, 0 to 50% by weight of an acrylic acid ester, and 0 to 49% by weight of at least one other vinyl monomer copolymerizable therewith can be polymerized to obtain a rubber-containing polymer having an outer shell (a polymerized layer formed from the monomer composition) on the surface of a core (a layer containing the elastic copolymer).

[0026] The rubber-containing polymer can be produced, for example, by polymerizing the components for the elastic copolymer in at least one reaction stage by emulsion polymerization or the like to obtain an elastic copolymer, and polymerizing the above-mentioned monomer containing methacrylic acid ester in at least one reaction stage in the presence of the elastic copolymer by emulsion polymerization or the like. By such multiple-stage polymerization, the monomer containing methacrylic acid ester used in the latter stage is graft-copolymerized to the elastic copolymer to produce a crosslinked elastic copolymer having a graft chain. That is, the rubber-containing polymer becomes a graft copolymer having a multi-layer structure containing alkyl acrylate as the main component of rubber. In addition, when the polymerization of the elastic copolymer is carried out in two or more stages, or when the polymerization of the monomer mainly composed of methacrylic acid ester is carried out in two or more stages, in either case, it is sufficient that the overall monomer composition is within the above range, not the monomer composition of each stage.

[0027] In the rubber-containing polymer, examples of the alkyl acrylate used to form the elastic copolymer include those having an alkyl group with a carbon number of 1 to 8. Among them, those having an alkyl group with a carbon number of 4 to 8, such as butyl acrylate and 2-ethylhexyl acrylate, are preferred. In the rubber-containing polymer, other vinyl monomers which are used as desired to form an elastic copolymer and are copolymerizable with the alkyl acrylate are preferably alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate, styrene, acrylonitrile, and the like.

[0028] In the rubber-containing polymer, the copolymerizable crosslinkable monomer used to form the elastic copolymer may be one having at least two polymerizable carbon-carbon double bonds in one molecule, and examples thereof include unsaturated carboxylic acid diesters of glycols such as ethylene glycol dimethacrylate and butanediol dimethacrylate, alkenyl esters of unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, and allyl cinnamate, polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, and triallyl isocyanurate, unsaturated carboxylic acid esters of polyhydric alcohols such as trimethylolpropane triacrylate, and divinylbenzene. Among these, alkenyl esters of unsaturated carboxylic acids and polyalkenyl esters of polybasic acids are preferred. These crosslinkable monomers may be used alone or in combination of two or more types as necessary.

[0029] The methacrylic acid ester to be grafted to the elastic copolymer is preferably an alkyl ester of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, etc. The acrylic acid ester may be, for example, an alkyl acrylate such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, etc., and the other vinyl monomer copolymerizable with the methacrylic acid ester and / or acrylic acid ester is not particularly limited, but may be, for example, styrene, acrylonitrile, etc.

[0030] The monomer to be grafted is preferably used in an amount of 10 to 400 parts by weight, more preferably 20 to 200 parts by weight, per 100 parts by weight of the elastic copolymer, and can be polymerized in at least one reaction stage. When the amount of the monomer to be grafted is 10 parts by weight or more, the elastic copolymer is less likely to aggregate, and the transparency is improved.

[0031] Further, a hard polymer layer mainly composed of methacrylic acid ester can be provided on the inner side of the elastic copolymer layer. In this case, the monomer of the hard layer constituting the innermost layer is first polymerized, and in the presence of the obtained hard polymer, the monomer constituting the elastic copolymer is polymerized, and further, in the presence of the obtained elastic copolymer, the monomer to be grafted mainly composed of the above-mentioned methacrylic acid ester is polymerized. Here, the hard layer to be the innermost layer is preferably a polymerized monomer composed of 70 to 100% by weight of methacrylic acid ester and 0 to 30% by weight of another vinyl monomer copolymerizable therewith. In this case, it is also effective to use a copolymerizable crosslinkable monomer as one of the other vinyl monomers. As the methacrylic acid ester, an alkyl methacrylate, particularly methyl methacrylate, is effective.

[0032] The average particle size of the rubber particles is preferably 0.05 to 0.40 μm, and more preferably 0.10 to 0.30 μm. By making the average particle size of the rubber particles 0.05 μm or more, the impact resistance of the transparent substrate can be easily improved, and by making the average particle size of the rubber particles 0.40 μm or less, the transparency of the transparent substrate can be easily improved. Note that two types of rubber particles having different average particle sizes may be used as the rubber particles. The average particle diameter of the rubber particles can be calculated, for example, by preparing a sample by cutting a transparent substrate vertically, staining the rubber particles or materials other than the rubber particles of the sample with a staining agent such as ruthenium oxide, taking a transmission electron image of the stained sample using an electron microscope, and averaging the diameters of 20 particles imaged. The average particle size of the rubber particles can be set to an appropriate value by adjusting the type and amount of the polymerization initiator, the polymerization time, and the like.

[0033] From the viewpoint of improving moldability while maintaining the function of the binder resin (e.g., the high surface hardness of acrylic resin), the compounding ratio of the binder resin to the rubber particles in the transparent substrate is preferably 10 to 1,000 parts by mass, more preferably 40 to 600 parts by mass, and even more preferably 100 to 250 parts by mass, of the rubber particles per 100 parts by mass of the binder resin.

[0034] The transparent substrate preferably has a thermal shrinkage of 1.0% or less, more preferably 0.7% or less, and even more preferably 0.5% or less, when heated for 30 minutes at 75° C. By reducing the thermal shrinkage of the transparent substrate, it is possible to easily prevent the island portions of the metal vapor deposition film from becoming in the state shown in FIG. 3(b) due to heating before molding, and it is possible to easily achieve excellent metallic luster after molding. In this specification, the heat shrinkage rate at 75° C. for 30 minutes is measured in accordance with JIS K7133:1999, and refers to the average of the MD and TD directions.

[0035] From the viewpoint of a balance between formability and protection of the metal vapor deposition film, the transparent substrate preferably has a thickness of 50 to 250 μm, more preferably 60 to 200 μm, and even more preferably 70 to 150 μm. The thickness of the transparent substrate can be measured, for example, by observing a vertical cross section with an electron microscope or the like.

[0036] The transparent substrate preferably has a haze according to JIS K7136:2000 of 5% or less, more preferably 3% or less, and even more preferably 1% or less. Furthermore, the transparent substrate preferably has a total light transmittance according to JIS K7361-1:1997 of 85% or more, and more preferably 90% or more.

[0037] Any additives, such as light stabilizers such as ultraviolet absorbers, antioxidants, lubricants, and antistatic agents, may be added to the transparent substrate as required.

[0038] <<Metal deposition film>> Examples of metals constituting the metal vapor deposition film include metals such as indium, tin, aluminum, nickel, copper, silver, gold, platinum, brass, chromium, and zinc, as well as alloys thereof, etc. Among these, it is preferable to use one or more metals selected from indium, tin, aluminum, zinc, and alloys thereof. Indium vapor deposition films are most preferred because they have excellent metallic luster and good weather resistance. Furthermore, since indium has a low melting point, indium vapor deposition films tend to have the above-mentioned island structure. Therefore, when the metal vapor deposition film is an indium vapor deposition film, it is effective in that the effects of the present invention can be easily achieved.

[0039] Examples of methods for forming metal vapor deposition films include physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, and ion plating. Among these, vacuum deposition is preferred because it can be used with any material. That is, examples of metal vapor deposition films include physical vapor deposition films, and among these, vacuum deposition films are preferred.

[0040] In the present invention, the metal deposition film is formed such that the area A per island is 4,400 to 56,000 nm 2 The shape of the substrate is to be such that: The area A of each island of the metal deposition film is 4,400 nm 2 If it is less than this, the metallic luster will be insufficient and the design of the metallic decorative molding will not be good. On the other hand, the area A of each island in the metal deposition film is 56,000 nm 2 If the area A of each island in the metal deposition film is more than 56,000 nm, the density of the islands in the metal deposition film becomes too high, and the islands of the metal deposition film tend to become as shown in Figure 3(b) when heated before molding, and the metal luster after molding cannot be excellent. 2 If the thickness exceeds 100 nm, even if heat is applied to the metallic decorative member during molding, the disordered island portions will not easily return to their original state, and the metallic luster will not easily be restored. In addition, the area A of each island of the metal deposition film is 56,000 nm 2 If the area A of each island is more than 56,000 nm, the metallic luster after molding cannot be excellent, even if the island of the metal deposition film does not reach the state shown in Figure 3(b) by heating before molding. 2 If the thickness exceeds this range, it is believed that the metal vapor deposition film is difficult to smooth due to the heat and pressure during molding. The area A of each island of the metal deposition film is 17,500 to 53,000 nm 2 It is preferable that the wavelength is 24,000 to 51,000 nm. 2 More preferably, the wavelength is 31,500 to 49,000 nm. 2 It is even more preferable that:

[0041] In this specification, the area A of each island portion is calculated by the following method. First, a surface photograph of the metal deposition film of the metal deposition film is taken with a scanning electron microscope (SEM), preferably at a magnification of 5,000 to 20,000 times. Next, a square frame that can hold 50 to 100 islands is placed on the photograph. The length of one side of the frame is L [nm]. "L" represents the actual size on the sample, and can be calculated, for example, based on the pixel size or scale bar of the SEM photograph. Next, count the number of islands (n1) that are entirely contained within the frame, the number of islands (n2) that are recognized as existing within the frame with 1 / 2 or more and less than 1 of the island's area, and the number of islands (n3) that are recognized as existing within the frame with less than 1 / 2 of the island's area. Based on the counted n1, n2, and n3, "n" shown in the following formula (i) is assumed to be the number of islands existing within the frame. n = n1 + (3n2 + n3) / 4 (i) Then, based on the length L [nm] of one side of the frame and the number (n) of islands in the frame calculated by formula (i), "a" shown in the following formula (ii) is calculated as the area [nm 2 ]. The area a [nm 2 ] includes the area of ​​the sea parts, although it is small. However, as is clear from Figs. 5 and 6, the area of ​​the sea parts in the plane is small, and the area a [nm 2 ] and the influence of the sea portion on the metallic luster after molding is so small that it can be ignored, so the influence of the sea portion is ignored in this specification. a=L 2 / n (ii) The above procedure was carried out at 20 locations, and the average value of "a" at the 20 locations was calculated as the area A [nm 2 ].

[0042] The area A per island can be adjusted, for example, by the deposition time (the area A increases as the deposition time increases). Observation with a scanning electron microscope (SEM) is preferably performed after the deposited film has been sufficiently adapted to an environment with a temperature of 23°C ± 5°C and a humidity of 40 to 65%. The accelerating voltage during imaging with a scanning electron microscope (SEM) is preferably in the range of 1 to 5 kV, and the pixel size of the image is preferably 5.0 to 10 nm.

[0043] <<Primer layer>> It is preferable to have a primer layer between the transparent substrate and the metal vapor deposition film in order to improve the adhesion of the metal vapor deposition film. The primer layer can also suppress the difference in thermal behavior in a small area of ​​the transparent substrate from being transmitted to the metal vapor deposition film, and can easily suppress the disorder of the arrangement of the island parts of the metal vapor deposition film when heated before molding. In addition, suppressing the disorder of the arrangement of the island parts of the metal vapor deposition film when heated before molding is effective in that the island parts whose arrangement has been disturbed can easily return to their original state due to the heat applied to the metallic decorative member during molding, which also leads to the recovery of metallic luster.

[0044] The primer layer can be made of various resins, such as acrylic resins, vinyl chloride resins, vinyl acetate resins, polyester resins, and urethane resins. The resin constituting the primer layer is preferably selected from those that enhance adhesion between the transparent substrate and the metal deposition film. For example, when the binder resin of the transparent substrate is an acrylic resin, the primer layer preferably contains an acrylic resin.

[0045] In addition, the primer layer preferably contains a cured product of the resin composition. By containing the cured product of the resin composition in the primer layer, it is possible to further suppress the difference in thermal behavior in a minute region of the transparent substrate from being transmitted to the metal vapor deposition film, and it is possible to easily suppress the arrangement of the islands of the metal vapor deposition film from being disturbed during heating before molding. The cured product of the resin composition may be, for example, a reaction product (cured product) of an acrylic polyol as a base material and an isocyanate compound as a curing agent. The cured product is also suitable in that it can improve adhesion to a transparent substrate containing an acrylic resin as a binder resin.

[0046] The acrylic polyol is not particularly limited as long as it is an acrylic polymer having two or more hydroxyl groups in the molecule. The acrylic polyol is preferably a copolymer obtained by copolymerizing a hydroxyl group-containing acrylate and a copolymerizable vinyl monomer that can be copolymerized with the hydroxyl group-containing acrylate. Examples of hydroxyl group-containing acrylates include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc. Preferred is 2-hydroxyethyl (meth)acrylate, etc. Examples of the copolymerizable vinyl monomer include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, and pentyl (meth)acrylate. Further examples include aromatic vinyls such as styrene, vinyl toluene, and α-methyl styrene; vinyl cyanides such as (meth)acrylonitrile; vinyl monomers containing a carboxyl group such as (meth)acrylic acid, fumaric acid, maleic acid, and itaconic acid; and alkyl esters thereof such as alkane polyol poly(meth)acrylates such as ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylates and copolymerizable vinyl monomers in the presence of a suitable solvent and a polymerization initiator. The number average molecular weight of the acrylic polyol is preferably 5,000 to 50,000, and more preferably 10,000 to 30,000. The number average molecular weight of the acrylic polyol is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).

[0047] As the isocyanate compound, various aromatic and aliphatic isocyanate compounds can be used. It is preferable to use one or more selected from tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). Among these, TDI is more preferable.

[0048] The molar ratio of the isocyanate group of the isocyanate compound to the hydroxyl group of the acrylic polyol (isocyanate group / hydroxyl group) is preferably 0.5 to 5.0, more preferably 0.6 to 3.0, and even more preferably 0.7 to 2.0. By making the molar ratio 0.5 or more, it is possible to easily satisfy condition 1, and by making the molar ratio 5.0 or less, it is possible to easily suppress the occurrence of cracks during molding.

[0049] The thickness of the primer layer is preferably 0.5 to 10 μm, and more preferably 1 to 5 μm. The primer layer may contain additives such as an ultraviolet absorber and a light stabilizer.

[0050] <Other layers> The metallic decorative member may have layers other than those exemplified above.

[0051] <<Protective layer>> The metallic decorative member may have a protective layer on the outer layer side of the metal vapor-deposited film (the outer layer side of the transparent substrate).

[0052] From the viewpoint of scratch resistance, the protective layer preferably contains a cured product of a curable resin composition. Examples of the cured product of the curable resin composition include a cured product of a heat-curable resin composition and a cured product of an ionizing radiation-curable resin composition, and among these, a cured product of an ionizing radiation-curable resin composition is preferred.

[0053] The thermosetting resin composition is a composition that contains at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. In the thermosetting resin composition, a curing agent is added to the curable resin as necessary.

[0054] The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as "ionizing radiation curable compound"). Examples of the ionizing radiation curable functional group include ethylenically unsaturated bond groups such as (meth)acryloyl groups, vinyl groups, and allyl groups, as well as epoxy groups and oxetanyl groups. The ionizing radiation curable resin is preferably a compound having an ethylenically unsaturated bond group. In addition, from the viewpoint of suppressing damage to the resin layer during the manufacturing process of the metallic decorative member, the ionizing radiation curable resin is more preferably a compound having two or more ethylenically unsaturated bond groups, and among them, a polyfunctional (meth)acrylate compound having two or more ethylenically unsaturated bond groups is even more preferable. The polyfunctional (meth)acrylate compound can be either a monomer or an oligomer. Here, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Usually, ultraviolet rays (UV) or electron beams (EB) are used, but other types of radiation, such as electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams, can also be used.

[0055] The thickness of the protective layer is preferably from 0.5 to 30 μm, more preferably from 1 to 20 μm, and further preferably from 3 to 10 μm.

[0056] <<Resin substrate>> It is preferable that the metallized film of the metallic decorative member has a resin substrate on the inner layer side. The resin substrate has a role of, for example, increasing the strength of the metallic decorative member and maintaining the shape of the metallic decorative molded article formed from the metallic decorative member.

[0057] The thickness of the resin substrate is not particularly limited and may be appropriately selected within the range of, for example, 0.1 to 10 mm. Note that the inner layer side of the metal vapor deposition film may have a plurality of resin substrates.

[0058] The resin substrate may be transparent, but in order to suppress surface reflection of the resin substrate, it is preferably achromatic (gray, black) other than white, and more preferably black. For this reason, it is preferable that the resin substrate contains a pigment to make it achromatic. The pigment for the resin substrate may be a black pigment alone, or a mixture of a black pigment and another pigment (such as a white pigment).

[0059] Examples of binder resins for resin substrates include polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, and olefin-based thermoplastic elastomers, ABS (acrylonitrile-butadiene-styrene copolymer) resin, styrene resin, vinyl chloride resin, acrylic resin, and polycarbonate resin. Among these binder resins, it is preferable to contain ABS resin from the viewpoint of suppressing cracks during molding. The proportion of ABS resin in the total binder resin of the resin substrate is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0060] If necessary, any additives such as light stabilizers such as ultraviolet absorbers, plasticizers, fillers, antioxidants, lubricants, and antistatic agents may be added to the resin substrate.

[0061] The resin substrate preferably has a thermal shrinkage of 1.0% or less, more preferably 0.5% or less, and even more preferably 0.1% or less, when heated for 30 minutes at 75° C. By reducing the thermal shrinkage of the resin substrate, it is possible to easily suppress deterioration of metallic luster caused by the resin substrate.

[0062] <<Adhesive layer>> The adhesive layer is a layer formed as necessary to enhance the adhesion of each layer constituting the metallic decorative member. For example, the adhesive layer is preferably disposed between the metal deposition film and the resin substrate. In addition, when there are a plurality of resin substrates, it is preferable to dispose the adhesive layer between the resin substrates. The adhesive layer may be a heat-sensitive adhesive layer (heat seal layer) or a pressure-sensitive adhesive layer (adhesive layer). The pressure-sensitive adhesive layer (adhesive layer) is more preferred due to the simplicity of the lamination process. The heat-sensitive adhesive layer (heat seal layer) is preferred because it is less likely to change shape than the pressure-sensitive adhesive layer (adhesive layer), making it easier to improve the metallic luster after molding.

[0063] As the heat-sensitive or pressure-sensitive resin, general-purpose acrylic resin, urethane resin, polyester resin, silicone resin, vinyl chloride resin, vinyl acetate resin, or a mixture or copolymer of two or more of these can be used. The thickness of the adhesive layer may be adjusted within the range of about 0.1 to 100 μm depending on the type of adhesive.

[0064] <Layer structure of metallic decorative materials> Specific examples of the layered structure of the metallic decorative member include the following (1) to (4). Note that " / " indicates the boundary between layers. The left side indicates the outer layer side of the metallic decorative member, and the right side indicates the inner layer side. (1)Transparent base material / metal deposited film (2) Transparent substrate / primer layer / metal vapor deposition film (3) Transparent base material / metal deposited film / adhesive layer / resin substrate (4) Transparent substrate / primer layer / metal vapor deposition film / adhesive layer / resin substrate

[0065] The member for metallic tone decoration of the present invention preferably further satisfies the following Condition 1. <Condition 1> Using a wave scan device, let the value of image sharpness measured from the outer layer side of the member for metallic tone decoration be D1. Next, dry the member for metallic tone decoration for which D1 has been measured at 75°C for 72 hours. After allowing the surface temperature on the outer layer side of the member for metallic tone decoration to cool to room temperature, using a wave scan device, let the image sharpness measured from the outer layer side of the dried member for metallic tone decoration be D2. Next, vacuum form the member for metallic tone decoration for which D2 has been measured. After allowing the surface temperature on the outer layer side of the member for metallic tone decoration to cool to room temperature, using a wave scan device, let the image sharpness measured from the outer layer side of the vacuum formed member for metallic tone decoration be D3. On such a premise, D2 / D1 < D3 / D1 is shown.

[0066] Showing the relationship of D2 / D1 < D3 / D1 and satisfying Condition 1 indicates that the image sharpness after molding is better than the image sharpness after heating before molding. For example, (1) the image sharpness decreased by heating before molding (drying at 75°C for 72 hours) is recovered by the heat during vacuum molding (the heat when drawing down the member for metallic tone decoration), (2) the image sharpness before and after heating before molding is equivalent, and the image sharpness is improved by vacuum molding, etc. Therefore, by satisfying Condition 1, the metallic luster initially expected can be realized. D3 / D1 is preferably 0.950 or more, and more preferably 0.960 or more. The upper limit of D3 / D1 is not particularly limited, but is about 0.999 in the case of (1) above, and about 1.150 in the case of (2) above. D2 / D1 is preferably 0.880 or more, and more preferably 0.900 or more. The upper limit of D2 / D1 is not particularly limited, but is about 0.990 in the case of (1) above, and about 1.050 in the case of (2) above.

[0067] Furthermore, in the metallic decorative member of the present invention, D3 / D2 is preferably 1.030 or more, and more preferably 1.050 or more. The upper limit of D3 / D2 is not particularly limited, but is about 1.150.

[0068] In condition 1, D1 (image clarity of the metallic decorative member in the initial state) is preferably measured in an environment with a temperature of 23°C ± 5°C and a humidity of 40 to 65%. If the metallic decorative member has another layer such as a resin substrate on the inner layer side of the metallized film and the transparent base material of the metallized film is subjected to high heat in the process of forming the other layer, it is preferable to measure D1 in the configuration before such high heat is applied. High heat is, for example, heat of 70°C or higher. In condition 1, after the metallic decorative member is vacuum-formed, it is preferable to allow it to cool in an environment with a temperature of 23° C.±5° C. and a humidity of 40 to 65%. In condition 1, room temperature means 23° C.±5° C. In Condition 1, the heating conditions during vacuum forming are preferably such that the surface temperature of the metallic decorative member reaches 180° C. in 170 seconds. In addition, under condition 1, the location where D3 is measured is preferably a location where the elongation is 50% or less, more preferably a location where the elongation is 30% or less. At the corners of the unevenness of the molded body, the inclination angle is inflected at the corners. If the measurement area includes an inclined surface where the inclination angle is inflected, accurate measurement of image clarity cannot be expected. For this reason, the location including the area where the inclination angle is inflected is excluded from the measurement of D3. In addition, in condition 1, D1, D2, and D3 are the average values ​​of the measurements at 20 points.

[0069] <Uses for metallic decorative materials> The metallic decorative member of the present invention can be suitably used for various molded articles that require high designability (for example, components for communication devices, interior and exterior parts of vehicles such as automobiles, home appliances, furniture, etc.).

[0070] [Metallic decorative molding] The metallic decorative molding of the present invention is formed from the metallic decorative member of the present invention described above.

[0071] <Method of manufacturing metallic decorative molding> The metallic decorated molded article can be produced, for example, by vacuum molding including the following steps (y1) and (y2). (y1) After placing the metallic decorative member on a mold having a molding surface of a predetermined shape, the metallic decorative member is heated and softened (the metallic decorative member is drawn down on the mold). If the mold is a male mold, the metallic decorative member is placed so that the inner layer side faces the mold (male mold), and if the mold is a female mold, the metallic decorative member is placed so that the outer layer side faces the mold (female mold). (y2) A vacuum is applied from the mold side to bring the softened metallic decorative member into close contact with the molding surface of the mold, thereby forming the metallic decorative member.

[0072] In addition, before the step (y1), a laminate may be prepared by bonding the inner layer side of the metallic decorative member and the adherend, and the laminate may be vacuum molded. In addition, when the metallic decorative member has a resin substrate, it is preferable to perform a moisture removal step by heating before the step (y1). EXAMPLES

[0073] The present invention will be specifically described below with reference to examples and comparative examples. Note that the present invention is not limited to the embodiments described in the examples.

[0074] 1. Measurement and Evaluation The metallic decorative member was subjected to the following evaluations and measurements. The results are shown in Table 1.

[0075] 1-1. Calculation of area A per island of metal deposition film According to the procedure described in the specification, a surface photograph of the metal deposition film of the metal deposition film was taken with a scanning electron microscope (SEM), and the area A [nm2] of each island of the metal deposition film was measured. 2The scanning electron microscope (SEM) used was a Hitachi High-Technologies Corporation model S-4800, with an accelerating voltage of 5 kV, a pixel size of 9.9 nm, and a working distance (WD) of 15.0 mm.

[0076] 1-2. Early metallic luster The metallic luster of the metallic decorative components in their initial state, before they were heated and molded, was evaluated visually. Twenty people evaluated the materials, giving them 2 points for a good metallic luster, 1 point for something that was neither good nor bad, and 0 point for something that was insufficient, and the average score was calculated. Each average score was then ranked according to the following criteria. A: Average score of 1.5 or higher B: Average score is 1.0 or more but less than 1.5 C: Average score is less than 1.0

[0077] 1-3. Changes in clarity of reflections Using a Wave Scan device (manufactured by BYK Japan, product name: Wave Scan Dual AW-4840), image clarity (D1) was measured from the transparent substrate side of the metallic decorative members of Examples 1 to 7 and Comparative Example 1 (metallic decorative members that were not heat-treated before molding). The display item for image clarity on the measuring device is "DOI (Distinctness of Image)". Similarly, image clarity (D2) was measured from the transparent substrate side of the metallic decorative members of Examples 1 to 7 and Comparative Example 1 that were heat-treated before molding. Furthermore, image clarity (D3) was measured for the metallic decorative molded bodies of Examples 1 to 7 and Comparative Example 1. The location for measuring D3 was selected from the area where the elongation rate was 30% or less. "D2 / D1", "D3 / D1" and "D2 / D3" are shown in Table 1. If "D3 / D1" is 0.950 or higher, there is little change in clarity from the initial DOI, and it can be said that the expected metallic luster is maintained after molding. In addition, since the metallic decorative member of Comparative Example 2 had poor initial metallic luster, a series of DOI measurements were not performed.

[0078] 1-4. Metallic luster after molding The metallic luster of the metallic decorative member after molding (the metallic decorative molding produced in "3" below) was visually evaluated. Twenty people evaluated the metallic luster, giving it 2 points for a good metallic luster, 1 point for a neutral metallic luster, and 0 point for an insufficient metallic luster. The average score was calculated. Each average score was then ranked according to the following criteria. AA: Average score of 1.7 or higher A: Average score is between 1.5 and 1.7 B: Average score is 1.0 or more but less than 1.5 C: Average score is less than 1.0

[0079] 2. Manufacturing of metallic decorative parts [Example 1] On a transparent substrate made of a 125 μm-thick acrylic resin film containing acrylic rubber particles (Kaneka product number "015NAH", total light transmittance: 92%, haze: 0.6%, heat shrinkage at 75°C for 30 minutes: 0.5% or less), the following primer layer-forming coating solution 1 was applied and dried to form a primer layer with a thickness of 2 μm. The molar ratio of isocyanate groups to hydroxyl groups in primer layer-forming coating solution 1 was 1:1. Next, a metal deposition film with an area per island of A [nm 2 The deposition time was adjusted so that the value of [Table 1] was obtained, thereby forming an indium deposition film, and a metal deposition film was obtained. Next, 100 parts by mass of an acrylic pressure-sensitive adhesive (manufactured by Soken Chemical & Engineering Co., Ltd., product name: SK Dyne 2094, solid content 25% by mass) was mixed with 0.27 parts by mass of an epoxy crosslinking agent (manufactured by Soken Chemical & Engineering Co., Ltd., product name: E-AX, solid content 5% by mass) to obtain an adhesive layer composition. The adhesive layer composition was applied to the release-treated surface of a silicone release-treated polyester film (manufactured by Toyobo Co., Ltd., product name: E7304) having a thickness of 38 μm so as to have a dried thickness of 40 μm, and then dried to form a pressure-sensitive adhesive layer. Next, the pressure-sensitive adhesive layer and the indium-deposited film side of the metal-deposited film were bonded together to obtain a laminate. The laminate was aged in a 40°C environment for 3 days, and then the 38 μm-thick polyester film that had been silicone-treated for release was peeled off, and the exposed pressure-sensitive adhesive layer was bonded to a resin substrate (a 3.0 mm-thick black ABS resin film with a thermal shrinkage rate of 2% or less at 100°C) to obtain the metallic decorative member of Example 1.

[0080] <Primer layer forming coating liquid 1> Acrylic polyol: 100 parts by weight (Product name: Aracoat DA105, manufactured by Arakawa Chemical Industries, Ltd.) Isocyanate compounds: 40 parts by weight (Product name: Aracoat CL102H, manufactured by Arakawa Chemical Industries, Ltd.) Methyl ethyl ketone: 25 parts by weight Butyl acetate: 20 parts by weight

[0081] [Examples 2 to 3] Area per island A [nm 2 Metallic decorative members of Examples 2 and 3 were obtained in the same manner as in Example 1, except that the value of [CuO2] in the formula was changed to the value in Table 1.

[0082] [Example 4] The primer layer-forming coating solution 1 was applied onto a transparent substrate made of a 125 μm-thick acrylic resin film containing acrylic rubber particles (Sumitomo Chemical Co., Ltd.'s product name "Technoloy (registered trademark) S001G", total light transmittance: 92%, haze: 1.3%, heat shrinkage rate at 100°C for 10 minutes: 0.5% or less), and then dried to form a primer layer with a thickness of 2 μm. Next, a metal deposition film with an area per island of A [nm 2 The deposition time was adjusted so that the value of [Table 1] was obtained, thereby forming an indium deposition film, and a metal deposition film was obtained. Next, a coating solution for the heat-sensitive adhesive layer having the following formulation was applied onto the indium vapor-deposited film so that the thickness after drying was 1.2 μm, and then dried to form a heat-sensitive adhesive layer, thereby obtaining laminate A having a heat-sensitive adhesive layer on the indium vapor-deposited film of the metal vapor-deposited film. Next, the laminate A was placed on a resin substrate (a black ABS resin film having a thickness of 3.0 mm and a thermal shrinkage rate of 2% or less at 100°C) with the heat-sensitive adhesive layer side facing the resin substrate, and the resin substrate and the laminate A were thermally laminated to obtain the metallic decorative component of Example 4.

[0083] <Coating solution for heat-sensitive adhesive layer> This is a mixture of 100 parts by mass of an acrylic heat-sensitive adhesive (manufactured by Showa Ink Industrial Co., Ltd., product name: T-14, solid content 30% by mass) and 5 parts by mass of an isocyanate-based crosslinking agent (manufactured by Showa Ink Industrial Co., Ltd., product name: OP No. 81, solid content 70% by mass).

[0084] [Examples 5 to 7] Area per island A [nm 2 The metallic decorative members of Examples 5 to 7 were obtained in the same manner as in Example 4, except that the value of [CuO2] in the formula was changed to that in Table 1.

[0085] [Comparative Examples 1 to 2] The deposition time was changed to change the area per island A [nm 2 Metallic decorative members of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1, except that the value of [CuO2] was changed to the value in Table 1.

[0086] 3. Heat treatment before molding, production of metallic decorated molded body The metallic decorative members of the examples and comparative examples were heated and dried at 75° C. for 72 hours to remove moisture from the resin substrate. Next, using a mold of the desired shape, the metallic decorative component was placed with the resin substrate (black ABS resin film) side facing the mold and vacuum molded (heating conditions: conditions in which the surface temperature of the resin substrate reached 180°C in 170 seconds) to obtain the metallic decorative molded bodies of Examples 1 to 7 and Comparative Examples 1 to 2. When the obtained metal-decorated molded body was visually observed indoors under fluorescent lighting from the transparent substrate side, no cracks were confirmed in any of them. In addition, the DOI measurements of 1-3 above were performed from the surface on the transparent substrate side of the metal-decorated molded bodies of Examples 1 to 7 and Comparative Example 1.

[0087]

Table 1

[0088] From the results in Table 1, it can be confirmed that the metal-decorated member of the example has D3 / D1 of 0.950 or more, can make the metallic luster of the metal-decorated molded body obtained by molding excellent, and the metallic luster after molding is difficult to decrease. Further, since the metal-decorated member of the example shows D2 / D1 < D3 / D1, it can be confirmed that the sharpness (metallic luster) decreased or maintained by the pre-molding heating is restored by the heat applied to the metal-decorated member during molding. In addition, it can be confirmed that the metal-decorated members of Examples 4 to 7 have more excellent effects described above.

Explanation of Signs

[0089] 10: Metal vapor deposition film 11: Transparent substrate 12: Metal vapor deposition layer 12a: Island part 13: Primer layer 20: Adhesive layer 30: Resin substrate 100: Metal-decorated member

Claims

【Request 1】 A metallic decorative member comprising a transparent substrate and a metal deposition film having a metal deposition film disposed on the transparent substrate, the transparent substrate facing the outer layer side, the transparent substrate being a transparent resin substrate containing rubber particles and a binder resin, the metal deposition film having islands and seas between the islands, each of the islands having an area A of 4,400 to 56,000 nm ２ This is a metallic decorative component.

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