JP6051502B2 - Molded laminate - Google Patents

Description

  The present invention relates to a molding laminate that can be used for the production of a molded article having metallic luster.

  Various decorations such as various color tones, woodgrains, and carbon tones have been applied to various resin molded products such as household appliances such as personal computers and mobile phones, automobile interior and exterior components, and three-dimensional signs. Things are used. In order to express a high-grade appearance, a resin-molded product having a metallic appearance is required.

  As a decorating technique for imparting a metallic appearance to a resin molded product, painting is most commonly used. However, the coating can easily impart various design properties to the molded product, but has a large environmental load due to the use of a large amount of organic solvent, and the metallic brightness is insufficient.

  As another method for imparting a metallic appearance, there is a method in which metal plating is directly applied to a resin molded product. However, this method has a problem that the external appearance has high brightness, but the organic solvent and heavy metals are discharged as waste liquid, so that the environmental load is large as in the case of painting.

  In order to solve these problems, a technique has been proposed in which a metal-deposited film having a metallic luster is used instead of metal plating to give a resin molded product a high-brightness metallic appearance. In this method, a metal vapor-deposited layer is provided on the surface of a plastic film as a substrate, and in some cases, a metal vapor-deposited film in which an adhesive layer is further provided on the surface is used. As a result, a molded product having a metallic appearance is obtained (see Patent Document 1).

JP 2011-68081 A

  However, in Patent Document 1, since the metal vapor deposition layer of the metal vapor deposition film is as thick as 200 nm to 400 nm, an excellent metal-like appearance can be imparted in the case of molding with a small molding rate, that is, with a small film expansion rate. Although it is possible, in the case of molding called deep drawing with a large molding rate, it has been difficult to give a uniform metallic appearance, such as the film stretch rate increases and cracks occur in the metal deposition layer. .

  In addition, in some resin molded products such as three-dimensional molded signboards and automobile decoration members, a so-called backlight configuration is used in which a light source is installed on the back of the resin molded product and design is imparted by transmitted light from the resin molded product. May be used. In this case, with metal plating, light transmission cannot be obtained in the resin molded product, so that transmitted light cannot be obtained, and design properties in the backlight configuration cannot be imparted. And also in the metal vapor deposition film of patent document 1, since a metal vapor deposition layer is thick, there is no light transmittance, and since a metal vapor deposition layer is easy to generate | occur | produce a crack at the time of deep drawing, a uniform metal tone appearance was not obtained. .

  In the present invention, the metallic luster and light transmittance due to the good visible light reflectance before molding can be maintained at a good visible light reflectance even after the so-called deep-draw molding, in which the stretch ratio is large. When a light source from the back of the molded body such as a backlight configuration is used, the molded body can be made to have a metallic luster and good brightness even when used at night by transmitting light through the molded body. An object is to provide a moldable laminate.

The present invention comprises a thermoplastic substrate (A), a light-transmissive metal layer (B) having a thickness of 200 to 800 mm,
And comprising a pressure-sensitive adhesive layer (C) having a maximum laminate reflectance of 40% or more in the wavelength region of 380 to 780 nm and a maximum transmittance of 2 to 30% in the wavelength region of 380 to 780 nm. To do.

  According to the present invention configured as described above, even when the molding laminate is deep-drawn, the metallic luster and light transmittance can be maintained from the good visible light reflectance. Furthermore, even when the molded body is used in a backlight configuration, metallic gloss and good brightness can be obtained.

  The present invention has a metallic gloss and light transmittance due to a good visible light reflectance before molding, which has a large elongation ratio, and a metallic gloss due to maintaining a good visible light reflectance even after so-called deep drawing. can get. Therefore, when a light source from the back of the molded body is used, such as a so-called backlight configuration, the light is transmitted through the molded body, so that a metallic luster and good brightness can be obtained even during night use. A molding laminate capable of molding the body could be provided.

  The molding laminate of the present invention preferably includes a thermoplastic substrate (A), a light-transmissive metal layer (B) having a thickness of 200 to 800 mm, and an adhesive layer (C).

  For example, the thermoplastic base material (A) is preferably a material that does not easily break and is good in elongation, that is, has a good elongation rate, when bonded to the thermoplastic resin sheet (D) as described later. . Specific examples include polyurethane films, polymethyl methacrylate films, acrylonitrile-butadiene-styrene films, polycarbonate films, polyethylene terephthalate films, polypropylene films, polyethylene films, polyvinyl chloride films, fluorine films, and the like. The thickness of the thermoplastic substrate (A) is preferably 20 μm or more and 200 μm or less, and more preferably 25 μm or more and 100 μm or less from the viewpoint of the elongation ratio.

  A thermoplastic base material (A) can be equipped with an easily bonding layer for the purpose of improving adhesiveness with a light-transmissive metal layer (B). The easy adhesion layer is preferably dry treatment such as corona treatment or plasma treatment, or wet treatment using a resin, but wet treatment is more preferred from the viewpoint of adhesion. Examples of the resin include urethane resin, acrylic resin, polyester resin, and vinyl resin. These easy-adhesion layers may be formed by one layer, or may be formed by laminating two or more layers. The method for forming the easy-adhesion layer is not particularly limited, and conventionally known methods such as a gravure coating method and a reverse coating method can be used. The thickness of the easy-adhesion layer is preferably 0.1 μm to 5 μm, more preferably 0.3 μm to 3 μm, from the viewpoints of adhesion and extensibility.

  The thickness of the light transmissive metal layer (B) is preferably 200 mm or more and 800 mm or less, and more preferably 300 mm or more and 600 mm or less. When the thickness of the light transmissive metal layer (B) is 200 mm or more, it becomes easy to achieve both light reflectance and metallic luster. On the other hand, when the thickness is 800 mm or less, the metal layer is less likely to break even in the case of molding with a high stretch rate as in deep drawing.

  Moreover, it is preferable that a light transmissive metal layer (B) contains a columnar crystal. When the metal layer includes columnar crystals, the gap between the columnar crystals transmits light, so that both light reflectance and light transmittance are easily achieved. In addition, when the metal layer stretches a laminate including columnar crystals, the interval between the columnar crystals is widened, so that the metal layer is less likely to break, or the breakage to the extent that can be visually confirmed tends not to occur.

  The light transmissive metal layer (B) can be formed by a known method. For example, a vacuum deposition method, a sputtering method, a high frequency induction heating method, an ion plating method, and the like can be mentioned. In order to form a metal layer with a uniform thickness, a vacuum deposition method or a sputtering method is preferable.

  Moreover, as a metal which can form a light transmissive metal layer (B), what was conventionally used for the metal vapor deposition layer which comprises a metal vapor deposition film can be used, for example, tin, indium, aluminum, zinc, Silver, copper, nickel, titanium and the like, or alloys containing these metals are preferable. Among these, indium, tin, or an alloy such as indium tin (ITO) containing these is preferable from the viewpoints of ease of stretching and metallic gloss.

  The pressure-sensitive adhesive layer (C) is preferably formed by applying a pressure-sensitive adhesive. Specifically, for example, general rubber, synthetic isoprene rubber, recycled rubber, styrene-butadiene rubber, polyisoprene rubber, styrene-isoprene-styrene rubber, etc., rubber adhesive, acrylic adhesive Urethane-based adhesives and silicon-based adhesives can be used.

  The laminate for molding of the present invention preferably has a maximum reflectance of 40% or more and a maximum transmittance of 2 to 30% in a wavelength region of 380 to 780 nm, that is, a visible light region. When the maximum reflectance in the visible light region is 40% or more, an excellent metallic gloss tends to be easily obtained. Furthermore, when the maximum transmittance is 2 to 30%, the metallic gloss tends to be easily obtained while maintaining the light transmittance as the laminate. Therefore, it can be suitably used as a resin molded product having the above-described backlight configuration.

  The laminate for molding of the present invention is further obtained by stretching at least one of the longitudinal direction and the transverse direction of the laminate at 150 ° C. until the length becomes 1.5 times the original length. The reflectance at a wavelength of 380 nm to 780 nm is preferably 50 or more when the reflectance before stretching is 100. When the laminate film has a stretchability in at least one of the vertical direction and the horizontal direction of 1.5 times or more, it becomes easy to cope with deep drawing. When the reflectance at this time is 50 or more when the maximum reflectance before stretching is 100, excellent metallic luster tends to be maintained even after molding stretching.

  In the molding laminate of the present invention, it is preferable that at least one of the thermoplastic substrate (A), the easy-adhesion layer and the pressure-sensitive adhesive layer (C) contains a colorant. Since the laminate for molding contains a colorant, that is, is colored, not only a monotone such as a silver color but also a color tone of gold, bronze, blue metal, red metal, and the like can be obtained. Here, when obtaining a golden or bronze color tone, it is preferable to color the thermoplastic substrate (A) or the easy-adhesion layer. Further, when the pressure-sensitive adhesive layer (C) is colored, when a backlight light source is used for the molded body, a metallic luster is obtained when the light source is not lit, and when the light source is lit, the coloring is taken into account. A metallic gloss is obtained. In other words, it is possible to obtain metallic toning optics with different color tones in the day and night, such as a silver luster due to sunlight and a metallic luster reflecting the color tone of the colorant at night, which could not be realized with conventional metal paints. it can. Therefore, for example, when used for an outdoor signboard, it is easy to obtain a unique design.

  It does not specifically limit as a coloring method, A well-known method can be used. For example, for coloring the thermoplastic substrate (A), a colored thermoplastic substrate (A) can be obtained by mixing an arbitrary colorant, for example, a pigment or a dye, with the thermoplastic resin. Similarly, in the case of coloring the easy-adhesion layer or the pressure-sensitive adhesive layer (C), a colorant is mixed with the resin constituting the easy-adhesion layer or the pressure-sensitive adhesive layer, and each layer is formed to form a colored easy-adhesion layer. And an adhesive layer (C) can be obtained.

  In particular, in order to obtain a golden appearance, it is preferable that at least one of the thermoplastic substrate (A), the easy-adhesion layer and the pressure-sensitive adhesive layer (C) contains a yellow colorant. When at least one of the thermoplastic substrate (A) and the easy-adhesion layer is colored yellow, the appearance of the reflected light is a golden metallic tone. When the pressure-sensitive adhesive layer (C) is colored yellow, the appearance at the time of light transmission is a golden metallic tone. Thereby, it is possible to easily obtain a golden appearance which has been a problem in cost and workability in the conventional metal plating.

The molded body of the present invention is preferably obtained by molding a laminated body including a molding laminate and a thermoplastic resin sheet (D).
As the thermoplastic resin sheet (D), a resin sheet generally used in various molding methods can be used. For example, acrylic, polycarbonate, acrylonitrile-butadiene-styrene (also referred to as ABS), polyethylene terephthalate, polyethylene, polypropylene, Examples thereof include a thermoplastic resin sheet made of a thermoplastic resin such as polyvinyl chloride. Here, the sheet includes a plate-like or film-like form.
The thickness of the thermoplastic resin sheet (D) is preferably 10 μm to 10 mm. And when a sheet | seat (D) is plate shape, 2-6 mm is more preferable, and when a sheet | seat (D) is a film form, 20 micrometers-100 micrometers are more preferable.

  The lamination method of the laminate for molding and the thermoplastic resin sheet (D) is not particularly limited, and examples thereof include a dry lamination method and a wet lamination method. The dry laminating method is a method of directly bonding the molding laminate to the thermoplastic resin sheet (D) using a laminating machine or the like. The wet laminating method is to spray water or soapy water on the bonding surface of the thermoplastic resin sheet and the pressure-sensitive adhesive layer surface of the molding laminate, and then push out the water remaining at the bonding interface with a squeegee or the like. This is a bonding method for reducing the air remaining on the bonding surface.

  The molding method is not particularly limited, and generally known molding methods can be used. Specifically, for example, it can be formed by a vacuum forming method, a vacuum / pressure forming method, or the like. The vacuum forming method and the vacuum / pressure forming method are as follows. First, the pressure-sensitive adhesive layer (C) side surface of the molding laminate is applied to the entire surface or a part of the thermoplastic resin sheet to obtain a laminate, and this laminate is obtained. Install in a predetermined position of the molding machine, heat and soften to the softening temperature of the thermoplastic substrate (D), feed the molding die from below, draw it in vacuum and adhere to the die (vacuum molding method), or draw in vacuum At the same time, it is pressed from the opposite side with compressed air to be brought into close contact with the mold (vacuum / compressed air molding method), and the molded body is removed from the mold after cooling to obtain a molded body.

  The softening temperature (E) of the thermoplastic base material (A) constituting the molded body and the softening temperature (F) of the thermoplastic resin sheet (D) are the softening temperature (E) when the softening temperature (E) is 100. F) is preferably a ratio of 70-80. By adjusting the range of the softening temperature (E) and the softening temperature (F) within the above range, by heating the laminate comprising the molding laminate and the thermoplastic resin sheet (D) to the softening temperature (F). The thermoplastic base material (A) is also sufficiently softened, and the thermoplastic base material (A) and the light transmissive metal layer (B) tend to be less likely to break or crack.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by the following examples.

[Example 1]
An indium vapor-deposited layer having a thickness of 500 mm is formed on one side of a transparent acrylic resin substrate having a thickness of 75 μm and a softening temperature of 100 ° C. by a vacuum vapor deposition method, and a 25 μm acrylic adhesive layer is provided on the vapor-deposited layer. A laminate was obtained.

[Example 2]
An easy-adhesion layer made of urethane resin with a thickness of 0.5 μm is formed on one side of a transparent acrylic resin base material having a thickness of 75 μm and a softening temperature of 100 ° C. by gravure coating, and thickened by vacuum deposition on the easy-adhesion layer. An indium vapor-deposited layer having a thickness of 500 mm was formed, and a 25 μm acrylic pressure-sensitive adhesive layer was further provided on the vapor-deposited layer to obtain a molding laminate.

[Example 3]
Instead of the transparent acrylic resin base material having a thickness of 75 μm and a softening temperature of 100 ° C., a molding laminate was prepared in the same manner as in Example 1 except that a yellow colored acrylic resin base material having a thickness of 75 μm and a softening temperature of 100 ° C. was used. Obtained.

[Comparative Example 1]
A molding laminate was obtained in the same manner as in Example 1 except that an indium deposited layer having a thickness of 2000 mm was formed instead of the 500 mm thick indium deposited layer.

[Comparative Example 2]
A molding laminate was obtained in the same manner as in Example 1 except that an indium vapor deposition layer having a thickness of 50 mm was formed instead of the 500 mm thickness indium vapor deposition layer.

  The following tests were conducted using the molding laminates obtained in Examples 1-3 and Comparative Examples 1-2. The test results are shown in Table 1.

(1) Reflectance and transmittance Using a spectrophotometer “V-570” (manufactured by JASCO Corporation), the light reflectance and light transmittance of the molding laminate in the wavelength region of 380 nm to 780 nm were measured, The maximum reflectance and maximum transmittance in the wavelength region were read and evaluated according to the following five levels. An evaluation score of 3 or higher is a practical level. The light incident surface was the thermoplastic substrate (A) side, the measurement wavelength was 380 nm to 780 nm, and the measurement wavelength width was 2.0 nm.

[Reflectance]
5: 90% or more 4: 60% or more and less than 90% 3: 40% or more and less than 60% 2: 20% or more and less than 40% 1: less than 20%

[Transmissivity]
5: 6% or more but less than 15% 4: 4% or more but less than 6% or 15% or more but less than 20% 3: 2% or more but less than 4% or 20% or more but less than 30% 2: 1% or more but less than 2% or 30% or more Less than 50% 1: 1 or less than 50%

(2) Appearance after stretching The laminate for molding is cut into a width of 40 mm and a length of 100 mm, and attached to a tensile tester with a thermo-hygrostat (manufactured by Tester Sangyo Co., Ltd.) so that the gap between the chucks is 60 mm. Per minute at 150 ° C. in an atmosphere of temperature, the elongation after stretching was 1.5 times (so that the distance between chucks was 90 mm). The appearance after stretching was visually evaluated in five stages. An evaluation score of 3 or higher is a practical level.

[Visual evaluation criteria]
5: Good metallic appearance can be maintained 4: Metal gloss is slightly reduced 3: Metal gloss is slightly reduced, but there are no defects such as cracks in the metal layer 2: Metal gloss is significantly reduced, or metal Cracks occur in the layer 1: Cracks and breaks occur from the substrate

(3) Light reflectance after stretching When the reflectance of the laminate stretched in the appearance test after (2) stretching is measured by the same method as in test (1), and the reflectance before stretching is 100 The reflectance was calculated by the following calculation formula and evaluated in five stages. An evaluation score of 3 or higher is a practical level.

[Reflection calculation formula after stretching]
[Light reflectance after stretching] = [Light reflectance after stretching (%)] / [Light reflectance before stretching (%)] × 100

[Evaluation criteria]
5:80 or more 4:60 or more and less than 80 3:50 or more and less than 60 2:30 or more but less than 50 1:30

[Examples 4-6, Comparative Examples 4-5]
The laminates obtained in Examples 1 to 3 and Comparative Examples 1 and 2 and a transparent acrylic resin sheet (Acrylite E, manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 3 mm are laminated, and a vacuum forming machine “FORMECH300X” Using a Pyramid type with a board surface temperature of 150 ° C (in the shape of the upper part of a regular square pillar cut parallel to the bottom surface, the cut top surface is a square with a side of 7 cm, the bottom surface is a square with a side of 15 cm, and the height is 8 cm. ) To obtain a molded body.

The appearance of the molded bodies obtained in Examples 4 to 6 and Comparative Examples 4 to 5 was visually evaluated in five stages. An evaluation score of 3 or higher is a practical level. The test results are shown in Table 2.
[Visual evaluation criteria]
5: Maintaining a good metallic appearance 4: Slightly decreased metallic luster 3: Although the metallic luster has decreased, there are no defects such as cracks in the metal layer 2: Cracks occurred in the metal layer 1: Base Cracks and breaks from the material

  As shown in Table 1 and Table 2, it can be seen that the molding laminates of Examples 1 to 3 are both light-reflective and light-transmitting and maintain an excellent metallic appearance even after molding. On the other hand, the laminates of Comparative Examples 1 and 2 have insufficient light reflectance and light transmittance, and the appearance after molding extension is inferior.

Claims (11)

A thermoplastic substrate (A);
A light-transmissive metal layer (B) having a thickness of 500 mm ;
Pressure-sensitive adhesive layer and (C) only contains,
For vacuum or vacuum / pneumatic molding, the maximum reflectivity in the wavelength range of 380 to 780 nm measured using a light-transmitting metal layer of 500 mm thickness is 60% or more and the maximum transmittance is 6% or more and less than 15%. Laminated body. The maximum reflectance at a wavelength of 380 to 780 nm when the laminate is stretched in the vertical direction or at least one of the horizontal directions at 150 ° C. until the length becomes 1.5 times longer is the reflectance before stretching. claim 1 Symbol placement of the vacuum or vacuum-pressure molding laminate, characterized in that the 50 or more is 100. The laminate for vacuum or vacuum / pressure forming according to claim 1 or 2, wherein the light transmissive metal layer (B) contains columnar crystals. The laminate for vacuum or vacuum / pressure forming according to any one of claims 1 to 3, wherein the light transmissive metal layer (B) is formed by vapor deposition or sputtering. The laminate for vacuum or vacuum / pressure forming according to any one of claims 1 to 4, wherein the light transmissive metal layer (B) contains at least indium or tin. The laminate for vacuum or vacuum / pressure forming according to any one of claims 1 to 5, wherein the thermoplastic substrate (A) comprises an easy-adhesion layer. The laminate for vacuum or vacuum / pressure forming according to claim 6 , wherein at least one of the thermoplastic substrate (A), the easily adhesive layer and the pressure-sensitive adhesive layer (C) contains a colorant. . The laminate for vacuum or vacuum / pressure forming according to claim 7 , wherein the colorant is a yellow pigment or dye. A vacuum or vacuum / pneumatic molded body formed by molding a laminate including the vacuum or vacuum / pressure forming laminate according to any one of claims 1 to 8 and a thermoplastic resin sheet (D). When the softening temperature (E) of the thermoplastic substrate (A) and the softening temperature (F) of the thermoplastic resin sheet (D) are 100, the softening temperature (F) is 70 to 70. The vacuum or vacuum / pressure-air molded body according to claim 9 , wherein the ratio is 80. On thermoplastic substrate (A), a light permeable metal layer having a thickness of 50 0 Å (B), and will be pressure-sensitive adhesive layer (C) provided, and by using a light-transmitting metal layer having a thickness of 500Å measured A step of producing a vacuum or vacuum / pressure forming laminate having a maximum reflectance in the wavelength region of 380 to 780 nm of 60% or more and a maximum transmittance of 6% or more and less than 15% ;
Bonding the thermoplastic resin sheet (D) and the surface of the pressure-sensitive adhesive layer (C) to produce a laminate; and
Forming the laminate by a vacuum forming method or a vacuum / pressure forming method;
The manufacturing method of the molded object characterized by including.