JP7215045B2 - Laminates and decorative articles - Google Patents

Description

TECHNICAL FIELD The present invention relates to laminates and decorative articles.

2. Description of the Related Art Conventionally, decorative resin molded products obtained by laminating a decorative sheet on the surface of a resin molded product have been used for interior and exterior parts of vehicles, interior materials for building materials, housings of home electric appliances, and the like. In the production of such a decorative resin molded product, a molding method is used in which a decorative sheet having a design provided in advance is integrated with a resin by injection molding. As a representative example of such a molding method, a decorative sheet is previously formed into a three-dimensional shape using a vacuum forming mold, the decorative sheet is inserted into an injection mold, and a fluid resin is injected into the mold. An insert molding method that integrates the resin and the decorative sheet by means of such a method can be used.

Since the decorative resin molded product obtained by such a molding method is used in various applications such as vehicle interior and exterior parts as described above, it has three-dimensional moldability that can follow three-dimensional molding and scratch resistance on the surface. Along with the diversification of consumer tastes in recent years, in addition to surface characteristics such as flexibility, a variety of designs are required. For example, developments have been made to impart a texture to a resin molded product by imparting a matte finish or irregularities to a specific patterned portion (for example, Patent Document 1). In addition, a synthetic resin molded part having a changing design surface has been proposed as one having a variety of design impressions (for example, Patent Document 2).

Furthermore, a decorative sheet has been proposed in which a light source is arranged on the opposite side of the decorative sheet from the viewer's side, and a different design is exhibited when the light source is turned on and when it is turned off (for example, Patent Document 3).

JP 2009-132145 A JP 2010-125817 A JP 2013-14051 A

As described above, there are known decorative sheets that exhibit different designs when the light source is turned on and when the light source is turned off. In such a decorative sheet, when the light source is turned off, it is desirable that the design that appears when the light source is turned on is not visible, and that the design is visible only when the light source is turned on.

However, in the conventional decorative sheet, even when the light source is turned off, the design that appears when the light source is turned on may be visible. In particular, in a decorative sheet in which two design layers are arranged to express different designs when the light source is turned on and when the light source is turned off, a monochromatic design layer is provided on the entire surface on the viewer side, and a patterned design is provided on the light source side. When a layer is provided, there is a problem that the design of the design layer on the light source side is easily visible from the observer side even when the light is turned off, which tends to cause such a problem.

In addition, in the process of preforming the decorative sheet into a three-dimensional shape in advance using a vacuum mold, or in the process of integrating the decorative sheet with the resin by injection molding, etc., high heat and pressure are applied to the decorative sheet. Even if such problems do not occur, problems may occur after molding.

A main object of the present invention is to provide a laminate that exhibits different designs when the light source is turned on and when the light source is turned off. Another object of the present invention is to provide a decorative article using the laminate.

The present inventors have made earnest studies to solve the above problems. As a result, it has a first main surface arranged on the viewer side and a second main surface arranged on the light source side, and at least a transparent base layer and a first design layer are provided in order from the second main surface side. and the second design layer, at least one layer located closer to the first main surface than the transparent substrate layer is provided with an uneven shape, thereby making it difficult for the above problems to occur and preventing It was found that different designs are expressed when the light is off and when the light is off.

The present invention is an invention completed by further studies based on these findings.

That is, the present invention provides inventions in the following aspects.
Section 1. A first main surface arranged on the viewer side and a second main surface arranged on the light source side,
A laminate comprising at least a transparent substrate layer, a first design layer, and a second design layer in order from the second main surface side,
A laminate, wherein at least one layer located closer to the first main surface than the transparent substrate layer is provided with an uneven shape.
Section 2. Item 2. The laminate according to Item 1, wherein the second design layer has the uneven shape.
Item 3. The first design layer has a patterned design,
Item 3. The laminate according to Item 1 or 2, wherein the second design layer has a monochromatic design on the entire surface.
Section 4. 4. The laminate according to any one of items 1 to 3, which has a surface protective layer on the outermost surface on the first main surface side.
Item 5. 5. The laminate according to any one of Items 1 to 4, wherein the uneven shape is provided so as to extend from the second design layer side to the transparent substrate layer.
Item 6. Item 6. The laminate according to any one of Items 1 to 5, wherein the outermost surface of the laminate on the first main surface side has an uneven shape.
Item 7. Item 7. The laminate according to any one of Items 1 to 6, wherein the laminate is in the form of a sheet.
Item 8. Item 8. The laminate according to any one of Items 1 to 7, further comprising a transparent molded resin layer on the second main surface side of the first design layer.
Item 9. A laminate according to any one of Items 1 to 8,
a light source arranged on the second main surface side of the laminate;
A decorative article.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body which expresses a different design when a light source is turned on and when it is turned off can be provided. Furthermore, according to the present invention, it is possible to provide a decorative article using the laminate.

1 is a schematic cross-sectional view of an example of a laminate of the present invention; FIG. 1 is a schematic cross-sectional view of an example of a laminate of the present invention; FIG. 1 is a schematic cross-sectional view of an example of a laminate of the present invention; FIG. 1 is a schematic cross-sectional view of an example of a laminate of the present invention; FIG. 1 is a schematic cross-sectional view of an example of a laminate of the present invention; FIG. 1 is a schematic cross-sectional view of an example of a laminate of the present invention; FIG. 1 is a schematic cross-sectional view of an example of a decorative article using the laminate of the present invention; FIG.

1. Laminate The laminate of the present invention has a first main surface arranged on the viewer side and a second main surface arranged on the light source side, and at least a transparent substrate layer is provided in order from the second main surface side. and a laminate comprising a first design layer and a second design layer, wherein at least one layer located closer to the first main surface than the transparent substrate layer is provided with an uneven shape. Characterized by By having such a configuration, the laminate of the present invention can exhibit different designs when the light source is turned on and when the light source is turned off.

The laminate of the present invention can be suitably used for decorating the surface of resin molded products such as vehicle interior and exterior parts, building interior materials, home appliance housings, and the like. Therefore, the laminate of the present invention can be suitably used as a decorative sheet for three-dimensional molding. In particular, when the laminate of the present invention is in the form of a sheet, it can be molded as a decorative sheet for three-dimensional molding, and laminated with a molded resin layer 4 described later to form a suitably decorated resin molded product.

The laminate of the present invention will be described in detail below with reference to FIGS. 1 to 7. FIG. In this specification, the numerical range indicated by "-" means "above" and "below", except where "above" and "below" are specified. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, in this specification, "(meth)acrylate" means "acrylate or methacrylate", and other similar terms have the same meaning.

Laminated Structure of Laminate The laminate 10 of the present invention has, for example, as shown in FIGS. 12. Specifically, when the laminate 10 of the present invention is used for various applications such as vehicle interior and exterior parts, building interior materials, home appliance housings, etc., the first main surface 11 is arranged on the viewer side, Two main surfaces 12 are arranged on the light source side.

The laminate 10 of the present invention is composed of a laminate including at least a transparent substrate layer 1, a first design layer 21, and a second design layer 22 in order from the second main surface 12 side. In addition, in the laminate 10 of the present invention, at least one layer positioned closer to the first main surface 11 than the transparent substrate layer 1 is provided with an uneven shape.

As shown in FIGS. 1 to 7, different designs appear when the light source is turned on and when the light source is turned off. When the light source is turned off, the design based on the second design layer 22 is visible and the design based on the first design layer 21 is visible. From the viewpoint of making it difficult to see, it is preferable that at least the second design layer 22 has an uneven shape. Since light is scattered by the second design layer 22 having an uneven shape, the design based on the first design layer 21 becomes difficult to see when the light is turned off.

When the second design layer 22 has an uneven shape, the uneven shape may be provided on the first main surface 11 side as shown in FIG. 1, or may be provided on the second main surface 12 side as shown in FIG. Alternatively, as shown in FIGS. 3 to 7, it may be provided on both the first main surface 11 side and the second main surface 12 side. Further, as shown in FIG. 1 or FIG. 3, the outermost surface on the first main surface side of the laminate 10 of the present invention may be provided with an uneven shape.

Moreover, in the laminate 10 of the present invention, the first design layer 21 may have an uneven shape. When the first design layer 21 has an uneven shape, the uneven shape is preferably provided at least on the first main surface 11 side, as shown in FIGS. Moreover, as shown in FIGS. 4 to 7, it is also preferable that the uneven shape is provided on both the first main surface 11 side and the second main surface 12 side. The uneven shape of the first design layer 21 corresponds to, for example, the uneven shape of the second design layer 22 .

Furthermore, in the laminate 10 of the present invention, the transparent substrate layer 1 may have an uneven shape. When the transparent substrate layer 1 has an uneven shape, the uneven shape is preferably provided on the first main surface 11 side, as shown in FIGS. The uneven shape of the transparent substrate layer 1 corresponds to, for example, the uneven shape of the first design layer 21 and the uneven shape of the second design layer 22 . That is, in the laminate 10 of the present invention, the uneven shape of the second design layer 22 can be provided so as to extend from the second design layer 22 side to the transparent substrate layer 1 .

In the laminate 10 of the present invention, the uneven shape of each layer can be provided by, for example, embossing as described later.

For example, as shown in FIGS. 3 to 7, in the laminate 10 of the present invention, for the purpose of imparting surface protection performance such as scratch resistance and chemical resistance to the surface, a A surface protective layer 3 may be provided on (the first main surface 11 side). A primer layer (not shown) may be provided as necessary for the purpose of improving the adhesion between the surface protective layer 3 and the underlying layer (second design layer 22, etc.). good. Furthermore, for example, as shown in FIG. 6, when the molded resin layer 4 is laminated on the second main surface 12 side of the transparent substrate layer 1, the adhesion between the laminate 10 of the present invention and the molded resin layer 4 is For the purpose of increasing the strength, a back surface adhesive layer (not shown) may be provided on the second main surface 12 side of the transparent substrate layer 1 (the back surface side of the transparent substrate layer 1), if necessary. .

One or more other layers may be further laminated on the laminate of the present invention depending on the function to be imparted to the laminate or the decorative article.

As the laminate structure of the laminate of the present invention, a laminate structure in which a transparent substrate layer/first design layer/second design layer are laminated in this order; transparent substrate layer/first design layer/second design layer/surface protection. Laminated structure in which layers are laminated in this order; laminated structure in which molded resin layer/transparent substrate layer/first design layer/second design layer/surface protective layer are laminated in this order; molded resin layer/transparent substrate layer/ Laminated structure in which first design layer/second design layer/primer layer/surface protective layer are laminated in this order; molded resin layer/back adhesive layer/transparent substrate layer/first design layer/second design layer/primer layer / A laminated structure in which surface protective layers are laminated in this order. 1 to 3 are schematic cross-sectional views of an example of a laminate in which a transparent substrate layer/first design layer/second design layer are laminated in this order, as one aspect of the laminate structure of the laminate of the present invention. show. 4 and 5 schematically show an example of a laminate in which a transparent substrate layer/first design layer/second design layer/surface protective layer are laminated in this order, as one aspect of the laminate structure of the laminate of the present invention. A cross-sectional view is shown. FIG. 6 shows an example of a laminate in which a molded resin layer/transparent substrate layer/first design layer/second design layer/surface protective layer are laminated in this order, as one aspect of the laminate structure of the laminate of the present invention. 1 shows a schematic cross-sectional view; FIG.

Each layer forming the laminate [transparent substrate layer 1]
The transparent substrate layer 1 is a layer provided to impart rigidity to the laminate 10 to retain its shape. Moreover, when the laminate 10 is in the form of a sheet, it is provided to make the laminate suitable for vacuum forming (three-dimensional forming) by an insert molding method or the like.

As shown in FIG. 7, the transparent base material layer 1 is transparent enough to transmit light from the light source when the light source 30 is arranged on the second main surface 12 side (in the present invention, transparent means semi-transparent). (including transparency). That is, the transparent base material layer 1 is usually transparent (colorless transparent, colored transparent, semi-transparent), and when the laminate 10 of the present invention is observed from the first main surface 11 side, the first design layer 1 at the time of lighting. 21 may be colored as long as the design is visible. For example, the transparent substrate layer 1 may contain a matting agent such as silica, a coloring agent, or the like. As the coloring agent, the coloring agents exemplified for the first design layer 21 described later can be used. In addition, the transparent substrate layer 1 may be coated for adjusting the color, formed with a pattern for imparting a design property, or the like.

As described above, the transparent substrate layer 1 may have an uneven shape. When the transparent substrate layer 1 has an uneven shape, the uneven shape is preferably provided on the first main surface 11 side, as shown in FIGS. The uneven shape of the transparent substrate layer 1 corresponds to, for example, the uneven shape of the first design layer 21 and further the uneven shape of the second design layer 22, which will be described later. That is, in the laminate 10 of the present invention, the uneven shape can be provided so as to extend from the second design layer 22 side to the transparent substrate layer 1 .

The transparent base material layer 1 is made of a transparent resin, a paper base material, or the like, from the viewpoint of making the laminate 10 suitable for three-dimensional molding and suitably expressing different designs when the light source is turned on and when the light source is turned off. be able to. The transparent resin is preferably made of a transparent thermoplastic resin. Examples of transparent thermoplastic resins include, but are not limited to, transparent acrylonitrile-butadiene-styrene resins (hereinafter sometimes referred to as "ABS resin"), acrylic resins; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resin; polyethylene terephthalate (PET) resin; acrylonitrile-styrene-acrylic acid ester resin; Among these materials, the transparent substrate layer 1 is preferably made of transparent ABS resin. The number of resins forming the transparent substrate layer 1 may be one, or two or more.

The thickness of the transparent base material layer 1 is not particularly limited, but from the viewpoint of making the laminate 10 suitable for three-dimensional molding and suitably expressing different designs when the light source is turned on and when the light source is turned off, the lower limit is is preferably 50 μm or more, more preferably 100 μm or more, and the upper limit is preferably 1000 μm or less, more preferably 500 μm or less, and preferable ranges are about 50 to 1000 μm and about 100 to 500 μm. be done. More specifically, when a transparent ABS resin is used as the transparent substrate layer 1, the thickness is more preferably about 100 to 500 μm, still more preferably 200 to 400 μm. In addition, when the transparent base material layer 1 has uneven|corrugated shape, the thickness of the transparent base material layer 1 is the thickness in the position of the convex part of uneven|corrugated shape.

In order to improve adhesion with adjacent layers, the transparent substrate layer 1 may optionally be subjected to a physical or chemical surface treatment such as an oxidation method or a roughening method on one or both sides thereof. good. Examples of the oxidation method for the surface treatment of the transparent substrate layer 1 include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment, and the like. Further, examples of the roughening method performed as the surface treatment of the transparent substrate layer 1 include a sandblasting method, a solvent treatment method, and the like. These surface treatments are appropriately selected according to the type of resin constituting the transparent substrate layer 1, but from the viewpoint of effects, operability, etc., a corona discharge treatment method is preferred.

[First design layer 21]
The first design layer 21 is a layer provided on the transparent substrate layer 1 for the purpose of imparting decorativeness to the laminate 10 . The design of the first design layer 21 is a design visible from the first main surface 11 side when the light source on the second main surface 12 side is turned on, and when the light source is turned off, the design of the first design layer 21 is The design of the second design layer 22 is visually recognized, and is difficult to be visually recognized from the first main surface 11 side.

The first design layer 21 can be, for example, a layer in which a desired pattern is formed using an ink composition. For example, when the first design layer 21 has a patterned design and the second design layer 22 described later has a monochromatic design on the entire surface, when the light source is turned off, the entire surface of the second design layer 22 is monochromatic. The design is visually recognized, but the design of the first design layer 21 is not visually recognized, and when the light source is turned on, the pattern-like design of the first design layer 21 (for example, a pattern described later such as a symbol or character information) is visually recognized. It is possible to configure as follows.

The first design layer 21 may be partially provided on the transparent substrate layer 1 or may be provided entirely.

The first design layer 21 can be formed, for example, by printing ink for forming the first design layer on the transparent substrate layer 1 by a conventionally known printing method such as gravure printing, silk screen printing, or offset printing. can. As the ink composition used to form the first design layer 21, a mixture of a binder, a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. is used. be done.

The binder used in the ink composition is not particularly limited, but examples include polyurethane resins, vinyl chloride/vinyl acetate copolymer resins, vinyl chloride/vinyl acetate/acrylic copolymer resins, chlorinated polypropylene resins, and acrylic resins. , polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins, and the like. These binders may be used singly or in combination of two or more.

Colorants used in the ink composition are not particularly limited, but examples include carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue. organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metal pigments consisting of scale-like foil pieces such as aluminum and brass; scale-like foils such as titanium dioxide-coated mica and basic lead carbonate A pearl luster (pearl) pigment consisting of flakes and the like can be mentioned.

The pattern formed by the first design layer 21 is also not particularly limited, but may be, for example, symbols, character information, or even a grain pattern imitating the surface of a rock such as a wood grain pattern or a marble pattern (for example, a travertine marble pattern). , fabric patterns that imitate textures and cloth-like patterns, tile patterns, brickwork patterns, etc., and may be patterns such as marquetry and patchwork that combine these, or monochromatic solid colors (so-called full solid) may be These patterns are formed by multi-color printing using the usual process colors of yellow, red, blue, and black, but they can also be formed by special-color multi-color printing by preparing individual color plates that make up the pattern. can be formed.

Also, the first design layer 21 may include a portion composed of a metal thin film. Examples of metals forming the metal thin film include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. The method for forming the metal thin film is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above metals. Further, in order to improve adhesion with adjacent layers, a primer layer using a known resin may be provided on the front and rear surfaces of the metal thin film.

Further, as described above, the first design layer 21 may have an uneven shape. When the first design layer 21 has an uneven shape, the uneven shape is preferably provided at least on the first main surface 11 side, as shown in FIGS. Moreover, as shown in FIGS. 4 to 7, it is also preferable that the uneven shape is provided on both the first main surface 11 side and the second main surface 12 side. The uneven shape of the first design layer 21 corresponds to, for example, the uneven shape of the second design layer 22 described later.

The thickness of the first design layer 21 is not particularly limited, but the lower limit is preferably 1 μm or more, and the upper limit is preferably 30 μm or less, more preferably 20 μm or less. about 30 μm, and about 1 to 20 μm. In addition, when the first design layer 21 has an uneven shape, the thickness of the first design layer 21 is the thickness at the position of the convex portion of the uneven shape.

[Second design layer 22]
The second design layer 22 is a layer provided on the transparent substrate layer 1 and the first design layer 21 for the purpose of imparting decorativeness to the laminate. The design of the second design layer 22 is a design that is visible from the first main surface 11 side when the light source on the second main surface 12 side is turned off, and when the light source is turned on, the design of the first design layer 21 is It is visually recognized through the second design layer 22 .

Different designs are expressed when the light source is turned on and when it is turned off, and when the light source is turned off, the design based on the second design layer 22 is visible, and the design based on the first design layer 21 is difficult to be seen. As described above, at least the second design layer 22 preferably has an uneven shape. Since light is scattered by the second design layer 22 having an uneven shape, the design based on the first design layer 21 becomes difficult to see when the light is turned off.

When the second design layer 22 has an uneven shape, the uneven shape may be provided on the first main surface 11 side as shown in FIG. 1, or may be provided on the second main surface 12 side as shown in FIG. Alternatively, as shown in FIGS. 3 to 7, it may be provided on both the first main surface 11 side and the second main surface 12 side.

From the viewpoint of making the design based on the second design layer 22 visible and the design based on the first design layer 21 less visible when the light source is turned off, the The depth D of the uneven concave portion of the second design layer 22 is preferably about 5 to 100 μm, more preferably 8 to 80 μm. The depth of the recess can be measured, for example, by cross-sectional observation with a microscope. The depth D of the recess is the height from the recess to the projection of the second design layer 22 on the first main surface 11 side, as shown in FIG. The depth D of the concave portion is appropriately adjusted according to the thickness of the second design layer 22 and the like.

From the same point of view, the width W of the concave portion of the uneven shape of the second design layer 22 is preferably about 50 to 500 μm, more preferably about 300 to 500 μm. The width W of the recess can be measured, for example, by cross-sectional observation with a microscope. The width W of the recess is the distance between adjacent protrusions of the second design layer 22 on the first main surface 11 side, as shown in FIG.

The uneven shape of the second design layer 22 can be preferably formed by, for example, embossing. For example, in the case of providing an uneven shape on the first main surface 11 side, a laminate in which at least the transparent substrate layer 1, the first design layer 21, and the second design layer 22 are laminated is prepared. By applying embossing from the main surface 11 side, an uneven shape can be formed on the first main surface 11 side of the second design layer 22 . At this time, by adjusting the depth of the recesses formed by embossing, it is possible to form uneven shapes in the first design layer 21 and the transparent substrate layer 1 by one embossing. Also, a laminate of the transparent substrate layer 1 and the first design layer 21 is prepared, embossing is performed from the first design layer 21 side to form an uneven shape on the first design layer 21, and the second design is formed thereon. By stacking layers 22, it is possible to form the second design layer 22 having an uneven shape on the second main surface 12 side.

Embossing is a known method, for example, a method in which a heat-softened layer is pressed with an embossing plate to shape the uneven pattern formed on the embossing plate on the surface of the laminate, cooled, and fixed. . A known sheet-fed or rotary embossing machine can be used for embossing.

Even when other layers such as the surface protective layer 3 and the primer layer are provided, for example, a laminate obtained by laminating these layers on the transparent substrate layer 1 is embossed to form an uneven shape. , these layers can also have an uneven shape.

The second design layer 22 can be, for example, a layer in which a desired pattern is formed using an ink composition. As described above, for example, when the second design layer 22 has a monochromatic design on the entire surface and the first design layer 21 has a patterned design, when the light source is turned off, the entire surface of the second design layer 22 The monochromatic design is visually recognized and the design of the first design layer 21 is not visually recognized, and when the light source is turned on, the patterned design of the first design layer 21 (for example, the above-mentioned patterns such as symbols and character information) is visible. It can be configured to be visible.

The second design layer 22 may be partially provided on the transparent substrate layer 1 or may be provided over the entire surface, but is preferably provided over the entire surface.

As with the first design layer 21, the second design layer 22 is formed by, for example, applying ink for forming the second design layer to the first design layer 21 by a conventionally known printing method such as gravure printing, silk screen printing, or offset printing. can be formed by printing on the Examples of the ink composition used for forming the second design layer 22 are the same as those exemplified for the first design layer 21, including binders, colorants, and the like.

Examples of the pattern formed by the second design layer 22 are the same as those exemplified for the first design layer 21, but as described above, the second design layer 22 has a monochromatic design on the entire surface. preferably.

Also, the second design layer 22 may include a portion composed of a metal thin film. As for the metal forming the metal thin film and the forming method, the same ones as those exemplified for the first design layer 21 are exemplified.

The thickness of the second design layer 22 is not particularly limited. Up to about 20 μm and about 1 to 10 μm can be mentioned. In addition, when the second design layer 22 has an uneven shape, the thickness of the second design layer 22 is the thickness at the position of the convex portion of the uneven shape.

[Surface protective layer 3]
The surface protective layer 3 is a layer provided as necessary to protect the surface of the laminate 10 . As described above, even when the laminate 10 has the surface protective layer 3, the laminate obtained by laminating the surface protective layer 3 and the like on the transparent substrate layer 1 is embossed to form an uneven shape. , the surface protective layer 3 can be formed with an uneven shape. Therefore, as shown in the schematic diagrams of FIGS. 4 to 7, the surface protective layer 3 may have an uneven shape. The uneven shape may be provided on the first main surface 11 side, may be provided on the second main surface 12 side, or may be provided on the first main surface 11 side and the second main surface. It may be provided on both sides of the 12 side.

In the laminate 10 of the present invention, the surface protective layer 3 may be provided on the entire surface of the first main surface 11 side, or may be provided partially. However, from the viewpoint of suitably protecting the surface of the laminate 10, it is preferable that the surface protective layer 3 is provided on the entire surface on the first main surface 11 side.

In addition, the surface protective layer 3 is usually transparent (colorless transparent, colored transparent, translucent), but when the laminate 10 of the present invention is observed from the first main surface 11 side, when the light source is turned on, the first As long as the design of the design layer 21 can be visually recognized, it may be colored or may contain a matting agent such as silica. As the coloring agent, the coloring agents exemplified for the first design layer 21 described above can be used.

Materials constituting the surface protective layer 3 are not particularly limited, and examples thereof include thermoplastic resins, thermosetting resins, and ionizing radiation-curable resins. Among these, the surface protective layer 3 is preferably composed of a cured product of an ionizing radiation-curable resin composition from the viewpoint of improving scratch resistance and the like. The ionizing radiation-curable resin used for forming the surface protective layer 3 will be described in detail below.

(Ionizing radiation curable resin)
The ionizing radiation-curable resin used for forming the surface protective layer 3 is a resin that crosslinks and cures when irradiated with ionizing radiation. A suitable mixture of at least one of prepolymers, oligomers, and monomers having Here, the ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used. ray, electromagnetic waves such as γ-rays, charged particle beams such as α-rays and ion beams. Among ionizing radiation curable resins, electron beam curable resins are suitable for forming the surface protective layer 3 because they can be solvent-free, require no photopolymerization initiator, and provide stable curing properties. used for

As the monomer used as the ionizing radiation-curable resin, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and a polyfunctional (meth)acrylate monomer is particularly preferable. The polyfunctional (meth)acrylate monomer may be a (meth)acrylate monomer having two or more (difunctional or more), preferably three or more (trifunctional or more) polymerizable unsaturated bonds in the molecule. Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di( meth) acrylate, neopentyl glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, neopentyl glycol hydroxypivalate di(meth) acrylate, dicyclopentanyl di(meth) acrylate, caprolactone-modified dicyclopentenyl di( meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate , dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate , propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. These monomers may be used singly or in combination of two or more.

In addition, as the oligomer used as the ionizing radiation-curable resin, a (meth)acrylate oligomer having a radically polymerizable unsaturated group in the molecule is suitable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth)acrylate oligomer having (2 or more functionalities) is preferred. Examples of polyfunctional (meth)acrylate oligomers include polycarbonate (meth)acrylate, acrylic silicone (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. , polybutadiene (meth)acrylate, silicone (meth)acrylate, oligomers having a cationic polymerizable functional group in the molecule (e.g., novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.). . Here, the polycarbonate (meth)acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth)acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid. Polycarbonate (meth)acrylate may be, for example, urethane (meth)acrylate having a polycarbonate skeleton. A urethane (meth)acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and a hydroxy (meth)acrylate. Acrylic silicone (meth)acrylates can be obtained by radically copolymerizing silicone macromonomers with (meth)acrylate monomers. Urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate compound with (meth)acrylic acid. Epoxy (meth)acrylate can be obtained, for example, by reacting (meth)acrylic acid with an oxirane ring of a relatively low-molecular-weight bisphenol-type epoxy resin or novolac-type epoxy resin for esterification. A carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic acid anhydride can also be used. Polyester (meth)acrylate is obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyhydric carboxylic acid and polyhydric alcohol with (meth)acrylic acid, or to polyhydric carboxylic acid. It can be obtained by esterifying the terminal hydroxyl group of the oligomer obtained by adding alkylene oxide with (meth)acrylic acid. Polyether (meth)acrylate can be obtained by esterifying the hydroxyl groups of polyether polyol with (meth)acrylic acid. Polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of polybutadiene oligomer. A silicone (meth)acrylate can be obtained by adding (meth)acrylic acid to the terminal or side chain of a silicone having a polysiloxane bond in its main chain. These oligomers may be used singly or in combination of two or more.

Among the above-mentioned ionizing radiation-curable resins, polycarbonate (meth)acrylate is used from the viewpoint of obtaining superior three-dimensional moldability while further improving the appearance of the design, wear resistance, and moldability. is preferred. It is also preferable to use a combination of polycarbonate (meth)acrylate and urethane (meth)acrylate.

(other additive ingredients)
Various additives can be added to the surface protective layer 3 according to the desired physical properties of the surface protective layer 3 . Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents, colorants and the like. These additives can be appropriately selected and used from commonly used ones. As the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used.

(Formation of surface protective layer 3)
Formation of the surface protective layer 3 having an uneven shape is performed, for example, by preparing an ionizing radiation-curable resin composition containing an ionizing radiation-curable resin, applying this to form an uncured resin layer, and then forming the uncured resin layer. It can be carried out by cross-linking curing.

The viscosity of the ionizing radiation-curable resin composition may be any viscosity that allows the formation of an uncured resin layer by the application method described below.

In the present invention, the prepared resin is applied by known methods such as gravure coating, bar coating, roll coating, reverse roll coating and comma coating, preferably gravure coating, to form an uncured resin layer.

The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer, thereby forming the surface protective layer 3 . Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the thickness of the resin and the layer used, but the acceleration voltage is usually about 70 to 300 kV.

In electron beam irradiation, the higher the acceleration voltage, the higher the penetration ability. The acceleration voltage is chosen so that the thickness of layer 3 is substantially equal. As a result, it is possible to suppress the irradiation of excess electron beams to the layers located under the surface protective layer 3, and to minimize the deterioration of each layer due to the excess electron beams.

The irradiation dose is preferably an amount that saturates the crosslink density of the surface protective layer 3, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

Furthermore, the electron beam source is not particularly limited, and various electron beam accelerators such as Cockroft-Walton type, Vandegraft type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. can be used.

When ultraviolet rays are used as the ionizing radiation, rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. Examples of ultraviolet light sources include, but are not limited to, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps.

By adding various additives to the thus formed surface protective layer 3, a hard coating function, an anti-fog coating function, an antifouling coating function, an anti-glare coating function, an anti-reflection coating function, an ultraviolet shielding coating function, A process for imparting a function such as an infrared shielding coating function may be performed.

The thickness of the surface protective layer 3 is not particularly limited, but from the viewpoint of imparting surface protection performance such as surface scratch resistance and chemical resistance, the lower limit is preferably 5 μm or more, more preferably 10 μm or more. The upper limit is preferably 30 μm or less, more preferably 20 μm or less, and preferable ranges are about 5 to 20 μm, about 5 to 10 μm, and about 5 to 15 μm.

[Primer layer]
The primer layer is provided on the second main surface 12 side of the surface protective layer 3 (the second design layer 22 side) as necessary for the purpose of improving the adhesion between the surface protective layer 3 and the underlying layer. ) is a layer provided so as to be in contact with the surface of the

Examples of the primer composition constituting the primer layer include urethane resin, (meth)acrylic resin, (meth)acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, A resin containing chlorinated polyethylene or the like as a binder resin is preferably used, and these resins can be used singly or in combination of two or more. Among these, urethane resins, (meth)acrylic resins, and (meth)acrylic-urethane copolymer resins are preferred.

As the urethane resin, a polyurethane containing polyol (polyhydric alcohol) as a main component and isocyanate as a cross-linking agent (curing agent) can be used. As the polyol, those having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used. Examples of the isocyanate include polyisocyanates having two or more isocyanate groups in the molecule, aromatic isocyanates such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as are used. It is also possible to mix urethane resin and butyral resin.

A combination of acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a cross-linking agent is preferred, and a combination of acrylic polyol and hexamethylene diisocyanate is particularly preferred.

The (meth)acrylic resin may be a homopolymer of a (meth)acrylic acid ester, a copolymer of two or more different (meth)acrylic acid ester monomers, or a copolymer of a (meth)acrylic acid ester and another monomer. Polymers include, specifically, polymethyl (meth)acrylate, polyethyl (meth)acrylate, poly(meth)propyl acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate- Butyl (meth)acrylate copolymer, ethyl (meth)acrylate-butyl (meth)acrylate copolymer, ethylene-methyl (meth)acrylate copolymer, styrene-methyl (meth)acrylate copolymer A (meth)acrylic resin comprising a homopolymer or a copolymer containing a (meth)acrylic acid ester such as is preferably used.

As the (meth)acrylic-urethane copolymer resin, for example, an acrylic-urethane (polyester urethane) block copolymer resin is preferable. As the curing agent, the various isocyanates described above are used. If desired, the acrylic/urethane ratio (mass ratio) of the acrylic-urethane (polyester urethane) block copolymer resin is preferably adjusted within the range of 9/1 to 1/9, more preferably 8/2 to 2/8. is preferred.

Although the thickness of the primer layer is not particularly limited, it is, for example, about 0.5 to 20 μm, preferably about 1 to 5 μm.

The primer layer is formed by gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheel coating, dip coating, solid coating by silk screen, wire bar coating, and flow coating using the primer composition. It is formed by a normal coating method such as coating, comma coating, flow coating, brush coating, spray coating, or a transfer coating method. Here, the transfer coating method is a method in which a coating film such as a primer layer or an adhesive layer is formed on a thin sheet (film substrate), and then the surface of the target layer in the laminate is coated.

[Back adhesive layer]
The back surface adhesive layer (not shown) is formed on the transparent substrate layer 1 for the purpose of enhancing adhesion with the molded resin layer 4 when the laminated body 10 is molded when the molded resin layer 4 is provided on the laminated body 10. is a layer provided on the second main surface 12 side of (the side opposite to the first design layer 21) as necessary.

A thermoplastic resin or a curable resin is used for the back adhesive layer according to the type of the molding resin layer 4 used in the laminate 10 .

Thermoplastic resins used for forming the back adhesive layer include, for example, acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride/vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, and polyamides. Resins, rubber-based resins, and the like can be mentioned. These thermoplastic resins may be used singly or in combination of two or more.

Thermosetting resins used for forming the back adhesive layer include, for example, urethane resins and epoxy resins. These thermosetting resins may be used singly or in combination of two or more.

The thickness of the back adhesive layer is not particularly limited as long as the molded resin layer 4 can be adhered thereon, and is, for example, about 0.1 to 20 μm.

[Molding resin layer 4]
In the laminate 10 of the present invention, the transparent molding resin layer 4 may be integrated with the second main surface 12 side of the transparent substrate layer 1 and molded. That is, as shown in FIG. 6, the laminate 10 of the present invention comprises at least a molded resin layer 4, a transparent substrate layer 1, a first design layer 21, and a second design layer 22 in this order. At least one layer which consists of a body and is located on the first main surface 11 side of the transparent substrate layer 1 may be provided with an uneven shape. As with the transparent substrate layer 1 , the molded resin layer 4 is transparent enough to transmit the light from the light source when the light source 30 is arranged on the second main surface 12 side. That is, the molded resin layer 4 is usually transparent (colorless transparent, colored transparent, translucent), and when the laminate 10 of the present invention is observed from the first main surface 11 side, the first design layer 21 As long as the design is visible, it may be colored. For example, the molded resin layer 4 may contain a matting agent such as silica, a coloring agent, or the like. As the coloring agent, the coloring agents exemplified for the first design layer 21 described above can be used.

The molded resin layer 4 can be made of a transparent resin or the like. The transparent resin is preferably made of a transparent thermoplastic resin. Examples of transparent thermoplastic resins include, but are not limited to, transparent acrylonitrile-butadiene-styrene resins (hereinafter sometimes referred to as "ABS resin"), acrylic resins; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; Vinyl chloride resin; polyethylene terephthalate (PET) resin; acrylonitrile-styrene-acrylic acid ester resin and the like. Among these, the molded resin layer 4 is preferably made of a polycarbonate resin because of its excellent transparency. The number of resins forming the transparent substrate layer 1 may be one, or two or more. Further, examples of the shape of the molded resin layer 4 include a plate-like body and a molded body.

The laminate 10 including the molded resin layer 4 is produced by laminating by a known method so that the surface on the transparent substrate layer 1 side faces the molded resin layer 4 . When the molding resin layer 4 is a resin molding, it may be produced by an injection molding method such as an insert molding method.

In the insert molding method, first, in a vacuum forming step, a laminated body before lamination of the molded resin layer 4 (that is, from the second main surface 12 side, at least the transparent substrate layer 1, the first design layer 21, The laminate including the second design layer 22) is previously vacuum-formed (off-line pre-forming) into the surface shape of the molded article using a vacuum molding die, and then, if necessary, the excess portion is trimmed to obtain a molded sheet. This molding sheet is inserted into an injection mold, the injection mold is clamped, and a resin in a fluid state is injected into the mold from the transparent base material layer 1 side of the laminate and solidified, and the resin is injected and molded at the same time. The laminated body 10 including the molded resin layer 4 is manufactured by integrating the molded sheet with the outer surface of the molded product.

More specifically, the laminate 10 including the molded resin layer 4 is manufactured by an insert molding method including the following steps.
A vacuum forming process in which the laminate before laminating the molded resin layer 4 is formed into a three-dimensional shape in advance by a vacuum forming mold, a trimming process in which an excess portion of the vacuum-formed laminate is trimmed to obtain a formed sheet, and a formed sheet. is inserted into an injection molding die, the injection molding die is closed, and a resin in a fluid state is injected into the injection molding die from the transparent substrate layer 1 side to integrate the resin and the molding sheet.

In the vacuum forming step in the insert molding method, the laminate may be heated and formed. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the laminate, the thickness of the laminate, and the like. In addition, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but it can usually be about 180.degree. C. to 320.degree.

As described above, the molding resin layer 4 may be formed by selecting a resin according to the application. The molding resin that forms the molding resin layer 4 may be the thermoplastic resin described above, or may be a thermosetting resin.

Examples of thermosetting resins include urethane resins and epoxy resins. These thermosetting resins may be used singly or in combination of two or more.

The laminate 10 of the present invention exhibits different designs when the light source is turned on and when the light source is turned off. fittings such as; interior materials for buildings such as walls, floors, and ceilings; housings for home electric appliances such as television receivers and air conditioners;

[Decorative goods]
A decorative article 20 of the present invention utilizes the laminate 10 of the present invention and includes the laminate 10 and a light source 30 . As shown in FIG. 7 , the light source 30 is arranged on the second main surface 12 side of the laminate 10 . The details of the laminate 10 of the present invention are as described above.

The type of light source is not particularly limited, and includes, for example, light emitting diode (LED) light bulbs, incandescent light bulbs, fluorescent lights, and natural light.

The decorative article of the present invention expresses a different design when the light source is turned on and when the light source is turned off. Interior materials for buildings such as ceilings; housings for home electric appliances such as television receivers and air conditioners; containers; and the like.

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. However, the invention is not limited to the examples.

[Production of laminate]
<Example 1>
A laminate (decorative sheet) was produced by the following procedure. A transparent ABS resin film having a thickness of 475 μm was used as the base layer. Next, an ink composition containing an acrylic resin was used to form a design layer with a textured pattern as a first design layer on the substrate layer by gravure printing. Next, a black patterned layer (thickness: 2 μm) was formed on the entire surface as a second design layer by gravure printing. Next, on the second design layer, a binder resin made of a two-liquid curing resin containing 100 parts by mass of a main agent (acrylic polyol/urethane, mass ratio 9/1) and 7 parts by mass of a curing agent (hexamethylene diisocyanate) is included. A primer layer having a thickness of 2 μm was formed by applying a resin composition for a primer layer and drying to obtain a laminate in which a substrate layer/first design layer/second design layer/primer layer were laminated in this order. .

Next, the primer layer side of the obtained laminate was embossed using an embossing plate having a geometric pattern and an embossing plate depth of 60 μm to form an uneven shape on the primer layer. Details of the embossed plate will be described later. Next, in order to form a surface protective layer, a resin composition containing an ionizing radiation resin (EB resin) is applied to the primer layer on which the uneven shape is formed, and the thickness after curing (the uneven shape of the surface protective layer It was applied so that the thickness of the convex portion of ) was 10 μm. This resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface protective layer having an uneven shape to obtain a decorative sheet (laminate). The uneven shape of the surface protective layer corresponds to the uneven shape of the primer layer.

The decorative sheet (laminate before molding) obtained above was heated with an infrared heater and softened until the sheet temperature reached 160°C. Then, vacuum forming was performed using a vacuum forming mold (maximum draw ratio: 100%) to form the internal shape of the mold. After the molded decorative sheet was cooled, it was released from the mold. After trimming the molded decorative sheet and inserting it into the injection mold, the injection resin is injected into the cavity of the mold, the decorative sheet and the injected resin are integrally molded, removed from the mold and processed. A decorative resin molding was obtained. A transparent polycarbonate resin was used as the injection resin.

<Comparative Example 1>
A decorative sheet and a decorative resin molded product were produced in the same manner as in Example 1, except that embossing was not performed in the production of the decorative sheet of Example 1.

[Evaluation of design when lights are off]
The decorative sheet (laminate before molding) obtained above and the decorative resin molded product (after molding) were visually observed from the surface protective layer side (observation surface dimensions: 230.4 mm × 135.4 mm). Appearance visual evaluation was performed on a light panel having a correlated color temperature of 5200 (±300 K) and an average luminance of 1500±300 cd/m ² when the light was turned off. The following criteria evaluated the design property at the time of light extinction. Table 1 shows the results.
A: Only the design based on the second design layer can be confirmed B: The outline of the design based on the first design and the design based on the second design layer can be confirmed C: The design based on the first design layer is based on the second design layer It can be confirmed by overlapping with the design

[Evaluation of design during lighting]
The decorative sheet (laminate before molding) obtained above and the decorative resin molded product (after molding) were visually observed from the surface protective layer side (observation surface dimensions: 230.4 mm × 135.4 mm). Appearance visual evaluation during lighting was performed on a light panel having a correlated color temperature of 5200 (±300 K) and an average luminance of 1500±300 cd/m ² . The following criteria evaluated the design property at the time of lighting. Table 1 shows the results.
A: The design based on the first design layer can be confirmed C: The design based on the first design layer can be confirmed overlapping the design based on the second design layer

DESCRIPTION OF SYMBOLS 1... Transparent base material layer 21... First design layer 22... Second design layer 3... Surface protection layer 4... Molded resin layer 10... Laminated body 11... First main surface 12... Second main surface

Claims (8)

A first main surface arranged on the viewer side and a second main surface arranged on the light source side,
A laminate comprising at least a transparent substrate layer, a first design layer, and a second design layer in order from the second main surface side,
At least one layer positioned closer to the first main surface than the transparent substrate layer is provided with an uneven shape ,
The second design layer has the uneven shape,
The depth of the concave portion of the uneven shape of the second design layer is 5 μm or more and 100 μm or less,
The laminate, wherein the width of the uneven concave portion of the second design layer is 50 μm or more and 500 μm or less . The first design layer has a patterned design,
2. The laminate according to claim 1 , wherein the second design layer has a monochromatic design on the entire surface. 3. The laminate according to claim 1 , further comprising a surface protective layer on the outermost surface on the first main surface side. The laminate according to any one of claims 1 to 3 , wherein the first design layer and the transparent substrate layer each have an uneven shape corresponding to the uneven shape of the second design layer. . The laminate according to any one of claims 1 to 4 , wherein the outermost surface of the laminate on the first main surface side has an uneven shape. The laminate according to any one of claims 1 to 5 , wherein the laminate is in the form of a sheet. Any one of claims 1 to 6 , comprising, in order from the second main surface side, at least a transparent molding resin layer, the transparent substrate layer, the first design layer, and the second design layer. The laminate according to the item. A laminate according to any one of claims 1 to 7 ,
a light source arranged on the second main surface side of the laminate;
A decorative article.

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