Laminate and decorative article

Abstract

The present invention relates to a laminate exhibiting different appearance designs when a light source is turned on and turned off, in which the appearance design exhibiting when the light source is turned off is not visible when the light source is turned on and is visible when the light source is turned off. The laminate has a first main surface disposed on the observer side and a second main surface disposed on the light source side, the first main surface having an uneven shape and having at least a first design layer, a transparent resin layer, and a second design layer in this order from the first main surface side, and the transparent resin layer is disposed on the first main surface side or the second main surface side of the second design layer. And a third design layer, the surface on the first main surface side of the second design layer is relatively flat compared with the concave-convex shape of the first main surface, and the third design layer is partially arranged.

Description

Technical Field

[0001] The present invention relates to a laminate and a decorative article. Background Art

[0002] Conventionally, in the fields of vehicle interior and exterior components, building interior decoration materials, home appliance casings, etc., a decorative resin molded product in which a decorative sheet is laminated on the surface of a resin molded product has been used. When manufacturing such a decorative resin molded product, a molding method such as integrating a decorative sheet with a pre-given design by injection molding is adopted. As a representative example of this molding method, an insert molding method can be cited in which a decorative sheet is pre-formed into a three-dimensional shape by a vacuum molding die, and then the decorative sheet is inserted into an injection molding die, and resin in a flowing state is injected into the die to integrate the resin with the decorative sheet.

[0003] Since the decorative resin molded products obtained by such molding methods are used for various purposes such as vehicle interior and exterior components as described above, in addition to the three-dimensional moldability and surface properties such as surface scratch resistance that can match three-dimensional molding, with the diversification of consumer tastes in recent years, diverse design senses are also required. For example, the following development has been carried out, that is, by matching specific parts of a pattern, matte or unevenness is imparted to the resin molded product to impart texture, etc. (for example, Patent Document 1). In addition, as a product having various design senses, a synthetic resin molded part having a variable design surface has been proposed (for example, Patent Document 2).

[0004] In addition, a decorative sheet has been proposed in which a light source is arranged on the side opposite to the observer side of the decorative sheet, and different appearance designs are exhibited when the light source is lit and extinguished (for example, Patent Document 3).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2009-132145

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2010-125817

[0009] Patent Document 3: Japanese Patent Application Laid-Open No. 2013-14051

[0010] Patent Document 4: Japanese Patent Application Laid-Open No. 2020-49844 Summary of the Invention

[0011] Technical Problem to be Solved by the Invention

[0012] As described above, a laminate that exhibits different appearance designs when a light source is lit and extinguished is known.

[0013] For example, Patent Document 4 discloses a laminate having a first main surface disposed on the observer side and a second main surface disposed on the light source side, and having at least a first design layer, a second design layer, and a transparent substrate layer in this order from the second main surface side. The surface of the transparent substrate layer on the second design layer side has an uneven shape. The advantage of this laminate is that the appearance design visible when the light source is lit is not visible when the light source is extinguished, and the appearance design is only visible (recognizable) when the light source is lit.

[0014] On the other hand, as a laminate that exhibits different appearance designs when the light source is lit and extinguished, there is a need for a laminate in which the appearance design visible when the light source is extinguished is not easily visible when the light source is lit, and the appearance design is visible when the light source is extinguished.

[0015] The main object of the present invention is to provide a laminate that exhibits different appearance designs when the light source is lit and extinguished, in which the appearance design visible when the light source is extinguished is not easily visible when the light source is lit, and the appearance design is visible when the light source is extinguished. Moreover, the object of the present invention is also to provide an ornamental article using such a laminate.

[0016] Technical solutions for solving technical problems

[0017] The inventor of the present invention conducted in-depth research to solve the above technical problems. As a result, it was found that the following laminate exhibits different appearance designs when the light source is lit and extinguished, and the appearance design visible when the light source is extinguished (specifically, the appearance design based on the uneven shape on the surface of the first main surface side of the laminate and the appearance design brought by the first design layer) is not easily visible when the light source is lit, and the appearance design is visible when the light source is extinguished. The laminate has a first main surface disposed on the observer side and a second main surface disposed on the light source side. The first main surface has an uneven shape. In this laminate, at least a first design layer, a transparent resin layer, a second design layer, and a third design layer located on the first main surface side or the second main surface side of the second design layer are further provided in this order from the first main surface side. The surface of the second design layer on the first main surface side is relatively flat compared to the uneven shape of the first main surface, and the third design layer is partially provided. The present invention was completed based on this recognition and further repeated research.

[0018] That is, the present invention provides an invention in the following manner.

[0019] Item 1: A laminate having a first main surface disposed on the observer side and a second main surface disposed on the light source side,

[0020] wherein the first main surface has an uneven shape,

[0021] Starting from one side of the above-mentioned first main surface, there are at least a first design layer, a transparent resin layer, and a second design layer in sequence.

[0022] On one side of the first main surface or the second main surface of the above-mentioned second design layer, there is also a third design layer.

[0023] The surface on the first main surface side of the above-mentioned second design layer is relatively flat compared to the concavo-convex shape of the above-mentioned first main surface.

[0024] The above-mentioned third design layer is partially provided.

[0025] Item 2: The laminate according to Item 1, wherein the surface on the first main surface side of the above-mentioned transparent resin layer has a concavo-convex shape corresponding to the concavo-convex shape of the above-mentioned first main surface.

[0026] Item 3: The laminate according to Item 1 or 2, wherein there is also a surface protection layer on the outermost surface on the first main surface side.

[0027] Item 4: The laminate according to any one of Items 1 to 3, wherein there is also a transparent substrate layer on the second main surface side of the above-mentioned second design layer and the above-mentioned third design layer.

[0028] Item 5: The laminate according to any one of Items 1 to 4, wherein the above-mentioned laminate is sheet-shaped.

[0029] Item 6: The laminate according to any one of Items 1 to 5, wherein starting from the second main surface side, there are at least a transparent molding resin layer, the above-mentioned second design layer, the above-mentioned transparent resin layer, and the above-mentioned first design layer in sequence.

[0030] Item 7: An ornamental article, which has the laminate according to any one of Items 1 to 6 and a light source disposed on the second main surface side of the above-mentioned laminate.

[0031] Advantages of the Invention

[0032] According to the present invention, it is possible to provide a laminate that exhibits different appearance designs when the light source is lit and when it is extinguished, the appearance design visible when the light source is extinguished is not easily visible when the light source is lit, and this appearance design is visible when the light source is extinguished. Moreover, according to the present invention, it is also possible to provide an ornamental article using this laminate. Brief Description of the Drawings

[0033] Figure 1 It is a cross-sectional schematic view of an example of the laminate of the present invention.

[0034] Figure 2 It is a cross-sectional schematic view of an example of the laminate of the present invention.

[0035] Figure 3 Cross-sectional schematic view of an example of the laminate of the present invention.

[0036] Figure 4 Cross-sectional schematic view of an example of the laminate of the present invention.

[0037] Figure 5 Cross-sectional schematic view of an example of an ornamental article using the laminate of the present invention.

[0038] Figure 6 An example of an image diagram showing the state of observing the laminate of the present invention from the first main surface side (the observer side) when the light source 30 is lit.

[0039] Figure 7 An example of an image diagram showing the state of observing the laminate of the present invention from the first main surface side (the observer side) when the light source 30 is lit. Detailed Description of the Invention

[0040] 1. Laminated body

[0041] The laminate of the present invention is characterized in that it has a first main surface disposed on the observer side and a second main surface disposed on the light source side. The first main surface has an uneven shape and successively has at least a first design layer, a transparent resin layer, and a second design layer from the first main surface side. On either the first main surface side or the second main surface side of the second design layer, there is also a third design layer. The surface on the first main surface side of the second design layer is relatively flat compared to the uneven shape of the first main surface, and the third design layer is partially provided. Due to the above characteristics, the laminate of the present invention can exhibit different appearance designs when the light source is lit and extinguished. The appearance design (specifically, the appearance design based on the uneven shape of the surface on the first main surface side of the laminate and the appearance design brought by the first design layer) that appears when the light source is extinguished is not easily visible when the light source is lit, but this appearance design is visible when the light source is extinguished.

[0042] The laminate of the present invention can be applied to the decoration of the surfaces of resin molded products such as interior and exterior vehicle parts, building interior decoration materials, and home appliance casings. Therefore, the laminate of the present invention can be suitably used as a decorative sheet for three-dimensional molding. Especially when the laminate of the present invention is in a sheet form, it can also be formed into a decorative sheet for three-dimensional molding, laminated with the molding resin layer 5 described later, and appropriately made into a decorative resin molded product.

[0043] Hereinafter, with reference to Figures 1 to 5The laminate of the present invention will be described in detail. It should be noted that in this specification, unless specifically stated as "above" or "below", the numerical range indicated by "~" means "…… or more, …… or less". For example, the description of 2~15mm means "2mm or more and 15mm or less". In addition, in this specification, "(meth)acrylate" means "acrylate or methacrylate", and other similar expressions have the same meaning.

[0044] Laminated structure and concave-convex shape of the laminated body

[0045] The laminate 10 of the present invention is, for example, as Figures 1 to 5 shown, and has a first main surface 11 disposed on the observer side and a second main surface 12 disposed on the light source side. Specifically, when the laminate 10 of the present invention is used for various purposes such as interior and exterior vehicle parts, building interior decoration materials, and home appliance housings, the first main surface 11 is disposed on the observer side and the second main surface 12 is disposed on the light source side.

[0046] The laminate 10 of the present invention includes: a laminate having at least a first design layer 21, a transparent resin layer 1, and a second design layer 22 in sequence from the first main surface 11 side, and further having a third design layer 23 on either the first main surface 11 side or the second main surface 12 side of the second design layer 22. In addition, in the laminate 10 of the present invention, the first main surface 11 has an uneven shape.

[0047] When observed from the first main surface 11 side, the laminate 10 exhibits different appearance designs when the light source 30 is lit and when it is extinguished. When the light source is extinguished, the appearance design based on the uneven shape of the surface on the first main surface 11 side and the appearance design derived from the first design layer 21 are visible. In addition, when the light source is lit, the appearance designs based on the second design layer 22 and the third design layer 23 are visible. In the laminate 10 of the present invention, the appearance design that appears when the light source 30 is extinguished is not easily visible when the light source 30 is lit; and when the light source is extinguished, this appearance design is visible. In order to exhibit such characteristics, it is important that in the laminate 10 of the present invention, the transparent resin layer 1 is disposed between the first design layer 21 and the second design layer 22, and moreover, the surface 22a on the first main surface 11 side of the second design layer 22 is relatively flat compared to the uneven shape of the first main surface 11.

[0048] It should be noted that the surface 22a on one side of the first main surface 11 of the second design layer 22 only needs to be in a shape that is relatively flat compared to the concave and convex shape of the first main surface 11. Specifically, the depth of the concave portion of the surface 22a on one side of the first main surface 11 of the second design layer 22 is relatively small compared to the depth of the concave portion of the concave and convex shape of the first main surface 11. From the perspective of better exerting the effects of the present invention, it is preferably that the surface 22a on one side of the first main surface 11 of the second design layer 22 is substantially flat. For example, the concave and convex shape of the first main surface 11 is preferably flat to such an extent that it does not affect the shape of the surface 22a on one side of the first main surface 11 of the second design layer 22, and in this case, some concave and convex shapes are also allowed.

[0049] The surface on the second main surface 12 side of the second design layer 22 is also preferably in a shape that is relatively flat compared to the concave and convex shape of the first main surface 11, and more preferably substantially flat.

[0050] For example, as Figure 4 and Figure 5 shown, in the laminate 10 of the present invention, for the purpose of imparting surface protection properties such as scratch resistance and chemical resistance (chemical corrosion resistance) to the surface, a surface protection layer 3 can also be further provided above the first design layer 21 (on the first main surface 11 side). In addition, for the purpose of improving the adhesion between the surface protection layer 3 and the layer below it (such as the first design layer 21), a primer layer (not shown) can also be provided as needed. In addition, for example, an adhesive layer (not shown) can also be provided on at least one side surface of the second design layer 22. In addition, for example, as Figure 5 shown, when the resin layer 5 is laminated and formed on the second main surface 12 side, for the purpose of improving the adhesion between the laminate 10 of the present invention and the resin layer 5, a back adhesive layer (not shown) can also be provided on the second main surface 12 side (the back side of the transparent substrate layer 4) of the transparent substrate layer 4 as needed.

[0051] The laminate of the present invention can also be further laminated with one or more other layers according to the functions given to the laminate and the decorative article.

[0052] As the laminate structure of the laminate of the present invention, there can be cited a laminate structure in which a first design layer / a transparent resin layer 1 / a second design layer / a third design layer are laminated in order from the first main surface side; a laminate structure in which a first design layer / a transparent resin layer 1 / a third design layer / a second design layer are laminated; a laminate structure in which a first design layer / a transparent resin layer 1 / a second design layer / a third design layer / a transparent base material layer are laminated; a laminate structure in which a first design layer / a transparent resin layer 1 / a third design layer / a second design layer / a transparent base material layer are laminated; a laminate structure in which a surface protective layer / a first design layer / a transparent resin layer 1 / a second design layer / a third design layer / a transparent base material layer are laminated; a laminate structure in which a surface protective layer / a first design layer / a transparent resin layer 1 / a third design layer / a second design layer / a transparent base material layer are laminated; a laminate structure in which a surface protective layer / a first design layer / a transparent resin layer 1 / a second design layer / an adhesive layer / a third design layer / a transparent base material layer are laminated; a laminate structure in which a surface protective layer / a first design layer / a transparent resin layer 1 / a third design layer / a second design layer / an adhesive layer / a transparent base material layer are laminated; a laminate structure in which a surface protective layer / a first design layer / a transparent resin layer 1 / an adhesive layer / a second design layer / a third design layer / a transparent base material layer are laminated; a laminate structure in which a surface protective layer / a first design layer / a transparent resin layer 1 / a third design layer / an adhesive layer / a second design layer / a transparent base material layer are laminated; a laminate structure in which a surface protective layer / a first design layer / a transparent resin layer 1 / a third design layer / a second design layer / a transparent base material layer / a molding resin layer are laminated; a laminate structure in which a surface protective layer / a first design layer / a transparent resin layer 1 / a second design layer / an adhesive layer / a third design layer / a transparent base material layer / a molding resin layer are laminated; a laminate structure in which a surface protective layer / a first design layer / a transparent resin layer 1 / a third design layer / a second design layer / a transparent base material layer / a back adhesive layer / a molding resin layer are laminated; a laminate structure in which a surface protective layer / a first design layer / a transparent resin layer 1 / a second design layer / an adhesive layer / a third design layer / a transparent base material layer / a back adhesive layer / a molding resin layer are laminated, etc.

[0053] Figure 1 Fig. shows a cross-sectional schematic view of an example of a laminate in which a first design layer / a transparent resin layer 1 / a second design layer / a third design layer are laminated in order from the first main surface side, which represents an embodiment of the laminate structure of the laminate of the present invention. Figure 2 Fig. shows a cross-sectional schematic view of an example of a laminate in which a first design layer / a transparent resin layer 1 / a third design layer / a second design layer are laminated in order from the first main surface side, which represents an embodiment of the laminate structure of the laminate of the present invention. Figure 3 Fig. shows a cross-sectional schematic view of an example of a laminate in which a first design layer / a transparent resin layer / a second design layer / a third design layer / a transparent base material layer are laminated in order from the first main surface side, which represents an embodiment of the laminate structure of the laminate of the present invention. Figure 4This shows a cross-sectional schematic view of an example of a laminate in which a surface protective layer / a first design layer / a transparent resin layer / a second design layer / a third design layer / a transparent base material layer are laminated in order from one side of the first main surface, which is an embodiment of the laminate structure of the laminate of the present invention. Figure 5 This shows a cross-sectional schematic view of an example of a laminate in which a surface protective layer / a first design layer / a transparent resin layer 1 / a second design layer / a third design layer / a transparent base material layer / a molding resin layer are laminated in order from one side of the first main surface, which is an embodiment of the laminate structure of the laminate of the present invention.

[0054] In addition, in the laminate 10 of the present invention, it is preferable that the surface on the first main surface 11 side of the first design layer 21 has an uneven shape 21a. It is preferable that the uneven shape of the first main surface 11 of the laminate 10 and the uneven shape 21a of the surface on the first main surface 11 side of the first design layer 21 are in a corresponding shape. As Figure 1 and Figure 2 shown, when the first design layer 21 constitutes the first main surface 11 of the laminate 10, the uneven shape 21a of the surface on the first main surface 11 side of the first design layer 21 is identical to the uneven shape of the first main surface 11.

[0055] In addition, in the laminate 10 of the present invention, it is preferable that the surface on the second main surface 12 side of the first design layer 21 also has an uneven shape. As Figure 1 and Figure 2 shown, it is preferable that the uneven shape 21a of the surface on the first main surface 11 side of the first design layer 21 and the uneven shape on the second main surface 12 side are in a corresponding shape.

[0056] Moreover, in the laminate 10 of the present invention, the transparent resin layer 1 may also have an uneven shape. When the transparent resin layer 1 has an uneven shape, as Figures 1 to 5 shown, it is preferable that the uneven shape is provided on the first main surface 11 side (that is, the uneven shape 1a on the first main surface 11 side of the transparent resin layer 1 having the transparent resin layer 1). The uneven shape 1a on the first main surface side of the transparent resin layer 1 corresponds to, for example, the uneven shape 21a of the surface on the first main surface 11 side of the first design layer 21. That is, in the laminate 10 of the present invention, the uneven shape corresponding to the uneven shape of the first main surface 11 can be provided, for example, from the first main surface 11 to the transparent resin layer 1 (especially up to the surface on the first main surface 11 side of the transparent resin layer 1).

[0057] From the viewpoint of better showing the effects of the present invention, in the laminate 10 of the present invention, the ratio of the depth D of the concave portion of the uneven shape of the first main surface 11 to the thickness of the transparent resin layer 1 is preferably 60% or less, and preferably 10% or more, and the preferable range is 10 to 60%.

[0058] In addition, from the viewpoint of better demonstrating the effects of the present invention, in the laminate 10 of the present invention, the depth D of the concave portion of the concavo-convex shape of the first main surface 11 is preferably 10 μm or more and 100 μm or less.

[0059] The depth of the concave portion can be measured by, for example, cross-sectional observation using a microscope. As Figures 1 to 3 shown, the depth D of the concave portion is the height from the concave portion to the convex portion of the concavo-convex shape of the first main surface 11.

[0060] In addition, based on the same viewpoint, the width W of the concave portion of the concavo-convex shape of the first main surface 11 is preferably about 30 to 500 μm, more preferably about 100 to 300 μm. The width W of the concave portion can be measured by, for example, cross-sectional observation using a microscope. As Figures 1 to 3 shown, the width W of the concave portion is the distance between adjacent convex portions of the concavo-convex shape of the first main surface 11.

[0061] The concavo-convex shape of the first main surface 11 can be appropriately formed by, for example, embossing. For example, by preparing a laminate in which at least a first design layer 21 and a transparent resin layer 1 are laminated, and performing embossing from the side of the first main surface 11, a concavo-convex shape can be formed on the side of the first main surface 11 of the first design layer 21. In this case, by adjusting the depth of the concave portion formed by embossing, it is also possible to form a concavo-convex shape in the first design layer 21 and the transparent resin layer 1 by one embossing process.

[0062] Embossing is a well-known method. For example, it is a method of pressing a heated and softened layer with an embossing plate, imparting an embossed pattern formed on the embossing plate to the surface of the laminate, and cooling and fixing it. Embossing can be performed using a well-known single-sheet or rotary embossing machine.

[0063] Even in the case where there are other layers such as a surface protective layer 3 and a primer coat, for example, by performing embossing on a laminate in which these other layers and the first design layer 21 are laminated on the transparent resin layer 1 to form a concavo-convex shape, a concavo-convex shape can also be formed on these other layers. In this case, the concavo-convex shapes formed on each layer can be made consistent. For example, as Figure 4 shown, the concavo-convex shape of the surface protective layer 3 corresponds to the concavo-convex shape of the first design layer 21.

[0064] Each layer forming the laminated body

[0065] [First design layer 21]

[0066] The first design layer 21 is provided on one side of the first main surface 11 of the transparent resin layer 1 for the purpose of imparting decoration or the like to the laminate. When observing the laminate 10 of the present invention from the side of the first main surface 11, when the light source 30 on the side of the second main surface 12 is turned off, the design of the first design layer 21 is a visible design. When the light source 30 is turned on, the design of the first design layer 21 is not easily visible from the side of the first main surface 11, and the designs brought by the second design layer 22 and the third design layer 23 are visible. On the other hand, when the light source 30 is turned off, when observing the laminate 10 of the present invention from the side of the first main surface 11, the designs brought by the second design layer 22 and the third design layer 23 are hardly visible.

[0067] Figure 6 And Figure 7 respectively represent images when observing the laminate 10 of the present invention from the side of the first main surface 11 (the observer's side) when the light source 30 is turned on. In Figure 6 And Figure 7 , the black part is the design of the third design layer 23, and the three rectangular parts therein ( Figure 6 is a geometric pattern, Figure 7 is a gray gradient pattern) are the designs of the second design layer 22. On the one hand, the third design layer 23 serves as a light-shielding layer that blocks light transmission, and on the other hand, the second design layer serves as a pattern layer that transmits light. The design of the first design layer 21 is not easily visible from the side of the first main surface 11. That is, in, for example, Figure 6 , the observer can observe three rectangles that emit light with a geometric pattern. In addition, in, for example, Figure 7 , the observer can observe three rectangles that emit light with a gradient.

[0068] From the viewpoint of better showing the effects of the present invention, it is preferable that the surface on the side of the first main surface 11 of the first design layer 21 has an uneven shape 21a. Moreover, it is preferable that the uneven shape of the first main surface 11 and the uneven shape 21a of the surface on the side of the first main surface 11 of the first design layer 21 are corresponding shapes. As shown in Figure 1 And Figure 2 , when the first design layer 21 constitutes the first main surface 11 of the laminate 10, the uneven shape 21a of the surface on the side of the first main surface 11 of the first design layer 21 coincides with the uneven shape of the first main surface 11.

[0069] In addition, in the laminate 10 of the present invention, it is preferable that the surface on the side of the second main surface 12 of the first design layer 21 also has an uneven shape. As shown in Figure 1 And Figure 2 , it is preferable that the uneven shape 21a of the surface on the side of the first main surface 11 of the first design layer 21 and the uneven shape on the side of the second main surface 12 are corresponding shapes.

[0070] Since the light is scattered by the action of the first design layer 21 having a concavo-convex shape, it is easy to achieve the effect that the appearance designs based on the second design layer 22 and the third design layer 23 are not visible when the light is turned off.

[0071] When the first design layer 21 has a concavo-convex shape, the concavo-convex shape can be provided only on one side of the first main surface 11, or as Figures 1 to 5 shown, it can also be provided on one side of the second main surface 12.

[0072] The first design layer 21 can be, for example, a layer formed by using an ink composition to form a desired pattern. For example, when the first design layer 21 has a monochromatic appearance design on the entire surface, and the second design layer 22 and the third design layer 23 have a pattern-like appearance design, it can also be configured such that when the light source is turned off, the monochromatic appearance design of the first design layer 21 on the entire surface is visible, and the appearance designs of the second design layer 22 and the third design layer 23 are not visible; and when the light source is turned on, the pattern-like appearance designs (such as symbols, text information, etc. of the above patterns) of the second design layer 22 and the third design layer 23 are visible.

[0073] It should be noted that the first design layer 21 can be partially provided on the transparent resin layer 1, or can be provided on the entire surface, and is preferably provided on the entire surface.

[0074] The first design layer 21 can be formed by printing an ink for forming the first design layer on the transparent resin layer 1 by using a conventional known printing method such as gravure printing, screen printing, offset printing, etc. As the ink composition for forming the first design layer 21, examples of the composition that can be cited include the same composition as the composition exemplified in the second design layer 22 described later, which contains a binder, a colorant, etc.

[0075] Examples of the pattern formed by the first design layer 21 can also include the same patterns as those exemplified in the second design layer 22 described later, but the first design layer 21 preferably has a monochromatic appearance design on the entire surface as described above.

[0076] In addition, the first design layer 21 can also include a part composed of a metal thin film. Examples of the metal for forming the metal thin film and the forming method, etc. can also include the same content as that exemplified in the second design layer 22.

[0077] The thickness of the first design layer 21 can be cited but is not particularly limited. The lower limit is preferably 1 μm or more, the upper limit is preferably 20 μm or less, and more preferably 10 μm or less. As a preferred range, 1 to 20 μm or so, 1 to 10 μm or so can be cited. It should be noted that when the first design layer 21 has a concavo-convex shape, the thickness of the first design layer 21 is the thickness at the convex portion position of the concavo-convex shape.

[0078] From the viewpoint of better demonstrating the effects of the present invention, the optical density (OD value) of the first design layer 22 is preferably 2.5 or less, and preferably 0.3 or more, and the preferred range is 0.3 to 2.5. It should be noted that it is preferred that the sum of the OD value of the first design layer and the OD value of the second design layer described later is less than 3.5.

[0079] [Transparent resin layer 1]

[0080] The transparent resin layer 1 is provided between the first design layer 21, the second design layer 22, and the third design layer 23, and is a layer that functions as follows: when the light source 30 is lit, the appearance design (such as the appearance design of the first design layer 21) that appears when the light source 30 is extinguished is not easily visible, while the appearance designs brought by the second design layer 22 and the third design layer 23 are easily visible; when the light source 30 is extinguished, the appearance design (such as the appearance design of the first design layer 21) that appears when the light source 30 is extinguished is easily visible, while the appearance designs brought by the second design layer 22 and the third design layer 23 are not easily visible. In the absence of the transparent resin layer 1, for example, when the light source 30 is lit, the appearance design (such as the appearance design of the first design layer 21) that appears when the light source 30 is extinguished will be as visible as the appearance designs brought by the second design layer 22 and the third design layer 23, making it difficult to achieve the object of the present invention.

[0081] As Figure 5 shown, when the light source 30 is arranged on the side of the second main surface 12, the transparent resin layer 1 is transparent to the extent that it can transmit the light from the light source 30 (in the present invention, transparent also includes translucent). That is, the transparent resin layer 1 is usually transparent (colorless transparent, colored transparent, translucent), but it can also be colored, as long as when observing the laminate 10 of the present invention from the side of the first main surface 11, when lit, the appearance designs based on the second design layer 22 and the third design layer 23 are visible. For example, the transparent resin layer 1 can contain a matting agent such as silica, a coloring agent, etc. As the coloring agent, the coloring agents exemplified in the second design layer 22 described later can be used. In addition, the transparent resin layer 1 can also be coated for color adjustment, or a pattern for imparting design can be formed, etc.

[0082] As described above, the transparent resin layer 1 can have an uneven shape. When the transparent resin layer 1 has an uneven shape, as Figures 1 to 5As shown, it is preferred that the concavo-convex shape is provided on one side of the first main surface 11 (the concavo-convex shape 1a on one side of the first main surface 11 having the transparent resin layer 1). The concavo-convex shape 1a on one side of the first main surface 11 of the transparent resin layer 1 corresponds to, for example, the concavo-convex shape of the first main surface 11 and the concavo-convex shape of the first design layer 21. That is, in the laminate 10 of the present invention, the concavo-convex shape can be provided from the first main surface 11 to the transparent resin layer 1. It should be noted that the surface on the second main surface 12 side of the transparent resin layer 1 is preferably a relatively flat shape compared to the concavo-convex shape of the first main surface 11 of the laminate 10, and more preferably substantially flat. When the surface on the second main surface 12 side of the transparent resin layer 1 is flat, the layer in contact with the surface on the second main surface 12 side of the transparent resin layer 1 (for example, the surface in contact with the surface on the second main surface 12 side of the transparent resin layer 1 in the second design layer 22, the surface in contact with the surface on the second main surface 12 side of the transparent resin layer 1 in the third design layer 23, etc.) is also preferably a relatively flat shape compared to the concavo-convex shape of the first main surface 11 of the laminate 10, and more preferably substantially flat. It should be noted that relatively flat is preferably but not particularly limited to the maximum height roughness Rz of the surface on the second main surface 12 side of the transparent resin layer 1 being 50% or less of the Rz of the concavo-convex shape of the first main surface 11. Rz is measured in accordance with JIS B0601 (1996).

[0083] From the viewpoint of making the laminate 10 suitable for three-dimensional molding and being able to well exhibit different appearance designs when the light source is lit and extinguished, the transparent resin layer 1 can be made of a transparent resin. It is preferred that the transparent resin is formed of a transparent thermoplastic resin. Examples of the transparent thermoplastic resin include, but are not particularly limited to, transparent acrylonitrile-butadiene-styrene resin (hereinafter referred to as "ABS resin"), acrylic resin; polyolefin resins such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET) resin; acrylonitrile-styrene-acrylic resin, etc. Among them, it is preferred that the transparent resin layer 1 is formed of a transparent acrylic resin. The resin forming the transparent resin layer 1 can be one kind or two or more kinds.

[0084] From the viewpoint of making the laminate 10 suitable for three-dimensional molding and being able to well exhibit different appearance designs when the light source is lit and extinguished, examples of the thickness of the transparent resin layer 1 include, but are not particularly limited to, the lower limit is preferably 50 μm or more, more preferably 70 μm or more, and the upper limit is preferably 200 μm or less, more preferably 150 μm or less. Preferred ranges include about 50 - 200 μm, about 50 - 150 μm, about 70 - 200 μm, and about 70 - 150 μm. It should be noted that when the transparent resin layer 1 has a concavo-convex shape, the thickness of the transparent resin layer 1 is the thickness at the convex portion position of the concavo-convex shape.

[0085] In order to improve the adhesion with the adjacent layer, the transparent resin layer 1 can be subjected to physical or chemical surface treatments such as oxidation method or roughening method (concavo-convex method) on one or both surfaces as needed. Examples of the oxidation method implemented as the surface treatment of the transparent resin layer 1 include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment method, etc. In addition, examples of the roughening method implemented as the surface treatment of the transparent resin layer 1 include sandblasting method, solvent treatment method, etc. These surface treatments can be appropriately selected according to the type of resin constituting the transparent resin layer 1, and from the viewpoints of effects and operability, etc., the corona discharge treatment method is preferably cited.

[0086] From the viewpoint of better demonstrating the effects of the present invention, the total spectral transmittance of the transparent resin layer 1 is preferably about 70% or more, more preferably about 80% or more, and further preferably about 90% or more. The total spectral transmittance is measured by a haze meter according to the standard of JIS K7361-1.

[0087] [Second design layer 22]

[0088] The second design layer 22 is a layer provided on the side of the second main surface 12 of the transparent resin layer 1 for the purpose of imparting decorativeness, etc. to the laminate 10. The exterior design of the second design layer 22 is an exterior design visible from the side of the first main surface 11 when the light source on the side of the second main surface 12 is lit, and when the light source 30 is extinguished, the exterior design of the second design layer 22 is not easily visible from the side of the first main surface 11, and the exterior design of the first design layer 21 is visible.

[0089] The second design layer 22 is provided so that when observing the laminate 10 of the present invention from the side of the first main surface 11, the exterior design is displayed together with the third design layer 23 described later when the light source 30 is lit. For example, in the case where the second design layer 22 and the third design layer 23 have a pattern-like exterior design and the above-mentioned first design layer 21 has a monochromatic whole-surface exterior design, it can be configured such that when the light source 30 is extinguished, the monochromatic whole-surface exterior design of the first design layer 21 is visible, while the exterior designs of the second design layer 22 and the third design layer 23 are not visible; when the light source 30 is lit, the pattern-like exterior designs (for example, patterns such as symbols and character information described later) of the second design layer 22 and the third design layer 23 are visible.

[0090] It should be noted that when one main surface of the laminate is a whole surface, the second design layer 22 can be provided partially or entirely, and it is preferably provided entirely.

[0091] The optical density (OD value) of the second design layer 22 is preferably 3.0 or less, and preferably 0.5 or more, and the preferred range is 0.5 to 3.0.

[0092] The second design layer 22 may be, for example, a layer formed with an ink composition having a desired pattern. The second design layer 22 can be formed by printing an ink for forming the second design layer using a conventional known printing method such as gravure printing, screen printing, offset printing, etc. As the ink composition used for forming the second design layer 22, a product obtained by appropriately mixing colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, etc. with a binder can be used.

[0093] Examples of the binder used in the ink composition include, but are not particularly limited to, for example, polyurethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc. These binders can be used alone or in combination of two or more.

[0094] Examples of the colorant used in the ink composition include, but are not particularly limited to, for example, inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, chrome yellow, titanium yellow, iron red, cadmium red, ultramarine, cobalt blue, etc.; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, etc.; metallic pigments made of flaky foils such as aluminum and brass; pearlescent (pearl) pigments formed by flaky foils such as titanium dioxide-coated mica and basic lead carbonate, etc.

[0095] Examples of the pattern formed on the second design layer 22 include, but are not particularly limited to, for example, symbols, character information, and geometric patterns such as dot patterns, line patterns, carbon patterns, etc., gradient patterns, wood grain patterns, stone grain patterns that imitate the surface of rocks such as travertine marble patterns, fabric patterns that imitate cloth textures and cloth-like patterns, tile patterns, brick patterns, etc. It can also be patterns such as mosaics and splicings formed by combining the above patterns, or single-color solid colors (i.e., the entire surface is painted). These patterns can be formed by multicolor printing using the usual printing colors such as yellow, red, blue, and black, or by multicolor printing using specific colors achieved by preparing various color plates that make up the pattern, etc.

[0096] In addition, the second design layer 22 may include a part made of a metal thin film. Examples of the metal for forming the metal thin film include, for example, tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of them. Examples of the method for forming the metal thin film include, but are not particularly limited to, for example, vapor deposition methods such as vacuum vapor deposition using the above metals, sputtering methods, ion plating methods, etc. In addition, in order to improve the adhesion to the adjacent layer, a primer layer using a known resin can also be provided on the surface and / or back surface of the metal thin film.

[0097] As described above, the surface 22a on one side of the first main surface 11 of the second design layer 22 is relatively flat compared to the concavo-convex shape of the first main surface 11. It is sufficient that the surface 22a on one side of the first main surface 11 of the second design layer 22 has a relatively flat shape compared to the concavo-convex shape of the first main surface 11. Specifically, the depth of the concave portion of the surface 22a on one side of the first main surface 11 of the second design layer 22 is relatively reduced compared to the depth of the concave portion of the concavo-convex shape of the first main surface 11. From the viewpoint of better exerting the effects of the present invention, the surface 22a on one side of the first main surface 11 of the second design layer 22 is preferably substantially flat. For example, it is preferably that the concavo-convex shape of the first main surface 11 is flat to such an extent that it does not affect the shape of the surface 22a on one side of the first main surface 11 of the second design layer 22, and in this case, some concavo-convex shapes are also allowed. The relatively flat is preferably but not particularly limited to that the maximum height roughness Rz of the surface on one side of the first main surface 11 on the second design layer 22 side is 50% or less of the Rz of the concavo-convex shape of the first main surface 11. Rz is measured in accordance with JIS B0601 (1996). It should be noted that in the region where the transparent resin layer 1 is in contact with the second design layer 22, the surface shape on the second main surface side of the transparent resin layer and the surface shape on the first main surface side of the second design layer are in a complementary relationship.

[0098] Similarly, the surface on one side of the second main surface 12 of the second design layer 22 is preferably a relatively flat shape compared to the concavo-convex shape of the first main surface 11, and more preferably substantially flat. It should be noted that the relatively flat is preferably but not particularly limited to that the maximum height roughness Rz of the surface on one side of the second main surface 12 on the second design layer 22 side is 50% or less of the Rz of the concavo-convex shape of the first main surface 11. Rz is measured in accordance with JIS B0601 (1996).

[0099] The thickness of the second design layer 22 may be, but is not particularly limited to, preferably 1 μm or more and preferably 30 μm or less, more preferably 20 μm or less as the lower limit. As a preferred range, about 1 to 30 μm, about 1 to 20 μm can be cited. It should be noted that when the second design layer 22 has a concavo-convex shape, the thickness of the second design layer 22 is the thickness at the position of the convex portion of the concavo-convex shape.

[0100] [Third design layer 23]

[0101] The third design layer 23 is a layer provided on one side of the first main surface 11 or the second main surface 12 of the second design layer 22 for the purpose of imparting decorativeness and the like to the laminate 10. Specifically, as Figure 2 shown, when the third design layer 23 is provided on one side of the first main surface 11 of the second design layer 22, the third design layer 23 is located between the transparent resin layer 1 and the second design layer 22. In addition, as Figure 3As shown, when the laminate 10 has a transparent substrate layer 4 described later and the third design layer 23 is provided on the second main surface 12 side of the second design layer 22, the third design layer 23 is located between the second design layer 22 and the transparent substrate layer 4. It should be noted that, as Figure 2 shown, when the third design layer 23 is provided on the first main surface 11 side of the second design layer 22, in the region where the second design layer is in direct contact with the transparent resin layer, the surface on the first main surface side of the second design layer only needs to be relatively flat compared to the concavo-convex shape of the first main surface. That is, in the region where the third design layer 23 is not provided, the surface on the first main surface side of the second design layer only needs to be relatively flat compared to the concavo-convex shape of the first main surface.

[0102] When the main surface of the laminate 10 is set to the entire surface, the third design layer 23 is partially provided. The third design layer 23 is provided such that when the laminate 10 of the present invention is viewed from the first main surface 11 side, the appearance design is displayed together with the above-mentioned second design layer 23 when the light source 30 is lit. As described above, for example, when the second design layer 22 and the third design layer 23 have a pattern-like appearance design and the above-mentioned first design layer 21 has a monochromatic appearance design on the entire surface, it can be configured such that when the light source 30 is turned off, the monochromatic appearance design of the first design layer 21 is visible, and the appearance designs of the second design layer 22 and the third design layer 23 are not visible; when the light source 30 is lit, the pattern-like appearance designs (such as symbols, character information, and other patterns described later) of the second design layer 22 and the third design layer 23 are visible.

[0103] The optical density (OD value) of the third design layer 23 is preferably 3.5 or more and preferably 7.0 or less. As a preferred range, it is 3.5 to 7.0.

[0104] The third design layer 23 can be formed by printing a third design layer-forming ink using a conventional known printing method such as gravure printing, screen printing, or offset printing. As the ink composition used for forming the third design layer 23, a composition similar to the composition exemplified in the above-mentioned second design layer 22 containing a binder, a colorant, etc. can be cited.

[0105] The patterns formed by the third design layer 23 can also include the same pattern examples as those exemplified in the above-mentioned second design layer 22. As described above, the third design layer 23 is preferably formed partially and displays the target appearance design together with the second design layer 22.

[0106] In addition, the third design layer 23 can include a part composed of a metal thin film. The metal for forming the metal thin film, the forming method, etc. can cite the same solutions as those exemplified in the second design layer 22.

[0107] The thickness of the third design layer 23 may be exemplified but not particularly limited. The lower limit is preferably 1 μm or more, the upper limit is preferably 20 μm or less, and more preferably 10 μm or less. As the preferred range, about 1 to 20 μm or about 1 to 10 μm can be exemplified.

[0108] [Transparent substrate layer 4]

[0109] The transparent substrate layer 4 is a layer provided on the second main surface 12 side of the second design layer 22 and the third design layer 23 as needed for the purpose of imparting rigidity to the laminate 10 and maintaining its shape. When the laminate 10 is in a sheet form, the transparent substrate layer 4 is provided to form a laminate suitable for vacuum forming (three-dimensional forming) by an insert molding method or the like.

[0110] As Figures 3 to 5 shown, when the light source 30 is disposed on the second main surface 12 side, the transparent substrate layer 4 has a transparency that can transmit light from the light source (as described above, in the present invention, transparent also includes translucent). That is, the transparent substrate layer 4 is usually transparent (colorless transparent, colored transparent, translucent), but may be colored as long as the design of the second design layer 22 and the third design layer 23 is visible when the laminate 10 of the present invention is viewed from the first main surface 11 side when lit. For example, the transparent substrate layer 4 may contain a matting agent such as silica, a coloring agent, etc. As the coloring agent, the coloring agents exemplified in the second design layer 22 above can be used.

[0111] From the viewpoint of making the laminate 10 suitable for three-dimensional forming and capable of well showing different designs when the light source is lit and extinguished, the transparent substrate layer 4 may be composed of a transparent resin, a paper substrate, etc. The transparent resin is preferably formed of a transparent thermoplastic resin. As the transparent thermoplastic resin, examples include but are not particularly limited to transparent acrylonitrile-butadiene-styrene resin (hereinafter also referred to as "ABS resin"), acrylic resin; polyolefin resins such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET) resin; acrylonitrile-styrene-acrylate resin, etc. Among them, it is preferred that the transparent substrate layer 4 is formed of a transparent ABS resin. The resin forming the transparent substrate layer 4 may be one kind or two or more kinds.

[0112] From the perspective of making the laminate 10 suitable for three-dimensional molding and being able to well exhibit different appearance designs when the light source is lit and extinguished, the thickness of the transparent base material layer 4 can be exemplified but is not particularly limited to that the lower limit is preferably 50 μm or more, more preferably 100 μm or more, the upper limit is preferably 1000 μm or less, more preferably 500 μm or less. As the preferred range, 50 to 1000 μm or so, 100 to 500 μm or so can be exemplified. More specifically, when the transparent base material layer 4 is made of transparent ABS resin, more preferably 100 to 500 μm or so, and further preferably 200 to 400 μm.

[0113] In order to improve the adhesion with the adjacent layer, the transparent base material layer 4 can be subjected to physical or chemical surface treatments such as oxidation method or roughening method on one or both surfaces as needed. As the oxidation method implemented as the surface treatment of the transparent base material layer 4, for example, corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment method, etc. can be exemplified. In addition, as the roughening method implemented as the surface treatment of the transparent base material layer 4, for example, sandblasting method, solvent treatment method, etc. can be exemplified. These surface treatments can be appropriately selected according to the type of resin constituting the transparent base material layer 4. From the viewpoints of effects and operability, etc., corona discharge treatment method is preferably exemplified.

[0114] [Surface protection layer 3]

[0115] The surface protection layer 3 is a layer provided as needed to protect the surface of the laminate 10. In the laminate 10, the surface protection layer 3 is provided on the outermost surface on the side of the first main surface 11.

[0116] As described above, even when the laminate 10 has the surface protection layer 3, uneven shapes can be formed by embossing in a laminated state together with the first design layer 21, the transparent resin layer 1, etc., and uneven shapes can be formed on the surface protection layer 3. Therefore, as shown in the schematic diagrams of Figure 4 and Figure 5 , the surface protection layer 3 can have uneven shapes 3a. The uneven shapes 3a can be provided on the side of the first main surface 11 or on the side of the second main surface 12.

[0117] From the perspective of better exerting the effects of the present invention, it is preferred that the surface on the side of the first main surface 11 of the surface protection layer 3 has uneven shapes 3a. Moreover, it is preferred that the uneven shapes on the first main surface 11 and the uneven shapes 3a on the surface on the side of the first main surface 11 of the surface protection layer 3 are in a corresponding shape. As shown in the schematic diagrams of Figure 4 and Figure 5As shown, when the surface protective layer 3 constitutes the first major surface 11 of the laminate 10, the concavo-convex shape 3a of the surface on the first major surface 11 side of the surface protective layer 3 is identical to the concavo-convex shape of the first major surface 11.

[0118] In the laminate 10 of the present invention, the surface protective layer 3 may be provided on the entire surface on the first major surface 11 side or may be provided partially. From the viewpoint of appropriately protecting the surface of the laminate 10, the surface protective layer 3 is preferably provided on the entire surface on the first major surface 11 side.

[0119] In addition, the surface protective layer 3 is usually transparent (colorless transparent, colored transparent, translucent), but may also be colored or may contain a matting agent such as silica, as long as the exterior design based on the second design layer 22 and the third design layer 23 is visible when the light source 30 is lit in the case of observing the laminate 10 of the present invention from the first major surface 11 side. As the coloring agent, the coloring agents exemplified in the above-described first design layer 21 can be used.

[0120] Examples of the material constituting the surface protective layer 3 include, but are not particularly limited to, for example, thermoplastic resins, thermosetting resins, and radiation-curable resins. Among them, from the viewpoint of improving scratch resistance and the like, it is preferable that the surface protective layer 3 is formed of a cured product of a radiation-curable resin composition. The radiation-curable resin for forming the surface protective layer 3 will be described in detail below.

[0121] (Radiation-curable resin)

[0122] The radiation-curable resin for forming the surface protective layer 3 refers to a resin that undergoes crosslinking and curing by irradiation with radiation. Specifically, examples include a mixture in which at least one of a prepolymer, oligomer, and monomer having a polymerizable unsaturated bond or an epoxy group in the molecule is appropriately mixed. Among them, radiation refers to radiation having an energy quantum capable of polymerizing or crosslinking molecules in electromagnetic waves or charged particle beams. Usually, ultraviolet rays (UV) or electron beams (EB) are used. In addition, it also includes electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams. In the radiation-curable resin, since the electron beam-curable resin can obtain stable curing performance without using a solvent (solvent-free) and without a photoinitiator, it is suitable for forming the surface protective layer 3.

[0123] As the above-mentioned monomer that can be used as an ionizing radiation-curable resin, it is preferable to use a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule, and a polyfunctional (meth)acrylate monomer is more preferable. As the polyfunctional (meth)acrylate monomer, a (meth)acrylate monomer having two or more (bifunctional or more) polymerizable unsaturated bonds in the molecule, preferably having three or more (trifunctional or more) polymerizable unsaturated bonds, may be used. Specific examples of the polyfunctional (meth)acrylate monomer 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, dicyclopentadiene di(meth)acrylate, caprolactone-modified dicyclopentadiene di(meth)acrylate, ethylene oxide-modified diphosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanuric acid 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(acryloyloxyethyl) 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 alone or in combination of two or more.

[0124] In addition, as the above oligomer used as a radiation-curable resin, a (meth)acrylate oligomer having a radically polymerizable unsaturated group in the molecule is preferably used. Among them, a polyfunctional (meth)acrylate oligomer having two or more (bifunctional or higher) polymerizable unsaturated bonds in the molecule is more preferable. Examples of the polyfunctional (meth)acrylate oligomer include polycarbonate (meth)acrylate, acrylic silicone (meth)acrylate, polyurethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene (meth)acrylate, silicone (meth)acrylate, and an oligomer having a cationically polymerizable functional group in the molecule (such as linear phenolic epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.). Among them, the polycarbonate (meth)acrylate is not particularly limited as long as it is a compound having a carbonate bond in the polymer main chain and a (meth)acrylate group at the terminal or side chain. For example, it can be obtained by esterifying polycarbonate polyol with (meth)acrylic acid. The polycarbonate (meth)acrylate may be, for example, a polyurethane (meth)acrylate having a polycarbonate skeleton. The polyurethane (meth)acrylate having a polycarbonate skeleton can be obtained by, for example, reacting polycarbonate polyol, polyvalent isocyanate compound, and (meth)acrylic acid hydroxy ester. The acrylic silicone (meth)acrylate can be obtained by radical copolymerization of a silicone macromonomer and a (meth)acrylate monomer. The polyurethane (meth)acrylate can be obtained by, for example, esterifying a polyurethane oligomer obtained by reacting polyether polyol or polyester polyol with a polyisocyanate compound with (meth)acrylic acid. The epoxy (meth)acrylate can be obtained by, for example, esterifying (meth)acrylic acid with an ethylene oxide ring of a bisphenol epoxy resin or a linear phenolic epoxy resin having a relatively low molecular weight. In addition, a carboxyl-modified epoxy (meth)acrylate obtained by partially modifying the epoxy (meth)acrylate with a dicarboxylic anhydride can also be used. The polyester (meth)acrylate can also be obtained by, for example, esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensing a polycarboxylic acid and a polyol with (meth)acrylic acid, or esterifying the hydroxyl group at the end of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth)acrylic acid. The polyether (meth)acrylate can be obtained by esterifying the hydroxyl group of a polyether polyol with (meth)acrylic acid. The polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of a polybutadiene oligomer. The 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 the main chain. These oligomers can be used alone or in combination of two or more kinds.

[0125] In the above-mentioned radiation-curable resin, from the viewpoints of further improving the visual design sense, wear resistance, and moldability, and simultaneously obtaining more excellent three-dimensional moldability, it is preferable to use polycarbonate (meth)acrylate. In addition, it is also preferable to use a combination of polycarbonate (meth)acrylate and polyurethane (meth)acrylate.

[0126] (Other additive components)

[0127] According to the required physical properties of the surface protective layer 3, various additives can be incorporated into the surface protective layer 3. Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, plasticizers, defoaming agents, fillers, solvents, colorants, and the like. These additives can be appropriately selected and used from commonly used additives. In addition, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as (meth)acryloyl in the molecule can also be used.

[0128] (Formation of the surface protective layer 3)

[0129] The formation of the surface protective layer 3 can be achieved, for example, by preparing a radiation-curable resin composition containing a radiation-curable resin, coating the composition to form an uncured resin layer, and crosslinking and curing the uncured resin layer.

[0130] The viscosity of the radiation-curable resin composition only needs to be a viscosity that can form an uncured resin layer by the coating method described later.

[0131] In the present invention, the prepared resin is coated by known methods such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., preferably by gravure coating, to form an uncured resin layer.

[0132] Ionizing radiation such as electron beams and ultraviolet rays is irradiated onto the thus formed uncured resin layer to cure the uncured resin layer and form the surface protective layer 3. Among them, when electron beams are used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used, the layer thickness, etc., and generally, an acceleration voltage of about 70 to 300 kV can be cited.

[0133] It should be noted that since the transmission ability increases with the increase of the acceleration voltage under the irradiation of electron beams, when a resin that is easily deteriorated by the irradiation of electron beams is used under the surface protective layer 3, an acceleration voltage is selected such that the transmission depth of the electron beams is substantially equal to the thickness of the surface protective layer 3. Thereby, it is possible to suppress the irradiation of excess electron beams to the layer located under the surface protective layer 3, and it is possible to control the deterioration of each layer caused by the excess electron beams to the minimum.

[0134] In addition, the irradiation dose is preferably a dose that saturates the crosslinking density of the surface protective layer 3, and is generally selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably in the range of 10 to 50 kGy (1 to 5 Mrad).

[0135] Moreover, as the electron beam source, various electron beam accelerators such as Cockroft Walton type, Van de Graff type, resonant transformer type, insulated core transformer type, linear type, high-frequency high-voltage (Dynamitron) type, high-frequency type, etc. can be used, but are not particularly limited thereto.

[0136] In the case where ultraviolet rays are used as the ionizing radiation, it is sufficient to emit light containing ultraviolet rays with a wavelength of 190 to 380 nm. Examples of the ultraviolet light source include, but are not limited to, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, carbon arc lamps, etc.

[0137] The surface protective layer 3 thus formed can also be subjected to treatment to impart functions such as a hard coating function, an antifogging coating function, an antifouling coating function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, etc. by adding various additives.

[0138] The thickness of the surface protective layer 3 is not particularly limited, but from the viewpoint of imparting surface protection properties such as surface scratch resistance and chemical resistance, it can be exemplified that the lower limit is preferably 5 μm or more, more preferably 10 μm or more, and the upper limit is preferably 30 μm or less, more preferably 20 μm or less. As a preferred range, it can be exemplified that it is about 5 to 20 μm, about 5 to 10 μm, or about 5 to 15 μm.

[0139] [Undercoat]

[0140] The undercoat is a layer provided between the surface protective layer 3 and the first design layer 21 for the purpose of improving the adhesion between the surface protective layer 3 and the layer thereunder, and is in surface contact with the surface on the side of the second main surface 12 of the surface protective layer 3 as needed.

[0141] As the undercoat composition constituting the undercoat, a composition using polyurethane resin, (meth)acrylic resin, (meth)acrylic-polyurethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene, chlorinated polyethylene, etc. as the binder resin is preferably used, and one or two or more of these resins can be used in combination. Among them, polyurethane resin, (meth)acrylic resin, and (meth)acrylic-polyurethane copolymer resin are preferred.

[0142] As the polyurethane resin, a polyurethane using a polyol as the main component and an isocyanate as the crosslinking agent (curing agent) can be used. As the polyol, a compound having two or more hydroxyl groups in the molecule can be used, such as polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol, etc. As the above-mentioned isocyanate, a polyisocyanate having two or more isocyanate groups in the molecule, an aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, or an aliphatic (or alicyclic) isocyanate such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated diphenylmethane diisocyanate can be used. In addition, it can also be formed by mixing polyurethane and butyral resin.

[0143] Preferably, an acrylic polyol or a polyester polyol as the polyol is combined with hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as the crosslinking agent, and particularly preferably, an acrylic polyol and hexamethylene diisocyanate are used in combination.

[0144] Examples of the (meth)acrylic resin include homopolymers of (meth)acrylate, copolymers of two or more different (meth)acrylate monomers, or copolymers of (meth)acrylate and other monomers. Specifically, it is preferably formed of a homopolymer or copolymer containing (meth)acrylate such as poly(methyl)acrylate, poly(methyl)acrylate ethyl, poly(methyl)acrylate propyl, poly(methyl)acrylate butyl, (methyl)acrylate methyl-(methyl)acrylate butyl copolymer, (methyl)acrylate ethyl-(methyl)acrylate butyl copolymer, ethylene-(methyl)acrylate methyl copolymer, styrene-(methyl)acrylate methyl copolymer.

[0145] As the (meth)acrylic-polyurethane copolymer resin, an acrylic-polyurethane (polyester polyurethane) block copolymer resin is preferred, for example. As the curing agent, the above-mentioned various isocyanates can be used. The acrylic-polyurethane (polyester polyurethane) block copolymer resin can adjust the ratio of acrylic / polyurethane (mass ratio) within a range preferably of 9 / 1 to 1 / 9, more preferably of 8 / 2 to 2 / 8 as needed.

[0146] The thickness of the undercoat can be, for example, but not particularly limited to about 0.5 to 20 μm, preferably about 1 to 5 μm.

[0147] The base coat uses a base coating agent composition and is formed by conventional coating methods such as gravure coating, reverse gravure coating, offset gravure coating, spin coating, roll coating, reverse roll coating, kiss coating, wheel coating, dip coating, full-surface coating using a screen, wire bar coating, flow coating, comma coating, curtain coating, brush coating, spray coating, etc., or transfer coating methods. Among them, the transfer coating method is a method of forming a coating film such as a base coat or an adhesive layer on a thin sheet (film substrate) and then covering the surface of the layer to be treated in the laminate.

[0148] [Adhesive layer]

[0149] The adhesive layer (not shown in the figure) is a layer provided as needed for the purpose of bonding between layers. The adhesive layer can be provided, for example, on at least one side of the second design layer 22 and can bond the second design layer 22 to the transparent resin layer 1, the third design layer 23, the transparent substrate layer 4, etc.

[0150] The adhesive layer can use a thermoplastic resin, a curable resin, etc. according to the type of the layer to be bonded.

[0151] Examples of the thermoplastic resin for forming the adhesive layer include acrylic resin, acryloyl-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride / vinyl acetate copolymer, thermoplastic polyurethane resin, thermoplastic polyester resin, polyamide resin, rubber-based resin, etc. These thermoplastic resins can be used alone or in combination of two or more.

[0152] In addition, examples of the thermosetting resin used for forming the adhesive layer include polyurethane resin, epoxy resin, etc. These thermosetting resins can be used alone or in combination of two or more.

[0153] Examples of the thickness of the adhesive layer include about 0.1 to 20 μm.

[0154] [Back adhesive layer]

[0155] The back adhesive layer (not shown in the figure) is a layer provided on the second major surface 12 side (the side opposite to the first design layer 21) of the transparent substrate layer 4 as needed for the purpose of improving the adhesion between the laminate 10 and the molding resin layer 5 when the laminate 10 is molded, in the case where the molding resin layer 5 is provided in the laminate 10.

[0156] The back adhesive layer can use a thermoplastic resin or a curable resin according to the type of the molding resin layer 5 used in the laminate 10.

[0157] As the thermoplastic resin for forming the back adhesive layer, for example, acrylic resin, acryloyl-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride / vinyl acetate copolymer, thermoplastic polyurethane resin, thermoplastic polyester resin, polyamide resin, rubber-based resin, etc. can be cited. These thermoplastic resins can be used alone or in combination of two or more.

[0158] In addition, as the thermosetting resin used for forming the back adhesive layer, for example, polyurethane resin, epoxy resin, etc. can be cited. These thermosetting resins can be used alone or in combination of two or more.

[0159] Regarding the thickness of the back adhesive layer, there is no particular limitation as long as it can bond the molding resin layer 5, and for example, about 0.1 to 20 μm can be cited.

[0160] [Molding resin layer 5]

[0161] In the laminate 10 of the present invention, the transparent molding resin layer 5 can be integrally molded on the side of the second main surface 12. That is, as Figure 5 shown, the laminate 10 of the present invention includes a laminate that sequentially has at least a molding resin layer 5, a second design layer, a transparent resin layer 1, and a first design layer 21, and also has a third design layer 23 on either the first main surface 11 side or the second main surface 12 side of the second design layer 22. When the light source 30 is arranged on the second main surface 12 side, the molding resin layer 5 has the same transparency as the transparent substrate layer 4 to allow the light from the light source to transmit. That is, the molding resin layer 5 is usually transparent (colorless transparent, colored transparent, semi-transparent), but it can also be colored as long as the appearance design based on the second design layer 22 and the third design layer 23 is visible when observing the laminate 10 of the present invention from the first main surface 11 side. For example, the molding resin layer 5 can contain a matting agent such as silica, a coloring agent, etc. As the coloring agent, the coloring agents exemplified in the above second design layer 22 can be used.

[0162] The molding resin layer 5 can be composed of a transparent resin, etc. The transparent resin is preferably formed from a transparent thermoplastic resin. As the transparent thermoplastic resin, but not particularly limited to, transparent acrylonitrile-butadiene-styrene resin (hereinafter also referred to as "ABS resin"), acrylic resin; polyolefin-based resins such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride-based resins; polyethylene terephthalate (PET) resin; acrylonitrile-styrene-acrylate resin, etc. Among them, due to excellent transparency, the molding resin layer 5 is preferably formed from polycarbonate resin. The resin forming the molding resin layer 5 can be one kind or two or more kinds. In addition, examples of the shape of the molding resin layer 5 can include a plate-like body, a molded body, etc.

[0163] The laminate 10 having the formed resin layer 5 can be prepared by laminating the formed resin layer 5 using a known method. In the case where the formed resin layer 5 is a resin molded body, it can also be manufactured by an injection molding method such as an insert molding method.

[0164] In the insert molding method, first, in the vacuum molding process, the laminate before laminating the formed resin layer 5 (that is, the laminate having at least the second design layer 22, the transparent resin layer 1, and the first design layer 21 in sequence from the side of the second main surface 12, and further having the third design layer 23 on either the first main surface 11 side or the second main surface 12 side of the second design layer 22) is pre-vacuum molded (offline pre-molding) into the surface shape of the molded product, and then the excess portion is trimmed as needed to obtain a formed sheet. The formed sheet is inserted into an injection molding die, the injection molding die is closed, and the resin in a flowing state is injected into the die from the side of the transparent base material layer 4 of the laminate and cured. While performing the injection molding, the formed sheet is integrated on the outer surface of the resin molded product, thereby manufacturing the laminate 10 having the formed resin layer 5.

[0165] More specifically, the laminate 10 having the formed resin layer 5 is manufactured by an insert molding method including the following processes. A vacuum molding process of pre-molding the laminate before laminating the formed resin layer 5 into a three-dimensional shape by a vacuum molding die; a trimming process of trimming the excess portion of the laminate obtained by vacuum molding to obtain a formed sheet; and an integration process of inserting the formed sheet into an injection molding die, closing the injection molding die, injecting the resin in a flowing state into the injection molding die from the side of the transparent base material layer 4, and integrating the resin with the formed sheet.

[0166] In the vacuum molding process of the insert molding method, the laminate can also be molded after heating. The heating temperature at this time is not particularly limited and can be appropriately selected according to the resin type constituting the laminate, the thickness of the laminate, etc., and can usually be set to about 120°C to 200°C. In addition, in the integration process, the temperature of the resin in a flowing state can usually be but is not particularly limited to about 180°C to 320°C.

[0167] As described above, the formed resin layer 5 can be formed by selecting a resin corresponding to the use. As the formed resin for forming the formed resin layer 5, the above-mentioned thermoplastic resin can be used, or a thermosetting resin can also be used.

[0168] As the thermosetting resin, for example, polyurethane resin, epoxy resin, etc. can be cited. These thermosetting resins can be used alone or in combination of two or more.

[0169] Since the laminate 10 of the present invention exhibits different appearance designs when the light source is lit and when it is extinguished, it can be used as, for example, interior or exterior components of vehicles such as automobiles; building components such as window frames and door frames; interior components of buildings such as walls, floors, and ceilings; housings of home appliances such as televisions and air conditioners; containers, etc.

[0170] [Decorative article]

[0171] The decorative article 20 of the present invention is a product that utilizes the laminate 10 of the present invention and has the laminate 10 and the light source 30. As Figure 5 shown, the light source 30 is disposed on the side of the second main surface 12 of the laminate 10. The details of the laminate 10 of the present invention are as described above.

[0172] As the type of the light source, examples include, but are not particularly limited to, for example, light emitting diode (LED) bulbs, incandescent bulbs, fluorescent lamps, natural light, etc.

[0173] Since the decorative article of the present invention exhibits different appearance designs when the light source is lit and when it is extinguished, it can be used as, for example, interior or exterior components of vehicles such as automobiles; building components such as window frames and door frames; interior components of buildings such as walls, floors, and ceilings; housings of home appliances such as televisions and air conditioners; containers, etc.

[0174] Examples

[0175] Examples and comparative examples are given below to illustrate the present invention in detail. However, the present invention is not limited to the examples.

[0176] [Manufacture of laminate]

[0177] <Example>

[0178] A laminate (decorative sheet) was produced according to the following steps. On the second major surface side of a transparent resin layer made of acrylic resin with a thickness of 125 μm and a total spectral transmittance of 90%, a pattern layer in the form of a geometric pattern made of acrylic resin containing carbon black (ink) as a colorant was formed as the second design layer. The total spectral transmittance was measured using a haze / transmittance meter HM-150L2N manufactured by Murakami Color Research Institute. Subsequently, a striped design layer made of acrylic resin containing carbon black (ink) as a colorant was printed as the third design layer. Subsequently, a single-color solid layer made of acrylic resin containing a metallic pigment of aluminum was formed as the first design layer on the first major surface side of the transparent resin layer. Subsequently, a transparent substrate layer made of ABS resin was thermally laminated on the third design layer side, and a laminate in which the first design layer / transparent resin layer / second design layer / third design layer / transparent substrate layer were laminated in sequence was obtained. Subsequently, embossing was performed on the first design layer side of the obtained laminate using an embossing plate with a geometric pattern and an embossing plate depth of 60 μm, and an uneven shape was formed on the first design layer. The decorative sheet of the example is a laminate having a first major surface disposed on the observer side and a second major surface disposed on the light source side, wherein the first major surface has an uneven shape and sequentially has at least a first design layer, a transparent resin layer, and a second design layer from the first major surface side, and on the second major surface side of the second design layer, there is also a third design layer. The surface on the first major surface side of the second design layer is relatively flat compared to the uneven shape of the first major surface. The third design layer is partially provided. The thickness of the transparent resin layer of the obtained decorative sheet is 125 μm, the depth of the concave portion formed by embossing is 60 μm, the thickness of the transparent substrate layer is 400 μm, the OD value of the first design layer is 0.8, the OD value of the second design layer is 1.2, and the OD value of the third design layer is 6.0. The OD value was measured using an X-rite 341C transmittance meter. The Rz of the uneven shape on the first major surface side measured according to JIS B0601 (1996) is 55 μm. In addition, the surface Rz on the second major surface side of the transparent resin layer is 3 μm. The cut-off value λc is 0.8 mm. It should be noted that in this method, the transparent resin layer is in full contact with the second design layer, and the surface shape on the second major surface side of the transparent resin layer and the surface shape on the first major surface side of the second design layer are in a complementary relationship.

[0179] <Comparative Example>

[0180] A laminate (decorative sheet) was produced according to the following steps. On one side of the first main surface of a transparent substrate layer made of ABS resin with a thickness of 475 μm, a striped design layer made of acrylic resin containing carbon black (ink) as a colorant was printed as the third design layer, and then a pattern layer of geometric patterns made of acrylic resin containing carbon black (ink) as a colorant was formed as the second design layer. Moreover, a single-color solid layer made of acrylic resin containing aluminum metal pigment was formed as the first design layer, and a laminate in which the first design layer / second design layer / third design layer / transparent substrate layer were laminated in sequence was obtained. Subsequently, embossing was performed on the side of the first design layer of the obtained laminate using an embossing plate with geometric patterns and an embossing plate depth of 60 μm, and an uneven shape was formed on the first design layer. The decorative sheet of the comparative example is different from the decorative sheet of the example in that there is no transparent resin layer between the first design layer and the second design layer. The depth of the concave portion formed by embossing of the obtained decorative sheet is 60 μm, the thickness of the transparent substrate layer is 475 μm, the OD value of the second design layer is 2.2, and the OD value of the third design layer is 6.0. The OD value was measured using an X-rite 341C transmittance measuring instrument.

[0181] [Appearance design evaluation of the second design layer when lit]

[0182] The above-obtained decorative sheet (pre-formed laminate) and decorative resin molded product (after molding) were visually observed from the side of the surface protective layer (observation surface size: 230.4 mm × 135.4 mm), and the appearance when lit on a light plate with a correlated color temperature of 5200 (±300 K) and an average luminance of 1500 ± 300 cd / m 2 was evaluated visually. The appearance designability of the second design layer when lit was evaluated according to the following criteria. The results are shown in Table 1.

[0183] ○: The appearance design based on the second design layer can be confirmed.

[0184] ×: It can be confirmed that the appearance design based on the first design layer overlaps with the appearance design based on the second design layer.

[0185] [Appearance design evaluation of the third design layer when lit]

[0186] The above-obtained decorative sheet (pre-formed laminate) and decorative resin molded product (after molding) were visually observed from the side of the surface protective layer (observation surface size: 230.4 mm × 135.4 mm), and the appearance when lit on a light plate with a correlated color temperature of 5200 (±300 K) and an average luminance of 1500 ± 300 cd / m 2 was evaluated visually. The appearance designability of the third design layer when lit was evaluated according to the following criteria. The results are shown in Table 1.

[0187] ○: The design based on the third design layer can be confirmed.

[0188] ×: It can be confirmed that the design based on the first design layer overlaps with the design based on the third design layer.

[0189] [Table 1]

[0190] Examples Comparative examples Evaluation of the designability of the second design layer when lit ○ × Evaluation of the designability of the third design layer when lit ○ ×

[0191] The decorative sheet of the embodiment is a laminate that exhibits different designs when the light source is lit and when it is extinguished. Among them, the design that appears when the light source is extinguished (the design based on the first design layer) is not easily visible when the light source is lit, and the designs based on the second design layer and the third design layer are visible; when the light source is extinguished, the design based on the first design layer is visible, and the designs based on the second design layer and the third design layer are not easily visible.

[0192] Symbol Explanation

[0193] 1: Transparent resin layer

[0194] 1a: Concavo-convex shape on one side of the first main surface of the transparent resin layer

[0195] 21: First design layer

[0196] 21a: Concavo-convex shape on one side of the first main surface of the first design layer

[0197] 22: Second design layer

[0198] 22a: Surface on one side of the first main surface of the second design layer

[0199] 23: Third design layer

[0200] 3: Surface protection layer

[0201] 3a: Concavo-convex shape on one side of the first main surface of the surface protection layer

[0202] 4: Transparent substrate layer

[0203] 5: Molding resin layer

[0204] 10: Laminate

[0205] 11: First main surface

[0206] 11a: Concavo-convex shape on one side of the first main surface

[0207] 12: Second main surface

[0208] 30: Light source

Claims

1. A laminate, characterized in that: it has a first main surface disposed on the observer side and a second main surface disposed on the light source side, the first main surface has a concavo-convex shape, starting from the first main surface side, it has at least a first design layer, a transparent resin layer, and a second design layer in sequence, on the first main surface side or the second main surface side of the second design layer, there is also a third design layer, the surface on the first main surface side of the second design layer is relatively flat compared to the concavo-convex shape of the first main surface, the third design layer is partially provided.

2. The laminate according to claim 1, characterized in that: the surface on the first main surface side of the transparent resin layer has a concavo-convex shape corresponding to the concavo-convex shape of the first main surface.

3. The laminate according to claim 1 or 2, characterized in that: on the outermost surface on the first main surface side, there is also a surface protection layer.

4. The laminate according to claim 1 or 2, characterized in that: on the second main surface side of the second design layer and the third design layer, there is also a transparent substrate layer.

5. The laminate according to claim 1 or 2, characterized in that: the laminate is in a sheet shape.

6. The laminate according to claim 1 or 2, characterized in that: starting from the second main surface side, it has at least a transparent molding resin layer, the second design layer, the transparent resin layer, and the first design layer in sequence.

7. An ornamental article, characterized in that, it has: the laminate according to claim 1 or 2, and a light source disposed on the second main surface side of the laminate.

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