JP2022157462A - Decorative sheet, decorative resin molding, and method for manufacturing decorative resin molding - Google Patents

Abstract

To provide a decorative sheet capable of imparting excellent apparent design feeling to a decorative resin molding.SOLUTION: A decorative sheet includes at least a base material layer, and a surface protective layer, wherein a surface on the side of the surface protective layer of the base material layer has an uneven shape composed of repeated projection parts and flat parts, the surface protective layer has an uneven shape corresponding to the uneven shape of the base material layer, and when the decorative sheet is heated from 25°C to 160°C, a difference between a surface roughness Sdr value (interface development area ratio) obtained by measuring a position of the projection part of the base material layer and a surface roughness Sdr value (interface development area ratio) obtained by measuring a position of the flat part of the base material layer of the surface protective layer is 0.1 or more.SELECTED DRAWING: None

Description

The present disclosure relates to a decorative sheet, a decorative resin molded product, and a method for manufacturing a decorative resin molded product.

BACKGROUND ART Decorated resin molded products obtained by laminating a decorative sheet on the surface of a resin molded product are used for vehicle interior parts, building interior materials, home appliance housings, and the like. As a method for molding such a decorative resin molded product, a decorative sheet is formed into a three-dimensional shape in advance using a vacuum forming mold, the molded sheet is inserted into an injection mold, and a resin in a fluid state is injected into the mold. An insert molding method that integrates resin and a molded sheet by injection (see, for example, Patent Document 1), a decorative sheet inserted into a mold during injection molding, and a molten resin that is injected into a cavity. Injection simultaneous decoration method for integrating and decorating the surface of a resin molded body (see, for example, Patent Document 2 and Patent Document 3), decorating a preformed resin mold while applying heat and pressure An overlay method of attaching a sheet (see, for example, Patent Document 4) and the like are known.

Japanese Patent Application Laid-Open No. 2004-322501 Japanese Patent Publication No. 50-19132 Japanese Patent Publication No. 61-17255 JP 2012-101549 A JP-A-63-249617 JP-A-10-235734

BACKGROUND ART In order to enhance the design of decorative sheets, many decorative sheets having uneven surfaces formed by embossing have been proposed and manufactured. Such a decorative sheet is passed between an emboss roll having an uneven pattern and a pressure roll while applying a predetermined temperature and pressure to form an uneven shape on the surface of the decorative sheet. Then, it is manufactured through a process of fixing the uneven shape by cooling. For example, in Patent Document 5, a preheated synthetic resin sheet is passed under pressure between an embossing roll (a concave portion filled with powder) and a rubber roll, and the powder is passed through the preheated synthetic resin sheet. A method for producing an embossed sheet is disclosed in which projections are formed by embedding in a resin sheet. Further, in Patent Document 6, a molten resin sheet is passed through a deep groove embossing roll under pressure, the deep groove embossing sheet is heated and aged with almost no tension, and then pressed again with a shallow groove embossing roll to form a deep groove. A method for manufacturing an embossed sheet with shallow grooves is disclosed.

However, when manufacturing a decorative resin molded product using a decorative sheet with an uneven surface formed on the surface, the decorative sheet is subjected to a high temperature and high pressure environment during the molding process such as injection molding after vacuum heat molding. exposed to Then, in the molding process, the uneven shape of the surface of the decorative sheet is flattened (the height difference between the convex portion and the flat portion is reduced), and the design of the decorative sheet before molding is impaired after molding. be.

Under such circumstances, the present disclosure utilizes the phenomenon that the surface state of only the convex portions on the surface of the decorative sheet changes to fine unevenness due to molding, and can impart an excellent design feeling to the decorative resin molded product. The main purpose is to provide a decorative sheet. Another object of the present disclosure is to provide a decorative resin molded product using the decorative sheet and a method for manufacturing the same.

The inventors of the present disclosure have diligently studied to solve the above problems. As a result, in a decorative sheet comprising at least a substrate layer and a surface protective layer, the surface of the substrate layer on the surface protective layer side has an uneven shape formed by repeating convex portions and flat portions. The surface protective layer has an uneven shape corresponding to the uneven shape of the base material layer, and when the decorative sheet is heated from 25 ° C. to 160 ° C., the surface protective layer is The difference between the surface roughness Sdr value (interface development area ratio) measured at the position of the convex portion and the surface roughness Sdr value (interface development area ratio) measured at the position of the flat portion of the base material layer is 0.5. It has been found that the decorative sheet, which is 1 or more, can give a decorative resin molded article an excellent design feeling by appearance.

In addition, the inventors of the present disclosure have found that in a decorative sheet comprising at least a substrate layer and a surface protective layer, the surface of the substrate layer on the surface protective layer side is configured by repeating convex portions and flat portions. The surface protective layer has an uneven shape corresponding to the uneven shape of the base material layer, and when the decorative sheet is heated from 25 ° C. to 160 ° C., the surface protection The layer has an incident angle of 15° (specifically, when the decorative sheet is placed horizontally, the incident angle is inclined 15° from the vertical direction, the reflection angle is also 15°), resolution 50 μm/pixel, distance from illumination light emitting surface to object 100 mm, illuminance 32000 Lx, luminance difference measured under specular reflection conditions (luminance at position of flat part - position of convex part (luminance) of 30 or more can provide a decorative resin molded article with an excellent visual design.

Furthermore, the inventors of the present disclosure have proposed a decorative sheet comprising at least a substrate layer and a surface protective layer, wherein the surface of the substrate layer on the surface protective layer side is formed by repeating convex portions and flat portions. When observing a cross section in the thickness direction of a convex portion that constitutes the uneven shape of the surface protective layer, the thickness of the surface protective layer at the center position of the convex portion is 7 μm or less. When observing the cross section in the thickness direction of the flat part of the surface protective layer, the decorative sheet has a thickness of 10 μm or more at the center position of the flat part. It was also found that it can be applied to decorative resin moldings.

The present disclosure has been completed through further studies based on the above findings.

That is, the present disclosure provides inventions in the following aspects.
Section 1. A decorative sheet comprising at least a substrate layer and a surface protective layer,
The surface of the base material layer on the surface protective layer side has an uneven shape formed by repeating convex portions and flat portions,
The surface protective layer has an uneven shape corresponding to the uneven shape of the base layer,
When the decorative sheet is heated from a temperature of 25° C. to a temperature of 160° C., the surface protective layer has a surface roughness Sdr value (interface expansion area ratio) measured at the position of the convex portion of the base material layer. A decorative sheet, wherein a difference in surface roughness Sdr values (interface developed area ratio) measured at positions of the flat portions of the base material layer is 0.1 or more.
Section 2. A decorative sheet comprising at least a substrate layer and a surface protective layer,
The surface of the base material layer on the surface protective layer side has an uneven shape formed by repeating convex portions and flat portions,
The surface protective layer has an uneven shape corresponding to the uneven shape of the base layer,
When the decorative sheet is heated from a temperature of 25° C. to a temperature of 160° C., the surface protective layer has an incident angle of 15° and a resolution of 50 μm/ pixels, the distance from the light emitting surface to the object is 100 mm, the illuminance is 32000 Lx, and the difference in luminance measured under regular reflection conditions (luminance at the position of the flat portion - luminance at the position of the convex portion) is 30 or more. decorative sheet.
Item 3. The surface protective layer has a thickness of 7 μm or less at the center position of the convex portion when a cross section in the thickness direction is observed for the convex portion constituting the uneven shape of the surface protective layer,
Item 3. The decorative sheet according to Item 1 or 2, wherein the surface protective layer has a thickness of 10 μm or more at the center position of the flat portion when a cross section of the flat portion of the surface protective layer is observed in the thickness direction.
Section 4. 4. The decorative sheet according to any one of Items 1 to 3, wherein the width of the protrusions of the base material layer is 100 μm or more and 350 μm or less.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the flat portion of the base layer has a width of 50 μm or more and 600 μm or less.
Item 6. 6. The decorative sheet according to any one of Items 1 to 5, wherein the height of the protrusions on the surface of the decorative sheet on the surface protective layer side is 10 μm or more and 50 μm or less.
Item 7. Items 1 to 1, wherein the surface protective layer has a thickness of 2 μm or more and 7 μm or less at the center position of the convex portion when observing a cross section in the thickness direction of the convex portion that constitutes the uneven shape of the surface protective layer. 7. The decorative sheet according to any one of 6.
Item 8. Item 8. The decorative sheet according to any one of Items 1 to 7, further comprising a decorative layer between the surface protective layer and the base layer.
Item 9. A decorative resin molded article comprising at least a molded resin layer, a substrate layer, and a surface protective layer in this order,
The surface of the base material layer on the surface protective layer side has an uneven shape formed by repeating convex portions and flat portions,
The surface protective layer has a surface roughness Sdr value (interface expansion area ratio) measured at the position of the convex portion of the base material layer and a surface roughness Sdr measured at the position of the flat portion of the base layer. A decorative resin molded article having a difference in values (interfacial expansion area ratio) of 0.1 or more.
Item 10. A decorative resin molded article comprising at least a molded resin layer, a substrate layer, and a surface protective layer in this order,
The surface of the base material layer on the surface protective layer side has an uneven shape formed by repeating convex portions and flat portions,
The surface protective layer has an incident angle of 15°, a resolution of 50 μm/pixel, a distance from the illumination light emitting surface to the object of 100 mm, an illuminance of 32000 Lx, and regular reflection at the positions of the convex portions and the flat portions of the base layer. A decorative resin molded product, wherein a difference in luminance measured under conditions (luminance at the position of the flat portion - luminance at the position of the convex portion) is 30 or more.
Item 11. Item 9. A method for producing a decorated resin molded product, comprising a step of laminating a molded resin layer on the base layer side of the decorative sheet according to any one of Items 1 to 8 by injecting a resin.

Advantageous Effects of Invention According to the present disclosure, it is possible to provide a decorative sheet that can give a decorative resin molded product an excellent visual design. Further, according to the present disclosure, it is also possible to provide a decorative resin molded product using the decorative sheet and a method for manufacturing the same.

1 is a schematic diagram of a cross-sectional structure of one form of a decorative sheet before heating of the present disclosure; FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a decorative sheet after heating according to the present disclosure; FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a decorative sheet before heating of the present disclosure; FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a decorative sheet after heating according to the present disclosure; FIG. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded product of this disclosure. FIG. 4 is a schematic diagram of an embossed pattern formed on the surface protective layer of the decorative sheet after heating of the present disclosure. FIG. 4 is a schematic diagram of an embossed pattern formed on the surface protective layer of the decorative sheet after heating of the present disclosure.

1. Decorative Sheet The decorative sheet according to the first embodiment of the present disclosure is a decorative sheet including at least a base material layer and a surface protective layer, wherein the surface of the base material layer on the surface protective layer side is The surface protective layer has an uneven shape formed by repeating convex portions and flat portions, and the surface protective layer has an uneven shape corresponding to the uneven shape of the base material layer. When heated to 160° C., the surface protective layer has a surface roughness Sdr value (interfacial development area ratio) measured at the positions of the convex portions of the base layer and a flat portion of the base layer. The difference in surface roughness Sdr value (interfacial development area ratio) is 0.1 or more. Since the decorative sheet according to the first embodiment of the present disclosure has such a specific configuration, it is possible to give the decorative resin molded product an excellent visual sense of design.

Further, a decorative sheet according to a second embodiment of the present disclosure is a decorative sheet including at least a base material layer and a surface protective layer, wherein the surface of the base material layer on the surface protective layer side is convex The surface protective layer has an uneven shape corresponding to the uneven shape of the base material layer, and the decorative sheet is heated at a temperature of 25°C to 160°C. ° C., the surface protective layer has an incident angle of 15° (specifically, when the decorative sheet is placed horizontally, the incident angle is 15° from the vertical direction, and the angle of reflection is also 15°), the resolution is 50 μm/pixel, the distance from the light emitting surface to the object is 100 mm, the illuminance is 32000 Lx, and the difference in brightness measured under specular reflection conditions (flat area (brightness at the position of -brightness at the position of the convex portion) is 30 or more. Since the decorative sheet according to the second embodiment of the present disclosure has such a specific configuration, it is possible to give the decorative resin molded product an excellent visual sense of design.

The decorative sheet of the present disclosure will be described in detail below. In this specification, the numerical range indicated by "-" means "more than" and "less than". For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, in this specification, "(meth)acrylate" means "acrylate or methacrylate", and other similar terms have the same meaning.

Laminated Structure of Decorative Sheet As shown in FIGS. 1 and 3, the decorative sheet 10 of the present disclosure has a laminated structure in which at least a base layer 1 and a surface protective layer 2 located on the surface are laminated. have. As will be described later, the surface of the base material layer 1 on the side of the surface protective layer 2 has an uneven shape formed by repeating the convex portions 11 and the flat portions 12 . Furthermore, the surface protective layer 2 has an uneven shape corresponding to the uneven shape of the base material layer 1 . In addition, in the uneven shapes of the base layer 1 and the surface protective layer 2 of the present disclosure, each convex portion is formed so as to protrude in the direction of the surface protective layer 2 side of the decorative sheet 10. The flat portion is located between the two convex portions.

As will be described later, FIGS. 1 and 3 illustrate the decorative sheet 10 of the present disclosure before being heated, and FIGS. 2 and 4 illustrate the decorative sheet 10a of the present disclosure after being heated. is illustrated. When the decorative sheets 10 shown in FIGS. 1 and 3 are respectively heated from a temperature of 25° C. to a temperature of 160° C. (for example, heated to such a temperature when manufacturing a decorative resin molded product by molding), In the decorative sheet 10a after heating, the protrusions 11 of the base layer 1 and the protrusions 21 of the surface protective layer 2 are crushed, and the position S of the protrusions 11 of the base layer 1 (the position S of the decorating sheet 10 before heating is A fine concave-convex shape is formed in the region where the convex portion existed (see FIGS. 2 and 4). As described later, in the decorative sheet 10 of the present disclosure, by heating from a temperature of 25 ° C. to a temperature of 160 ° C., in order to form a fine uneven shape at the position S of the convex part 11 of the base layer 1 For example, when forming the uneven shape of the base layer 1 of the decorative sheet 10 of the present disclosure by embossing, it is desirable to perform the embossing under low temperature conditions to leave a large internal stress in the base layer 1. Conventionally, in embossing, embossing is performed under high-temperature conditions in order to suppress the uneven convex portions provided on the decorative sheet from being crushed and flattened in the subsequent molding process. However, in the present disclosure, the phenomenon that the surface state of only the convex portion changes to fine unevenness due to the large stress remaining in the convex portion of the base layer is used. It is possible to form a fine uneven shape at the position S of the convex portion 11 of the base material layer 1, and to give the decorative resin molded product an excellent visual sense of design.

As shown in FIG. 3, in the decorative sheet of the present disclosure, a decorative layer 3 is provided between the base material layer 1 and the surface protective layer 2 as necessary for the purpose of enhancing the appearance of the design. may be provided. In addition to the pattern layer having a pattern, the decoration layer 3 may be provided with a masking layer, if necessary, for the purpose of suppressing color change and unevenness of the base material layer 1 . The concealing layer may be provided on the base material layer 1 side of the decorative layer. For the purpose of increasing the adhesion between the surface protective layer 2 and the underlying layer, if necessary, a primer layer may be added so as to be in contact with the surface of the surface protective layer 2 on the substrate layer 1 side. (not shown) may be provided.

Furthermore, in the decorative sheet of the present disclosure, the back surface of the base material layer 1 (the surface opposite to the surface protective layer 2) for the purpose of improving the adhesion with the molding resin when molding the decorative resin molded product ) may be provided with a back adhesive layer (not shown), if necessary.

Examples of the laminated structure of the decorative sheet of the present disclosure include a laminated structure in which base layer 1/surface protective layer 2 are laminated; a laminated structure in which base layer 1/decorative layer 3/surface protective layer 2 are laminated in order; Laminated structure in which back adhesive layer/base layer 1/decorative layer 3/surface protective layer 2 are laminated in order; laminated structure in which base layer 1/primer layer/surface protective layer 2 are laminated in order; base layer 1/ A laminated structure in which decorative layer 3/primer layer/surface protective layer 2 are laminated in this order; a laminated structure in which back adhesive layer/base layer 1/decorating layer 3/primer layer/surface protective layer 2 are laminated in this order; .

FIG. 1 shows a cross-sectional view of a decorative sheet in which a base layer 1/surface protective layer 2 are laminated as one aspect of the laminated structure of the decorative sheet 10 of the present disclosure. FIG. 3 shows a cross-sectional view of a decorative sheet in which base layer 1/decorative layer 3/surface protective layer 2 are laminated as one aspect of the laminated structure of the decorative sheet 10 of the present disclosure.

Concavo-convex shape of the decorative sheet As shown in FIGS. 1 and 3 , in the decorative sheet 10 of the present disclosure before being heated, the surface of the base layer 1 on the surface protective layer 2 side has convex portions and flat portions. It has an uneven shape configured by repeating Furthermore, the surface protective layer 2 has an uneven shape corresponding to the uneven shape of the base material layer 1 .

As shown in the schematic diagrams of FIGS. 2 and 4, the decorative sheet 10 of the present disclosure is heated from a temperature of 25.degree. An uneven shape is formed.

More specifically, for example, in the first embodiment of the decorative sheet 10 of the present disclosure, when the decorative sheet 10 of the present disclosure is heated from a temperature of 25° C. to a temperature of 160° C., the surface protective layer 2 is The surface roughness Sdr value (interface expansion area ratio) measured at the position S of the convex portion 11 of the base layer 1 and the surface roughness Sdr value (interface expansion) measured at the position T of the flat portion 12 of the base layer 1 area ratio) is 0.1 or more. A specific method for measuring these surface roughness Sdr values is as described in Examples. The surface roughness Sdr value is a composite parameter (parameter focused on both the height direction and the plane direction) for evaluating the three-dimensional surface texture (surface roughness) defined by the International Organization for Standardization (ISO) in the international standard ISO25178. ), which is a parameter representing how much the developed area (surface area) of the defined area increases with respect to the area of the defined area. For example, a perfectly flat surface has an Sdr value of zero.

From the viewpoint of particularly favorably exhibiting the effects of the present disclosure, in the first embodiment of the present disclosure, the difference (absolute value) in the surface roughness Sdr value is preferably about 0.12 or more, more preferably about 0. 0.15 or greater, more preferably about 0.2 or greater. The upper limit of the difference (absolute value) of the surface roughness Sdr values is, for example, 2.0 or less and 2.5 or less. The preferred range of the difference (absolute value) of the surface roughness Sdr value is about 0.1 to 2.5, about 0.1 to 2.0, about 0.12 to 2.5, 0.12 to 2 about 0.0, about 0.15 to 2.5, about 0.15 to 2.0, about 0.2 to 2.5, and about 0.2 to 2.0.

From the viewpoint of particularly favorably exhibiting the effects of the present disclosure, in the first embodiment of the present disclosure, the surface protective layer 2 has a surface roughness Sdr value ( interface expansion area ratio) is preferably about 0.05 or more, more preferably about 0.10 or more, and even more preferably about 0.15 or more. Examples of the upper limit of the surface roughness Sdr value include 3.5 or less and 3.0 or less. The preferred range of the surface roughness Sdr value is about 0.05 to 3.5, about 0.05 to 3.0, about 0.10 to 3.5, about 0.10 to 3.0, 0. Examples include about 15 to 3.5 and about 0.15 to 3.0.

Further, from the viewpoint of particularly favorably exhibiting the effects of the present disclosure, in the first embodiment of the present disclosure, the surface protective layer 2 has a surface roughness Sdr The value (interfacial expansion area ratio) is preferably about 0.2 or less, more preferably about 0.1 or less, and even more preferably about 0.05 or less. The lower limit of the surface roughness Sdr value is, for example, 0. Preferred ranges of the surface roughness Sdr value include about 0 to 0.2, about 0 to 0.1, and about 0 to 0.05.

Further, for example, in the second embodiment of the decorative sheet 10 of the present disclosure, when the decorative sheet 10 of the present disclosure is heated from a temperature of 25° C. to a temperature of 160° C., the surface protective layer 2 becomes the base layer 1 , the incident angle is 15° (specifically, when the decorative sheet is placed horizontally, the incident angle is inclined 15° from the vertical direction, the reflection angle also has an inclination of 15°), a resolution of 50 μm/pixel, a distance from the illumination emitting surface to the object of 100 mm, an illuminance of 32000 Lx, and a difference in luminance measured under specular reflection conditions (luminance at position T of flat portion 12−convex portion 11 ) is 30 or more. Specific methods for measuring these luminances are as described in Examples.

From the viewpoint of particularly favorably exhibiting the effects of the present disclosure, in the second embodiment of the present disclosure, the difference in luminance is preferably about 50 or more, more preferably about 60 or more, and still more preferably about 80 or more. . The upper limit of the luminance difference is, for example, 200 or less and 150 or less. The preferable range of the difference in luminance is about 30 to 200, about 30 to 200, about 50 to 200, about 50 to 200, about 60 to 200, about 60 to 200, about 80 to 200, about 80 to 200, etc. is mentioned.

From the viewpoint of particularly favorably exhibiting the effects of the present disclosure, in the second embodiment of the present disclosure, the surface protective layer 2 preferably has a brightness measured at the position T of the flat portion 12 of the base layer 1 of about It is 70 or more, more preferably about 100 or more, still more preferably about 130 or more, and even more preferably 150 or more. Examples of the upper limit of the luminance include 230 or less and 200 or less. Preferred ranges of the luminance include about 70 to 230, about 70 to 200, about 100 to 230, about 100 to 200, about 130 to 230, about 130 to 200, about 160 to 230, and about 160 to 200. be done.

In the second embodiment of the present disclosure, the surface protective layer 2 preferably has a brightness of about 140 or less, more preferably about 130 or less, measured at the position S of the protrusions 11 of the base layer 1. It is preferably about 120 or less, more preferably 100 or less, and even more preferably 70 or less. For example, the lower limit of the luminance is 0. Preferred ranges of the luminance include about 0 to 140, about 0 to 120, about 0 to 100, and about 0 to 70.

Also in the first embodiment of the present disclosure, like the second embodiment of the decorative sheet 10 of the present disclosure, it is preferable to satisfy the above luminance. Also in the second embodiment of the present disclosure, it is preferable to satisfy the surface roughness Sdr value as in the first embodiment of the decorative sheet 10 of the present disclosure.

From the viewpoint of particularly favorably exhibiting the effects of the present disclosure, the width H1 of the protrusions 11 of the base layer 1 is preferably about 50 μm or more, more preferably about 100 μm or more, even more preferably about 150 μm or more, and It is preferably about 350 μm or less, more preferably about 300 μm or less, and preferable ranges are about 50 to 350 μm, about 50 to 300 μm, about 100 to 350 μm, about 100 to 300 μm, about 150 to 350 μm, and about 150 to 300 μm. mentioned. In addition, in the decorative sheet 10 of the present disclosure, the surface protective layer 2 has an uneven shape corresponding to the uneven shape of the base layer 1, and the width of the protrusions 21 of the surface protective layer 2 is larger than that of the base. The width of the protrusions 21 of the surface protective layer 2, which is slightly larger than the width H1 of the protrusions 11 of the material layer 1, is also exemplified as preferable values.

Further, from the viewpoint of exhibiting the effects of the present disclosure particularly preferably, the width H2 of the flat portion 12 of the base material layer 1 is preferably about 50 μm or more, more preferably about 100 μm or more, and even more preferably about 150 μm or more. Also, it is preferably about 600 μm or less, more preferably about 500 μm or less, still more preferably about 350 μm or less, and the preferred ranges are about 50 to 600 μm, about 50 to 500 μm, about 50 to 350 μm, and about 100 to 600 μm. , about 100 to 500 μm, about 100 to 350 μm, about 150 to 600 μm, about 150 to 500 μm, and about 150 to 350 μm. In addition, in the decorative sheet 10 of the present disclosure, the surface protective layer 2 has an uneven shape corresponding to the uneven shape of the base material layer 1, and the width of the flat portion 22 of the surface protective layer 2 is larger than that of the base material. The width of the flat portion 22 of the surface protective layer 2, which is slightly smaller than the width H2 of the flat portion 12 of the material layer 1, is also exemplified as preferable values.

In addition, from the viewpoint of particularly suitably exhibiting the effects of the present disclosure, the height of the protrusions on the surface of the decorative sheet 10 of the present disclosure on the surface protection layer 2 side is preferably about 10 μm or more, more preferably about 15 μm or more. , more preferably about 20 μm or more, more preferably about 50 μm or less, more preferably about 40 μm or less, still more preferably about 30 μm or less. about 30 μm, about 15 to 50 μm, about 15 to 40 μm, about 15 to 30 μm, about 20 to 50 μm, about 20 to 40 μm, and about 20 to 30 μm.

In addition, from the viewpoint of particularly suitably exhibiting the effects of the present disclosure, when observing the cross section in the thickness direction of the convex portions 21 that constitute the uneven shape of the surface protective layer 2 of the decorative sheet 10 of the present disclosure, the convex portions The thickness D1 of the surface protective layer 2 at the central position of 21 is preferably about 2 μm or more, more preferably about 3 μm or more, still more preferably about 5 μm or more, and preferably about 15 μm or less, more preferably about 13 μm or less. , more preferably about 10 μm or less, more preferably about 7 μm or less. about 3 to 10 μm, about 3 to 7 μm, about 5 to 15 μm, about 5 to 13 μm, about 5 to 10 μm, and about 5 to 7 μm.

From the viewpoint of particularly suitably exhibiting the effects of the present disclosure, when observing the cross section in the thickness direction of the convex portions 21 of the surface protective layer 2 that constitute the uneven shape of the decorative sheet 10 of the present disclosure, the convex portions 21 The thickness D1 of the surface protective layer 2 at the center position is about 15 μm or less, and when observing the cross section in the thickness direction of the flat part 22 of the surface protective layer 2, the surface protection at the center position of the flat part 22 Preferably, the thickness of layer 2 is about 10 μm or more. Also, the thickness of the flat portion 22 of the protective layer 2 is thicker than the thickness of the convex portion 21 . As described above, the thickness D1 of the surface protective layer 2 at the central position of the convex portion 21 is preferably about 2 μm or more, more preferably about 3 μm or more, still more preferably about 5 μm or more, and preferably about 13 μm or less. It is more preferably about 10 μm or less, still more preferably 7 μm or less. About 3 to 10 μm, about 3 to 7 μm, about 5 to 15 μm, about 5 to 13 μm, about 5 to 10 μm, and about 5 to 7 μm can be mentioned. In addition, the thickness D2 of the surface protective layer 2 at the center position of the flat portion 22 is preferably about 10 μm or more, more preferably about 15 μm or more, and the upper limit is, for example, about 30 μm or less and about 25 μm or less. is about 10 to 30 μm, about 10 to 25 μm, about 15 to 30 μm, and about 15 to 25 μm. When the surface protective layer 2 contains particles (inorganic particles, organic particles, etc., which will be described later), the thicknesses of the convex portions 21 and the flat portions 22 of the surface protective layer 2 are respectively It refers to the thickness of the non-positioned part.

In the decorative sheet 10, the heated decorative sheet 10a, and the decorative resin molded product 20 of the present disclosure, the uneven pattern (pattern) expressed by the uneven shape is not particularly limited. For example, the uneven pattern represented by the uneven shape is parallel lines. More specifically, in the schematic diagram of FIG. 6, on the surface of the decorative sheet 10a after heating, a plurality of linearly extending linear portions (base material of the decorative sheet 10) in one direction (y direction). A design is formed by repeating the position S of the convex portion 11 of the layer 1 and the region therebetween (the position T of the flat portion 12 of the base layer 1 of the decorative sheet 10). The schematic diagram of FIG. 7 shows a carbon pattern pattern composed of a shape in which a plurality of lines are arranged in one direction and a shape in which a plurality of lines are arranged in a direction perpendicular to this. Specific examples of uneven patterns include hairline patterns, wood grain patterns, geometric patterns (dots, stripes, textiles, carbon, etc.).

Composition of each layer of the decorative sheet [base layer 1]
The base material layer 1 is a resin sheet (resin film) that serves as a support in the decorative sheet of the present disclosure. The resin component used in the base material layer 1 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the molding resin, etc., but preferably a resin film made of a thermoplastic resin. mentioned. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin") and acrylonitrile-styrene-acrylic acid ester resin (hereinafter referred to as "ASA resin"). polyolefin resins such as acrylic resins, polypropylene and polyethylene, polycarbonate resins, vinyl chloride resins, and polyethylene terephthalate (PET). Among these, ABS resins and acrylic resins are preferable from the viewpoint of three-dimensional moldability. Further, the substrate layer 1 may be formed of a single-layer sheet of these resins, or may be formed of a multi-layer sheet of the same or different resins.

The softening point of the thermoplastic resin is preferably about 80 to 155°C, more preferably about 90 to 140°C, still more preferably about 105 to 125°C.

The bending elastic modulus of the base material layer 1 is not particularly limited. For example, when the decorative sheet of the present disclosure is integrated with a molding resin by an insert molding method, the bending elastic modulus at 25 ° C. of the base layer 1 in the decorative sheet of the present disclosure is 500 to 4,000 MPa, preferably 750 to 3,000 MPa can be mentioned. Here, the flexural modulus at 25°C is a value measured according to JIS K7171. If the flexural modulus at 25° C. is 500 MPa or more, the decorative sheet will have sufficient rigidity, and even if it is subjected to the insert molding method, the surface properties and moldability will be much better. In addition, when the flexural modulus at 25° C. is 3,000 MPa or less, sufficient tension can be applied in the case of roll-to-roll production, and slack is less likely to occur, so the pattern is printed over and over again without shifting. The so-called pattern registration becomes good.

In order to improve the adhesion with the layer provided thereon, the substrate layer 1 is subjected to a physical or chemical surface treatment such as an oxidation method or roughening method on one side or both sides, if necessary. may Examples of the oxidation method for the surface treatment of the substrate layer 1 include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment, and the like. Further, examples of the roughening method performed as the surface treatment of the base material layer 1 include a sandblasting method, a solvent treatment method, and the like. These surface treatments are appropriately selected according to the type of the resin component that constitutes the substrate layer 1, but from the viewpoint of effects, operability, and the like, a corona discharge treatment method is preferred.

Further, the substrate layer 1 may be subjected to a treatment such as forming a known adhesive layer.

Furthermore, the base material layer 1 may be colored using a coloring agent, or may be uncolored. Moreover, the base material layer 1 may be in any form of colorless and transparent, colored and transparent, and translucent. The coloring agent used for the substrate layer 1 is not particularly limited, but preferably includes a coloring agent that does not change color even under temperature conditions of 150° C. or higher. Specifically, existing dry colors, paste colors, and masterbatch resins. composition and the like.

The thickness of the base material layer 1 is appropriately set according to the application of the decorative sheet, the molding method for integration with the molding resin, and the like, and is usually about 25 to 1000 μm and about 50 to 700 μm. More specifically, when the decorative sheet of the present disclosure is subjected to an insert molding method, the thickness of the base material layer 1 is usually about 50 to 1000 μm, preferably about 100 to 700 μm, more preferably 100 to 500 μm. degree. Further, when the decorative sheet of the present disclosure is subjected to the simultaneous injection molding decoration method, the thickness of the base material layer 1 is usually about 25 to 200 μm, preferably about 50 to 200 μm, more preferably about 70 to 200 μm. is mentioned. Further, when the decorative sheet of the present disclosure is subjected to an overlay method, the thickness of the base material layer 1 is usually about 50 to 350 μm, preferably about 100 to 300 μm. The thickness of the base material layer 1 is the thickness of the portion where the flat portion 22 of the surface protective layer 2 is located.

As shown in FIGS. 1 and 2, the surface of the substrate layer 1 on the side of the surface protective layer 2 is formed with an uneven shape corresponding to the uneven shape formed on the surface protective layer 2, which will be described later. preferable. As a result, it is possible to more effectively enhance the sense of design by appearance.

[Surface protective layer 2]
The surface protective layer 2 is a layer that is provided to protect the surface of the decorative resin molded product and to provide the decorative resin molded product with an excellent visual sense of design due to its uneven shape. The surface of the surface protective layer 2 is formed with an uneven shape. More specifically, uneven shapes are formed on both surfaces of the surface protective layer 2 . Therefore, the surface of the layer (for example, the base layer 1, the optionally provided primer layer, the decorative layer 3, etc.) that is in contact with the base layer 1 side of the surface protective layer 2 also has the uneven shape. Corresponding uneven shapes are formed. The details of the uneven shape of the surface protective layer 2 are as described above.

As described above, the design expressed on the surface of the decorative sheet by the uneven shape of the surface protective layer 2 is not particularly limited. Designs represented by the uneven shape include, for example, hairline patterns, wood grain patterns, geometric patterns (dots, stripes, textiles, carbon, etc.).

Materials constituting the surface protective layer 2 are not particularly limited, and examples thereof include thermoplastic resins, thermosetting resins, and ionizing radiation-curable resins. Among these, the surface protective layer 2 is preferably composed of a cured product of an ionizing radiation-curable resin composition, from the viewpoint of suitably imparting an excellent visual sense of design to the decorative resin molded product. The ionizing radiation-curable resin used for forming the surface protective layer 2 will be described in detail below.

(Ionizing radiation curable resin)
The ionizing radiation-curable resin used for forming the surface protective layer 2 is a resin that crosslinks and cures when irradiated with ionizing radiation. A suitable mixture of at least one of prepolymers, oligomers, and monomers having Here, the ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used. ray, electromagnetic waves such as γ-rays, charged particle beams such as α-rays and ion beams. Among the ionizing radiation curable resins, the electron beam curable resin is suitable for forming the surface protective layer 2 because it can be solvent-free, does not require a photopolymerization initiator, and provides stable curing properties. used for

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

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

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

Moreover, the surface protective layer 2 may contain at least one of inorganic particles and resin particles. In addition, in the surface protective layer 2 , the inorganic particles and the resin particles mainly have the function of reducing the luster of the surface protective layer 2 . When the surface protective layer 2 contains inorganic particles or resin particles, these particles are dispersed in the surface protective layer 2 .

The inorganic particles are not particularly limited as long as they are particles formed from an inorganic compound, and examples thereof include silica particles, calcium carbonate particles, barium sulfate particles, alumina particles, and glass balloon particles. One type of inorganic particles may be used alone, or two or more types may be used in combination. The particle diameter of the inorganic particles is, for example, about 0.5 to 20 μm, preferably about 1 to 10 μm. In the present invention, the particle diameter of the inorganic particles is determined by using a Shimadzu laser diffraction particle size distribution analyzer SALD-2100, using compressed air to inject powder to be measured from a nozzle, and dispersing it in the air. It is a value measured by a jet-type dry measurement method.

When the surface protective layer 2 contains inorganic particles, the content of the inorganic particles is not particularly limited, but is preferably about 1 to 60 parts by mass, more preferably about 1 to 60 parts by mass, with respect to 100 parts by mass of the ionizing radiation-curable resin. About 10 to 40 parts by mass can be mentioned. One type of inorganic particles may be used alone, or two or more types may be used in combination.

Also, the resin particles are not particularly limited as long as they are particles formed of a resin, and examples include urethane beads, nylon beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, polyethylene beads and the like. One type of resin particles may be used alone, or two or more types may be used in combination. The particle diameter of the resin particles is, for example, about 0.5 to 30 μm, preferably about 1 to 20 μm. The particle diameter of the resin particles is a value measured by the same method as for the inorganic particles.

When the surface protective layer 2 contains resin particles, the content of the resin particles is not particularly limited, but is preferably About 1 to 200 parts by mass, more preferably about 10 to 150 parts by mass.

In addition, when at least one of inorganic particles and resin particles is contained in the surface protective layer 2, a part of these particles may protrude from the surface of the surface protective layer 2, or the particles may be inside the surface protective layer 2. may be buried.

(other additive ingredients)
Various additives can be added to the surface protective layer 2 according to the desired physical properties of the surface protective layer 2 . Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents, colorants and the like. These additives can be appropriately selected and used from commonly used ones. As the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used.

(Formation of surface protective layer 2)
Formation of the surface protective layer 2 is performed, for example, by preparing an ionizing radiation-curable resin composition containing an ionizing radiation-curable resin, applying the composition, and cross-linking and curing the composition. The viscosity of the ionizing radiation-curable resin composition may be any viscosity that allows the formation of an uncured resin layer by the application method described below. As will be described later, in the present disclosure, it can be suitably manufactured by applying a resin that constitutes the surface protective layer 2 to the surface of the substrate layer 1 side on which the uneven shape is formed, and curing the resin.

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

The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer, thereby forming the surface protective layer 2 . Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the thickness of the resin and the layer used, but the acceleration voltage is usually about 70 to 300 kV.

In electron beam irradiation, the higher the accelerating voltage, the higher the penetrating ability. The acceleration voltage is chosen so that the thickness of layer 2 is substantially equal. As a result, it is possible to suppress the irradiation of excess electron beams to the layers located under the surface protective layer 2, and to minimize the deterioration of each layer due to the excess electron beams.

The irradiation dose is preferably an amount that saturates the crosslink density of the surface protective layer 2, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

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

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

By adding various additives to the thus formed surface protective layer 2, hard coat function, anti-fog coat function, anti-fouling coat function, anti-glare coat function, anti-reflection coat function, ultraviolet shielding coat function, A process for imparting a function such as an infrared shielding coating function may be performed.

[Decoration layer 3]
The decorative layer 3 is provided between the base layer 1 and the surface protective layer 2 for the purpose of imparting decorativeness to the decorative sheet, or between the base layer 1 and the primer layer when a primer layer is provided. It is a layer provided accordingly. From the viewpoint of enhancing the visual design, it is preferable that the decorative layer 3 is provided along the uneven shape of the surface protective layer 2 .

Examples of the decorative layer 3 include a pattern layer having a pattern, and a concealing layer having no pattern and intended to suppress color change and variation of the base material layer 1 .

The decorative layer 3 can be a layer formed with a desired pattern using an ink composition, for example. As the ink composition used for forming the decorative layer 3, a mixture of a binder, a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. is used. .

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

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

The pattern formed by the decorative layer 3 is also not particularly limited, but for example, a wood grain pattern, a marble pattern (e.g., travertine marble pattern), a stone grain pattern that imitates the surface of a rock, or a pattern that imitates a texture or cloth-like pattern. Examples include a fabric pattern, a tiled pattern, and a brickwork pattern, and may be a pattern such as a parquet or patchwork that combines these, or may be a single-color solid pattern (so-called all-over solid pattern). These patterns are formed by multi-color printing using the usual process colors of yellow, red, blue, and black, but they can also be formed by special-color multi-color printing by preparing individual color plates that make up the pattern. can be formed.

Although the thickness of the decoration layer 3 is not particularly limited, it is, for example, 1 to 30 μm, preferably 1 to 20 μm. The thickness of the decorative layer 3 is the thickness of the portion of the surface protective layer 2 where the flat portion 22 is located.

Also, the decorative layer 3 may be a metal thin film layer. Examples of metals forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. A method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above metals. The metal thin film layer may be provided on the entire surface or may be provided partially.

When the decorative layer 3 is a metal thin film layer, its thickness is not particularly limited, but from the viewpoint of enhancing the design of the decorative sheet, the optical density (OD value) is preferably 0.6 to 1.8. about 0.8 to 1.4, more preferably about 0.8 to 1.4. The thickness (OD value) of the metal thin film layer is the thickness at the portion where the flat portion 22 of the surface protective layer 2 is located.

(Hiding layer)
In the decorative layer 3, the concealing layer is provided between the base layer 1 and the surface protective layer 2, or between the base layer 1 and the surface protective layer 2 in the case of providing a primer layer, for the purpose of suppressing color change and variation of the base layer 1. This layer is provided between the primer layers, or between the base material layer 1 and the pattern layer when the pattern layer is provided on the decorative layer 3, as required.

The concealing layer is provided to prevent the base layer from adversely affecting the color tone and pattern of the decorative sheet, and is generally formed as an opaque layer.

The concealing layer is formed using an ink composition in which a coloring agent such as a pigment or a dye, an extender, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like are appropriately mixed with a binder. The ink composition for forming the masking layer is appropriately selected from those used for the decorative layer described above.

The concealing layer is usually set to have a thickness of about 1 to 20 μm, and is desirably formed as a so-called solid printing layer. The thickness of the masking layer is the thickness of the portion where the flat portion 22 of the surface protective layer 2 is located.

The concealing layer can be formed by ordinary printing methods such as gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, inkjet printing; gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll. It is formed by a normal coating method such as coating.

[Primer layer]
For the purpose of increasing the adhesion between the surface protective layer 2 and the underlying layer, the primer layer is, if necessary, so as to contact the surface of the surface protective layer 2 on the side of the substrate layer 1. layer to be provided. The primer layer is provided along the uneven shape of the surface protective layer 2 .

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

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

In terms of adhesion with the surface protective layer 2 after cross-linking, resistance to interaction after lamination of the surface protective layer 2, physical properties, and moldability, acrylic polyol or polyester polyol as the polyol and hexamethylene as the cross-linking agent. A combination of diisocyanate and 4,4-diphenylmethane diisocyanate is preferred, and a combination of acrylic polyol and hexamethylene diisocyanate is particularly preferred.

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

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

Although the thickness of the primer layer is not particularly limited, it is, for example, about 0.5 to 20 μm, preferably 1 to 5 μm. The thickness of the primer layer is the thickness of the portion where the flat portion 22 of the surface protective layer 2 is located.

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

[Back adhesive layer]
The back surface adhesive layer (not shown) is formed on the back surface of the base material layer 1 (the surface opposite to the surface protective layer 2) for the purpose of enhancing adhesion to the molding resin when molding the decorative resin molded product. It is a layer provided as needed.

A thermoplastic resin or a curable resin is used for the back adhesive layer depending on the molding resin used for the decorative resin molded product.

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

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

Method for manufacturing decorative sheet The decorative sheet of the present disclosure can be manufactured, for example, by a method comprising the following steps.
Step 1 of forming an uneven shape from one side of the base material layer 1
Step 2 of forming a surface protective layer 2 on the surface side of the substrate layer 1 on which the uneven shape is formed

For example, when the decorative sheet of the present disclosure includes only the base material layer 1 and the surface protective layer 2, the manufacturing method of the decorative sheet will be described as an example. to form an uneven shape. Next, in step 2, the decorative sheet of the present disclosure can be manufactured by forming the surface protective layer 2 on the surface side of the substrate layer 1 on which the uneven shape is formed.

Specifically, in step 2, the surface protective layer 2 is formed by applying a resin constituting the surface protective layer 2 to the surface of the substrate layer 1 side on which the uneven shape is formed.

In step 1, embossing can be suitably employed as a method of forming the uneven shape from one side of the base material layer 1 . Embossing is a known method, in which the surface of the object to be embossed is heated and softened, and then pressed with an embossing plate to shape the uneven shape formed on the embossing plate on the surface of the object to be embossed, It is a method of cooling and fixing. As described above, when forming the uneven shape of the base layer 1 of the decorative sheet 10 of the present disclosure by embossing, embossing is performed under low temperature conditions in order to impart a large internal stress to the base layer 1, It is desirable to leave a large internal stress in the base material layer 1 . Conventionally, in embossing, embossing is performed under high-temperature conditions in order to suppress the uneven convex portions provided on the decorative sheet from being crushed and flattened in the subsequent molding process. However, in the present disclosure, due to the large internal stress remaining in the protrusions of the base material layer, the surface state of only the protrusions changes to fine unevenness. As a result, it becomes possible to form a fine uneven shape at the position S of the convex portion 11 of the base material layer 1, and to give the decorative resin molded product an excellent visual sense of design. A known sheet-fed or rotary embossing machine can be used for embossing. By using an embossing plate corresponding to the uneven shape to be formed on the surface protective layer 2, the uneven shape of the surface protective layer 2 can be formed.

In the manufacturing method of the decorative sheet of the present disclosure, the details of the base material layer 1, the surface protective layer 2, the decorative layer 3 provided as necessary, and the primer layer are as described above.

In step 1, before providing the uneven shape on the surface of the base material layer 1, after laminating the decorative layer 3, the primer layer, etc., as necessary, the uneven shape is formed on the primer layer or the decorative layer 3. You may When laminating the decorative layer 3, the primer layer, etc., it is possible to form an uneven shape on the surface of the base material layer 1 by embossing from the side where these layers are laminated, and after that, The decorative layer 3 and the primer layer can be suitably formed along the uneven shape of the surface protective layer 2 to be formed.

Alternatively, in step 1, before laminating the decorative layer 3, the primer layer, etc., the surface of the base layer 1 is provided with an uneven shape, and then the decorative layer 3, the primer layer, etc. are laminated. good. In this case also, by laminating the decorative layer 3 and the primer layer so that the concave portions of the uneven shape are not completely filled, the uneven shape can be formed on the surface of the base material layer 1, and the uneven shape can be formed. A decorative layer 3 and a primer layer can be formed along.

2. Decorative Resin Molded Product The decorative resin molded product of the present disclosure is molded by integrating molding resin with the decorative sheet 10 of the present disclosure.

More specifically, the first embodiment of the decorative resin molded product 20 of the present disclosure is a decorative resin molded product that includes at least a molding resin layer, a base material layer, and a surface protective layer in this order. The surface of the substrate layer on the surface protective layer side has an uneven shape formed by repeating convex portions and flat portions, and the surface protective layer is measured with respect to the positions of the convex portions of the substrate layer. The difference between the surface roughness Sdr value (interface development area ratio) and the surface roughness Sdr value (interface development area ratio) measured at the position of the flat part of the base material layer is 0.1 or more. .

A second embodiment of the decorative resin molded product 20 of the present disclosure is a decorative resin molded product comprising at least a molding resin layer, a base material layer, and a surface protective layer in this order, wherein the base material The surface of the layer on the side of the surface protective layer has an uneven shape formed by repeating convex portions and flat portions. Angle 15°, resolution 50 μm/pixel, distance from illumination light emitting surface to object 100 mm, illuminance 32000Lx, luminance difference measured under regular reflection conditions (luminance at position of flat portion - luminance at position of convex portion) It is characterized by being 30 or more.

FIG. 5 shows a cross-sectional structure of one aspect of the decorative resin molded product of the present disclosure. 5 is a schematic cross-sectional view of a decorative resin molded product 20 in which the decorative sheet 10 having the laminated structure shown in FIG. 3 and the molded resin layer 4 are integrated. In the decorative resin molded product 20, the decorative sheet integrated with the molded resin layer 4 corresponds to the heated decorative sheet 10a.

The decorative resin molded product of the present disclosure can be manufactured by a method including the step of forming the molded resin layer 4 by injecting a resin onto the substrate layer 1 side of the decorative sheet 10 of the present disclosure. Specifically, using the decorative sheet of the present disclosure, it is produced by various injection molding methods such as an insert molding method, an injection molding simultaneous decoration method, a blow molding method, and a gas injection molding method.

In the insert molding method, first, in the vacuum forming process, the decorative sheet of the present disclosure is vacuum-formed (off-line preforming) in advance to the surface shape of the molded product using a vacuum forming mold, and then, if necessary, the excess portion is trimmed. Obtain a molded sheet. This molding sheet is inserted into an injection mold, the injection mold is clamped, and the resin in a fluid state is injected into the mold and solidified. A decorative resin molded product is manufactured by integrating the material layer 1 side.

More specifically, the decorative resin molded product of the present disclosure is manufactured by an insert molding method including the following steps.

A vacuum forming step of forming the decorative sheet of the present disclosure into a three-dimensional shape in advance with a vacuum forming mold;
A step of trimming the excess portion of the vacuum-formed decorative sheet to obtain a molded sheet, and inserting the molded sheet obtained in the above step into an injection mold, closing the injection mold, and pouring the resin in a fluid state into the mold. The process of injecting the resin and molding sheet into one.

In the vacuum forming step in the insert molding method, the decorative sheet may be heated and formed. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet and the thickness of the decorative sheet. For example, it can be usually about 100 to 250°C, preferably about 130 to 200°C. In addition, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but it is usually about 180 to 320.degree. C., preferably about 220 to 280.degree.

In the simultaneous injection molding and decorating method, the decorative sheet of the present disclosure is arranged in a female mold that is also used as a vacuum molding mold provided with injection molding suction holes, and preforming (inline preforming) is performed in this female mold. After that, the injection mold is clamped, the resin in a fluid state is injected into the mold, solidified, and simultaneously with the injection molding, the base layer of the decorative sheet of the present disclosure is applied to the outer surface of the resin molding. A decorative resin molded product is manufactured by integrating one side.

More specifically, the decorated resin molded product of the present disclosure is manufactured by the simultaneous injection molding and decorating method including the following steps.

After the decorative sheet of the present disclosure is placed so that the base material of the decorative sheet faces the molding surface of a movable mold having a molding surface of a predetermined shape, the decorative sheet is heated and softened. At the same time, a step of preforming a decorative sheet by vacuum suction from the movable mold side and bringing the softened decorative sheet into close contact along the molding surface of the movable mold;
After the movable mold and fixed mold having the decorative sheet adhered along the molding surface are clamped, the resin molding material in a fluid state is injected and filled into the cavity formed by both molds. An injection molding process in which the formed resin molded body and the decorative sheet are laminated and integrated by solidification, and a resin molded body in which all layers of the decorative sheet are laminated by separating the movable mold from the fixed mold. The process of removing the

In the preforming step of the simultaneous injection molding and decorating method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. When a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can be usually about 70 to 130°C. Also, in the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but it is usually about 180 to 320.degree. C., preferably about 220 to 280.degree.

In addition, the decorative resin molded product of the present disclosure can be obtained by a decoration method ( overlay method).

In the overlay method, first, the decorative sheet and the resin molded body of the present disclosure are placed in a vacuum crimping machine consisting of a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side, and the decorative sheet is placed in the first vacuum. It is placed in the vacuum crimping machine so that the chamber side, the resin molded body is on the second vacuum chamber side, and the base layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are evacuated. . The resin molded body is placed on a vertically movable platform provided on the side of the second vacuum chamber. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using a lifting table, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. affixed to the surface of Finally, the two vacuum chambers are opened to the atmospheric pressure, and the excess portion of the decorative sheet is trimmed as necessary to obtain the decorated resin molded product of the present disclosure.

In the overlay method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve formability before the step of pressing the molding against the decorative sheet. An overlay method including the process is sometimes called a vacuum thermocompression bonding method. The heating temperature in this step may be appropriately selected depending on the type of resin constituting the decorative sheet and the thickness of the decorative sheet. , usually about 60 to 200°C.

In the decorative resin molded product of the present disclosure, the molding resin layer may be formed by selecting molding resin according to the application. The molding resin may be a thermoplastic resin or a thermosetting resin.

Examples of thermoplastic resins used as molding resins include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins. These thermoplastic resins may be used singly or in combination of two or more.

Thermosetting resins used as molding resins include, for example, urethane resins and epoxy resins. These thermosetting resins may be used singly or in combination of two or more.

Since the decorative resin molded product of the present disclosure has an excellent design, it can be used, for example, for interior or exterior materials for vehicles such as automobiles; fittings; interior materials for buildings such as walls, floors and ceilings; housings for home electric appliances such as television receivers and air conditioners;

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

[Example 1-1]
A black ABS resin film (thickness: 200 μm, softening point: 130° C.) was used as the base layer. An ink composition containing a coloring agent and a resin (mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer) is used on the base layer to form a concealing layer with a thickness of 1 μm and a thickness of 2 μm on the entire surface of the base layer. A decorative layer of ˜10 μm was applied by gravure printing and dried to form a decorative layer. Next, the obtained laminate is heated to 120 to 140° C. to soften it, and the decorative layer side is in contact with the embossing roll (plate depth 60 μm). and then rapidly cooled down to 30° C. with a cooling roll to form an uneven shape on the decorative layer side of the laminate. Considering the melting point of the resin, the conditions for forming this rugged shape are lower than those for general rugged shapes using an embossing roll, and the conditions for increasing the residual stress due to the provision of the rugged shape are adopted. is doing. The formed uneven shape is a parallel line pattern in which a plurality of lines are arranged in one direction (see the schematic diagram of FIG. 6), and the width H1 (line width ) is 138 μm, and the width H2 (line interval) of the flat portion 12 is 188 μm.

Next, 95 parts by mass of ionizing radiation-curable resin composition A (bifunctional urethane acrylate having a polycarbonate skeleton (weight average molecular weight: 20,000) and hexafunctional urethane acrylate (weight-average molecular weight: 3,000) 5 parts by weight of ink containing 30% by weight of resin and 70% by weight of diluent solvent) was applied by gravure printing to form an uncured resin layer. Next, the uncured resin layer was irradiated with an electron beam at an acceleration voltage of 165 kV and a radiation dose of 50 kGy (5 Mrad) to provide a surface protective layer, thereby obtaining a decorative sheet having an uneven surface.

[Example 1-2]
Example except that the embossing roll was changed, the width H1 (line width) of the protrusions 11 formed on the base layer was set to 188 μm, and the width H2 (line spacing) of the flat portions 12 was set to 188 μm. A decorative sheet was obtained in the same manner as in 1-1.

[Example 1-3]
Example except that the embossing roll was changed, the width H1 (line width) of the protrusions 11 formed on the base layer was set to 288 μm, and the width H2 (line spacing) of the flat portions 12 was set to 188 μm. A decorative sheet was obtained in the same manner as in 1-1.

[Example 1-4]
Except for changing the embossing roll and setting the width H1 (line width) of the convex portion 11 formed on the base material layer to 288 μm and the width H2 (line spacing) of the flat portion of the flat portion 12 to 288 μm. A decorative sheet was obtained in the same manner as in 1-1.

[Example 1-5]
Example except that the embossing roll was changed, the width H1 (line width) of the protrusions 11 formed on the base material layer was set to 288 μm, and the width H2 (line spacing) of the flat portions 12 was set to 588 μm. A decorative sheet was obtained in the same manner as in 1-1.

[Comparative Example 1-1]
In the production of the decorative sheet of Example 1-1, "the obtained laminate was heated to 120 to 140° C. to soften it, and the laminate was formed so that the decorative layer side was in contact with an embossing roll (plate depth 60 μm). Instead of passing between the embossing roll and the rubber roll at a heating temperature of 70 to 90 ° C. and then rapidly cooling to 30 ° C. with a cooling roll, "the obtained laminate is heated to 180 to 200 ° C. to soften and decorate. The layer side is in contact with the embossing roll (plate depth 60 μm), the laminate is passed between the embossing roll and the rubber roll at a heating temperature of 140 to 160 ° C., and further cooled to 30 ° C. with a cooling roll. A decorative sheet having an uneven surface was obtained in the same manner as in Example 1-1. The conditions for forming the uneven shape are general conditions for forming an uneven shape using an embossing roll. That is, a condition is employed in which the base material layer is softened at a high temperature so that the residual stress due to the provision of the uneven shape becomes as small as possible. Flattening of the projections of the base material layer due to residual stress during molding of the decorative sheet is suppressed as much as possible.

[Comparative Example 1-2]
Except for changing the embossing roll and setting the width H1 (line width) of the convex portion 11 formed on the base material layer to 188 μm and the width H2 (line spacing) of the flat portion of the flat portion 12 to 188 μm, Comparative Example A decorative sheet was obtained in the same manner as in 1-1.

[Comparative Example 1-3]
Except for changing the embossing roll and setting the width H1 (line width) of the convex portion 11 formed on the base material layer to 288 μm and the width H2 (line spacing) of the flat portion of the flat portion 12 to 188 μm, Comparative Example A decorative sheet was obtained in the same manner as in 1-1.

[Comparative Example 1-4]
Comparative Example except that the embossing roll was changed, the width H1 (line width) of the convex portion 11 formed on the base layer was set to 288 μm, and the width H2 (line spacing) of the flat portion of the flat portion 12 was set to 288 μm. A decorative sheet was obtained in the same manner as in 1-1.

[Comparative Example 1-5]
Except for changing the embossing roll and setting the width H1 (line width) of the convex portion 11 formed on the base material layer to 288 μm and the width H2 (line spacing) of the flat portion of the flat portion 12 to 588 μm, Comparative Example A decorative sheet was obtained in the same manner as in 1-1.

<Manufacturing of decorative resin molded products>
The decorative sheet was heated with an infrared heater to soften the sheet temperature from 25°C to 160°C. Then, vacuum forming was performed using a vacuum forming mold (maximum draw ratio: 100%) to form the internal shape of the mold. After the molded decorative sheet was cooled, it was released from the mold. Thereafter, an injection resin (ABS resin melted at a temperature of 250° C.) is injected into the cavity of the mold, and the base layer side of the decorative sheet and the injection resin are integrally molded. A decorative resin molded product (decorative sheet after molding) was obtained.

<Measurement of Surface Roughness Sdr Value (Interface Expansion Area Ratio) of Decorative Sheet Before and After Molding>
To measure the surface roughness Sdr value of the decorative sheet, a laser microscope (VK-X1000 manufactured by Keyence Corporation) is used to observe the surface of the molded product magnified with a 20x objective lens while observing the surface protective layer. Five regions were specified for each of the convex portions and the flat portions, and the average value of the measurement results was adopted as the surface roughness Sdr value.

Regarding the decorative sheet before being subjected to <manufacture of decorative resin molded product>, the convex portions on the surface of the surface protective layer (positions corresponding to the convex portions on the base layer) and the flat portions on the surface of the surface protective layer The surface roughness Sdr value (interface development area ratio) of (the position corresponding to the flat part of the base material layer) was measured, and the difference was calculated. Table 1 shows the results.

In addition, the decorative sheet after being subjected to the <manufacturing of the decorative resin molded product> (the decorative sheet after molding, which is integrated with the molded resin layer and constitutes a part of the decorative resin molded product ), the surface roughness Sdr value of the convex portions on the surface of the surface protective layer (positions corresponding to the convex portions of the substrate layer) and the flat portions on the surface of the surface protective layer (positions corresponding to the flat portions of the substrate layer) (Interface development area ratio) was measured, and the difference was calculated. Table 1 shows the results.

<Measurement of brightness of decorative sheet after molding>
Using the Aviiva E2V camera manufactured by TELEDYNE and the LNSP lighting manufactured by CCS, the decorative sheet after being subjected to the above-mentioned <manufacturing of the decorative resin molded product> (the decorative resin molded product integrated with the resin molded product For the surface of the surface protective layer of the decorative sheet after molding, which constitutes a part of the base layer, measure the luminance at the positions of the convex and flat parts of the base layer, and measure the difference (the position of the flat part (brightness-brightness at the position of the convex portion) was calculated. The luminance measurement conditions were an incident angle of 15° (specifically, when the decorative sheet was placed horizontally, the incident angle was inclined by 15° from the vertical direction and the reflection angle was also inclined by 15°), and the resolution was 50 μm/ Pixels, distance from illumination light emitting surface to object: 100 mm, illuminance: 32000 Lx, specular reflection conditions. Table 1 shows the results.

<Measurement of thickness of surface protective layer of decorative sheet before molding>
The decorative sheet is cut in the thickness direction, and a cross-sectional image of the cross section in the thickness direction is obtained using a scanning electron microscope (SEM). The thickness D2 at each position was measured at five positions, and the average value was taken as the thickness of each. Table 1 shows the results.

<Evaluation of design feeling by appearance>
The decorative sheet after being subjected to the <manufacturing of the decorative resin molded product> (the decorative sheet after molding, which is integrated with the resin molded product and constitutes a part of the decorative resin molded product) The surface on the side of the surface protective layer was visually observed, and the three-dimensional design feeling was evaluated according to the following criteria based on shadows and the like observed due to the uneven shape. Table 1 shows the results.
A: Shadows are sufficiently expressed on the surface of the decorative sheet, and a three-dimensional design feeling can be sufficiently confirmed when irradiated with oblique light.
C: Shadows on the entire surface of the decorative sheet are weak, or when oblique light is irradiated, the shadows are insufficient due to the light irradiated to the recesses of the uneven shape, and a sufficient three-dimensional design feeling is not obtained. .

In Table 1, "-" means unmeasured.

[Example 2-1]
Using the ionizing radiation curable resin composition A for forming the surface coating layer, and changing the embossing roll to arrange a plurality of lines in one direction and a plurality of lines in a direction perpendicular to this. Same as Example 1-1 except that an embossing roll (the plate depth of the embossing roll is 45 μm) on which a carbon pattern (see the schematic diagram in FIG. 7) is formed, which is composed of a shape that has been formed. A decorative sheet was thus obtained. The width H1 (line width) of the convex portion 11 formed on the base layer is 120 μm, and the width H2 (line spacing) of the flat portion of the flat portion 12 is 80 μm.

[Example 2-2]
In the same manner as in Example 2-1, except that the embossing roll was changed to form a triangular geometric pattern (the depth of the embossing roll was 60 μm). A decorative sheet was obtained. The width H1 (line width) of the convex portion 11 formed on the base layer is 120 μm, and the width H2 (line spacing) of the flat portion of the flat portion 12 is 300 μm.

[Comparative Example 2-1]
Using the ionizing radiation curable resin composition A for forming the surface coating layer, and changing the embossing roll to arrange a plurality of lines in one direction and a plurality of lines in a direction perpendicular to this. A decorative sheet was obtained in the same manner as in Comparative Example 1-1, except for using an embossing roll (the plate depth of the embossing roll was 45 μm) formed with a carbon pattern, which was composed of a shaped shape. . The width H1 (line width) of the convex portion 11 formed on the base layer is 120 μm, and the width H2 (line spacing) of the flat portion of the flat portion 12 is 80 μm.

[Example 3-1]
Ionizing radiation curable resin composition B (bifunctional urethane acrylate having a polycarbonate skeleton (weight average molecular weight 20,000) 87 parts by weight and hexafunctional urethane acrylate (weight average molecular weight 3,000) 5 for forming the surface coating layer Ink containing 30% by mass of a resin composition consisting of 8 parts by mass of a resin and 8 parts by mass of acrylic resin beads and 70% by mass of a diluting solvent), and by changing the embossing roll, the width and interval are inconsistent. A decorative sheet was obtained in the same manner as in Example 1-1, except that an embossing roll (the plate depth of the embossing roll was 60 μm) that formed a line pattern composed of regular line shapes was used. . The width H1 (line width) of the convex portion 11 formed on the base layer is 100 to 200 μm, and the width H2 (line interval) of the flat portion of the flat portion 12 is 80 to 150 μm.

[Example 3-2]
Decorative sheet in the same manner as in Example 3-1 except that the embossing roll is changed to form a rhombus-shaped geometry (the plate depth of the embossing roll is 60 μm). got The width H1 (line width) of the convex portion 11 formed on the base layer is 80 μm, and the width H2 (line spacing) of the flat portion of the flat portion 12 is 100 μm.

For the decorative sheets obtained in Examples 2-1, 2-2, 3-1, 3-2 and Comparative Example 2-1, Examples 1-1 to 1-5 and Comparative Examples 1-1 to In the same manner as in 1-5, the production of the decorative resin molded product, the measurement of the surface roughness Sdr value (interface expansion area ratio) of the decorative sheet after molding, and the thickness of the surface protective layer of the decorative sheet before molding Measurement and visual evaluation of design feeling were carried out. Table 2 shows the results.

In Table 2, "-" means unmeasured.

1 base material layer 2 surface protective layer 3 decoration layer 4 molded resin layer 10 decorative sheet 10a decorative sheet 11 after molding convex portion 12 of base material layer flat portion 21 of base layer convex portion 22 of surface protective layer surface protection Flat portion of layer D1 Thickness at central position of convex portion of surface protective layer D2 Thickness at central position of flat portion of surface protective layer H1 Width of convex portion of substrate layer H2 Width of flat portion of substrate layer S After heating Position T of convex portion of base layer of decorative sheet Position of flat portion of base layer of decorative sheet after heating

Claims (11)

A decorative sheet comprising at least a substrate layer and a surface protective layer,
The surface of the base material layer on the surface protective layer side has an uneven shape formed by repeating convex portions and flat portions,
The surface protective layer has an uneven shape corresponding to the uneven shape of the base layer,
When the decorative sheet is heated from a temperature of 25° C. to a temperature of 160° C., the surface protective layer has a surface roughness Sdr value (interface expansion area ratio) measured at the position of the convex portion of the base material layer. A decorative sheet, wherein a difference in surface roughness Sdr values (interface developed area ratio) measured at positions of the flat portions of the base material layer is 0.1 or more. A decorative sheet comprising at least a substrate layer and a surface protective layer,
The surface of the base material layer on the surface protective layer side has an uneven shape formed by repeating convex portions and flat portions,
The surface protective layer has an uneven shape corresponding to the uneven shape of the base layer,
When the decorative sheet is heated from a temperature of 25° C. to a temperature of 160° C., the surface protective layer has an incident angle of 15° and a resolution of 50 μm/ pixels, the distance from the light emitting surface to the object is 100 mm, the illuminance is 32000 Lx, and the difference in luminance measured under regular reflection conditions (luminance at the position of the flat portion - luminance at the position of the convex portion) is 30 or more. decorative sheet. The surface protective layer has a thickness of 7 μm or less at the center position of the convex portion when a cross section in the thickness direction is observed for the convex portion constituting the uneven shape of the surface protective layer,
3. The decorative sheet according to claim 1, wherein the surface protective layer has a thickness of 10 μm or more at the center position of the flat portion when a cross section in the thickness direction of the flat portion of the surface protective layer is observed. . The decorative sheet according to any one of claims 1 to 3, wherein the width of the protrusions of the base material layer is 100 µm or more and 350 µm or less. The decorative sheet according to any one of claims 1 to 4, wherein the flat portion of the base layer has a width of 50 µm or more and 600 µm or less. The decorative sheet according to any one of claims 1 to 5, wherein the height of the projections on the surface of the decorative sheet facing the surface protection layer is 10 µm or more and 50 µm or less. 2. The surface protective layer has a thickness of 2 μm or more and 7 μm or less at a central position of the convex portion when a cross section in the thickness direction of the convex portion forming the uneven shape of the surface protective layer is observed. 7. The decorative sheet according to any one of 6. The decorative sheet according to any one of claims 1 to 7, further comprising a decorative layer between said surface protective layer and said base layer. A decorative resin molded article comprising at least a molded resin layer, a substrate layer, and a surface protective layer in this order,
The surface of the base material layer on the surface protective layer side has an uneven shape formed by repeating convex portions and flat portions,
The surface protective layer has a surface roughness Sdr value (interface expansion area ratio) measured at the position of the convex portion of the base material layer and a surface roughness Sdr measured at the position of the flat portion of the base layer. A decorative resin molded article having a difference in values (interfacial expansion area ratio) of 0.1 or more. A decorative resin molded article comprising at least a molded resin layer, a substrate layer, and a surface protective layer in this order,
The surface of the base material layer on the surface protective layer side has an uneven shape formed by repeating convex portions and flat portions,
The surface protective layer has an incident angle of 15°, a resolution of 50 μm/pixel, a distance from the illumination light emitting surface to the object of 100 mm, an illuminance of 32000 Lx, and regular reflection at the positions of the convex portions and the flat portions of the base layer. A decorative resin molded product, wherein a difference in luminance measured under conditions (luminance at the position of the flat portion - luminance at the position of the convex portion) is 30 or more. A method for producing a decorated resin molded product, comprising the step of laminating a molded resin layer by injecting a resin onto the base layer side of the decorative sheet according to any one of claims 1 to 8.

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