JP7070597B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

The present invention relates to a decorative sheet having a metallic design. Further, the present invention relates to a decorative resin molded product using the decorative sheet.

Conventionally, in order to give a metallic design to vehicle interior / exterior parts, building material interior materials, home appliance housings, etc., members having a resin surface coated with metal such as metal plating or metal coating have been used. However, when performing metal plating, metal coating, etc., it is necessary to take measures such as treatment of wastewater containing metal and measures against solvent vapor. Also, in general, the yield of these members is not good.

Therefore, in recent years, as these members, a decorative resin molded product in which a decorative sheet having a metallic tone is laminated on the surface of the resin molded product has been used (see, for example, Patent Document 1). In the production of a decorative resin molded product, a molding method in which a decorative sheet to which a design has been given in advance is integrated with a resin by injection molding or the like is used.

In such a decorative sheet, a metal thin film layer is formed on the base material layer, and the metal thin film layer is generally used for the purpose of improving the scratch resistance of the decorative resin molded product. A surface protective layer is formed on top of it.

As a method for expressing a metallic tone in a decorative sheet, for example, a method of laminating metals by a vapor deposition method, a sputtering method, or the like is known. However, when the metallic thin film layer formed by the vapor deposition method or the sputtering method is used to express a metallic tone, the metallic luster becomes too strong, the texture becomes cheap, and the reflected light is too strong (especially in automobile interior applications, it is distracting). It interferes with driving), which makes it difficult to understand the shape.

Japanese Unexamined Patent Publication No. 2011-167844

In recent years, consumer demand for decorative resin molded products has become more sophisticated and diversified in recent years, and decorative resin molded products with metallic designs have appropriate metallic luster and surface imageability. There is a demand for new products with excellent designs. As a method of suppressing the high metallic luster caused by the metallic thin film layer and exerting an appropriate metallic luster, a matting agent is added to the surface protective layer, or the surface of the surface protective layer is subjected to satin finish or sandblasting. It is conceivable to reduce the luster by providing a fine uneven shape on the surface of the surface protective layer. However, these methods of adjusting the metallic luster to an appropriate level by the surface protective layer have a problem that the imageability of the surface is deteriorated. On the other hand, in order to improve the image quality of the surface, it is conceivable to improve the smoothness of the surface, but if the smoothness of the surface is improved, there is a problem that the metallic luster becomes too strong.
Under such circumstances, it is a main object of the present invention to provide a decorative sheet capable of imparting a design having excellent image quality to a decorative resin molded product in addition to a design having an appropriate metallic luster. do.

The present inventor has made diligent studies to solve the above problems. As a result, at least the base material layer, the metal thin film layer, the fine particle-containing layer, and the surface protection layer are laminated in this order, and the surface of the fine particle-containing layer on the metal thin film layer side is the fine particle-containing layer. It has been found that the decorative sheet having an uneven shape due to the fine particles contained in the above can impart a design having excellent imageability to the decorative resin molded product in addition to a design having an appropriate metallic luster. The present invention is an invention completed by further studies based on these findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. At least, it is composed of a laminate in which a base material layer, a metal thin film layer, a fine particle-containing layer, and a surface protection layer are laminated in this order.
A decorative sheet having an uneven shape due to the fine particles contained in the fine particle-containing layer on the surface of the fine particle-containing layer on the side of the metal thin film layer.
Item 2. Between the layer and the surface protective layer, at least one layer of a first primer layer, a first resin layer, a color clear layer, a second resin layer, and a second primer layer is provided in this order from the surface protective layer side. Primer,
Item 2. The item 1 in which at least one of the first primer layer, the first resin layer, the color clear layer, the second resin layer, and the second primer layer constitutes the fine particle-containing layer. Decorative sheet.
Item 3. Item 2. The decorative sheet according to Item 2, wherein the color clear layer constitutes the fine particle-containing layer.
Item 4. Item 2. The decorative sheet according to Item 2 or 3, wherein the first resin layer constitutes the fine particle-containing layer.
Item 5. Item 2. The decorative sheet according to any one of Items 2 to 4, wherein the second resin layer constitutes the fine particle-containing layer.
Item 6. Item 2. The decorative sheet according to any one of Items 1 to 5, wherein in the fine particle-containing layer, the thickness of the portion where the fine particles are located is 1.2 times or more the thickness of the portion where the fine particles are not located. ..
Item 7. Item 2. The decorative sheet according to any one of Items 1 to 6, wherein the shortest distance between the portion of the fine particle-containing layer where the fine particles are located and the surface of the metal thin film layer on the fine particle-containing layer side is 10 μm or less. ..
Item 8. Item 2. The decorative sheet according to any one of Items 1 to 7, wherein the metal thin film layer is a layer formed by a vapor deposition method, a sputtering method, or an ion plating method.
Item 9. The metal thin film layer is formed of at least one metal selected from the group consisting of tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and an alloy containing at least one of these. The decorative sheet according to any one of Items 1 to 8.
Item 10. Item 2. The decorative sheet according to any one of Items 1 to 9, wherein the thickness of the metal thin film layer is 200 nm or less.
Item 11. Item 2. The decorative sheet according to any one of Items 1 to 10, wherein the surface protective layer is formed of an ionizing radiation curable resin or a resin film.
Item 12. At least, it is composed of a laminate in which a molding resin layer, a base material layer, a metal thin film layer, a fine particle-containing layer, and a surface protection layer are laminated in this order.
A decorative resin molded product having an uneven shape due to the fine particles contained in the fine particle-containing layer on the surface of the fine particle-containing layer on the side of the metal thin film layer.

According to the present invention, a decorative sheet capable of imparting a design having excellent image quality in addition to a design having an appropriate metallic luster to a decorative resin molded product, and a decorative resin molding using the decorative sheet. Goods can be provided.

It is a schematic sectional drawing of an example of the decorative sheet which concerns on this invention. It is a schematic sectional drawing of an example of the decorative sheet which concerns on this invention. It is a schematic sectional drawing of an example of the decorative sheet which concerns on this invention. It is a schematic sectional drawing of an example of the decorative sheet which concerns on this invention. It is a schematic sectional drawing of an example of the decorative sheet which concerns on this invention. It is a schematic sectional drawing of an example of the decorative sheet which concerns on this invention. It is a schematic sectional drawing of an example of the decorative resin molded article which concerns on this invention.

1. 1. Decorative sheet The decorative sheet of the present invention comprises at least a laminate in which a base material layer, a metal thin film layer, a fine particle-containing layer, and a surface protective layer are laminated in this order, and the metal thin film layer of the fine particle-containing layer. The side surface is characterized by having an uneven shape due to the fine particles contained in the fine particle-containing layer.

In the decorative sheet of the present invention, the surface of the fine particle-containing layer provided between the metal thin film layer and the surface protective layer on the metal thin film layer side has an uneven shape due to the fine particles contained in the fine particle-containing layer. Therefore, due to this uneven shape, the uneven shape is also formed on the surface of the metal thin film layer on the fine particle-containing layer side. Therefore, the decorative sheet exhibits an appropriate metallic luster due to the metal thin film layer. On the other hand, since an appropriate metallic luster is exhibited by the uneven shape of the metal thin film layer, it is not necessary to form an uneven shape for adjusting the glossiness by blending fine particles in the surface protective layer. Therefore, the surface of the surface protective layer can exhibit excellent image mapping. As described above, in the decorative sheet of the present invention, since the surface of the fine particle-containing layer provided between the metal thin film layer and the surface protective layer has an uneven shape, an appropriate metallic luster due to the metal thin film layer is obtained. And, excellent image quality can be exhibited by the surface protective layer. In the present invention, the "mapping property" means the sharpness of the image reflected on the surface, and specifically, means the one evaluated by the evaluation method in the examples. Hereinafter, the decorative sheet of the present invention will be described in detail with reference to FIGS. 1 to 6.

Laminated structure of decorative sheet The decorative sheet of the present invention has at least a laminated structure having a base material layer 1, a metal thin film layer 2, a fine particle-containing layer 3, and a surface protective layer 4 in this order. In the decorative sheet of the present invention, at least one layer located between the metal thin film layer 2 and the surface protective layer 4 constitutes the fine particle-containing layer 3. Examples of the layer that can form the fine particle-containing layer 3 include a first primer layer 6, a first resin layer 8, a color clear layer 5, a second resin layer 9, and a second primer layer in order from the surface protective layer 4 side. 7 and the like can be mentioned, and at least one of these can be laminated between the metal thin film layer 2 and the surface protective layer 4 to form the fine particle-containing layer 3.

The color clear layer 5 is provided between the metal thin film layer 2 and the surface protective layer 4 as necessary for the purpose of enhancing the metallic tone of the metal thin film layer 2, coloring the decorative sheet, and the like. Is. The first primer layer 6 is a layer provided as needed for the purpose of enhancing the adhesion between the surface protection layer 4 and the layer located below the surface protection layer 4. Further, the second primer layer 7 is a layer provided as needed for the purpose of enhancing the adhesion between the metal thin film layer 2 and the layer located on the metal thin film layer 2 (on the surface protection layer 4 side).

The first resin layer 8 is provided directly below the first primer layer 6 (on the base material layer 1 side), and is mainly provided for forming the fine particle-containing layer 3. The second resin layer 9 is provided directly above the second primer layer 7 (on the surface protective layer 4 side), and is mainly provided for forming the fine particle-containing layer 3.

In the decorative sheet of the present invention, an adhesive layer (not shown) is provided between the base material layer 1 and the metal thin film layer 2 as necessary for the purpose of improving the adhesion between the layers. You may. Further, an adhesive layer (not shown) may be provided under the base material layer 1.

As the laminated structure of the decorative sheet of the present invention, a laminated structure in which a base material layer / a metal thin film layer / a color clear layer (fine particle-containing layer) / a surface protection layer are laminated in this order; a base material layer / a metal thin film layer / a color clear Layer / first primer layer (fine particle-containing layer) / surface protection layer laminated in this order; base material layer / metal thin film layer / second primer layer (fine film-containing layer) / color clear layer / surface protection layer Laminated structure in which the base material layer / metal thin film layer / second primer layer / color clear layer (fine particle-containing layer) / first primer layer / surface protection layer are laminated in this order; base material layer / Metallic thin film layer / Second primer layer / Color clear layer / First primer layer (fine particle-containing layer) / Surface protection layer laminated in this order; Base material layer / Metal thin film layer / Second primer layer (fine particles) (Containing layer) / Color clear layer / First primer layer / Surface protection layer are laminated in this order; Base material layer / Metal thin film layer / Second primer layer / Color clear layer / First resin layer (fine particle-containing layer) ) / First primer layer / Surface protection layer laminated in this order; Base material layer / Metal thin film layer / Second primer layer / Second resin layer (fine particle-containing layer) / Color clear layer / First primer layer / Laminated structure in which surface protective layers are laminated in this order; Adhesive layer / Base material layer / Metal thin film layer / Color clear layer (fine particle-containing layer) / Laminated structure in which surface protective layers are laminated in this order; Base material layer / Adhesion Examples thereof include a laminated structure in which a layer / a metal thin film layer / a color clear layer (fine particle-containing layer) / a surface protective layer are laminated in this order.

FIG. 1 shows an example of a decorative sheet in which a base material layer / a metal thin film layer / a color clear layer (fine particle-containing layer) / a surface protective layer are laminated in this order as one aspect of the laminated structure of the decorative sheet of the present invention. A schematic cross-sectional view is shown. In FIG. 2, as one aspect of the laminated structure of the decorative sheet of the present invention, the base material layer / metal thin film layer / second primer layer / color clear layer (fine particle-containing layer) / first primer layer / surface protection layer is the same. A schematic cross-sectional view of an example of decorative sheets laminated in order is shown. In FIG. 3, as one aspect of the laminated structure of the decorative sheet of the present invention, the base material layer / metal thin film layer / second primer layer / color clear layer / first primer layer (fine particle-containing layer) / surface protective layer is the same. A schematic cross-sectional view of an example of decorative sheets laminated in order is shown. In FIG. 4, as one aspect of the laminated structure of the decorative sheet of the present invention, the base material layer / metal thin film layer / second primer layer (fine particle-containing layer) / color clear layer / first primer layer / surface protection layer is the same. A schematic cross-sectional view of an example of decorative sheets laminated in order is shown. FIG. 5 shows, as one aspect of the laminated structure of the decorative sheet of the present invention, a base material layer / a metal thin film layer / a second primer layer / a color clear layer / a first resin layer (fine particle-containing layer) / a first primer layer / A schematic cross-sectional view of an example of a decorative sheet in which surface protective layers are laminated in this order is shown. FIG. 6 shows, as one aspect of the laminated structure of the decorative sheet of the present invention, a base material layer / a metal thin film layer / a second primer layer / a second resin layer (fine particle-containing layer) / a color clear layer / a first primer layer / A schematic cross-sectional view of an example of a decorative sheet in which surface protective layers are laminated in this order is shown.

Composition of each layer forming a decorative sheet [fine particle-containing layer 3]
The fine particle-containing layer 3 is the metal thin film layer 2 and the surface of the decorative sheet of the present invention in order to impart a design having an appropriate metallic luster and an excellent image quality to the decorative resin molded product. It is a layer provided between the protective layer 4 and the protective layer 4. In the decorative sheet of the present invention, the surface of the fine particle-containing layer 3 on the metal thin film layer 2 side has an uneven shape due to the fine particles 30 contained in the fine particle-containing layer 3. Therefore, the uneven shape causes the metal thin film layer. An uneven shape is also formed on the surface of 2. Therefore, the metal thin film layer 2 can produce a design having an appropriate metallic luster. On the other hand, since the uneven shape of the metal thin film layer 2 produces an appropriate metallic luster design, it is not necessary to form an uneven shape for adjusting the glossiness on the surface of the surface protective layer 4. Therefore, the surface of the surface protective layer can exhibit excellent image mapping.

In the decorative sheet of the present invention, at least one layer located between the metal thin film layer 2 and the surface protective layer 4 contains the fine particles 30 to form the fine particle-containing layer 3. Examples of the layer constituting the fine particle-containing layer 3 include a color clear layer 5, a first primer layer 6, a second primer layer 7, a first resin layer 8, a second resin layer 9, and the like, which will be described later. That is, by containing the fine particles 30, these layers become the fine particle-containing layer 3 having an uneven shape due to the fine particles 30. Details of these layers that can form the fine particle-containing layer 3 are described later.

The fine particle-containing layer 3 may be one layer or a plurality of two or more layers.

The fine particles 30 contained in the fine particle-containing layer 3 are not particularly limited, and examples thereof include known fine particles. Specific examples of the fine particles include silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, kaolin, and inorganic particles such as these hydrophobic treated products; acrylic beads, urethane beads, nylon beads, silicone beads, and silicone rubber beads. , Polycarbonate beads, synthetic resin particles such as polyolefin wax (polypropylene wax, polyethylene wax, mixtures thereof, etc.) and the like. Among these, silica particles are preferable. The fine particles 30 may be used alone or in combination of two or more.

The particle size of the fine particles 30 is not particularly limited, but is preferably about 0.1 to 10 μm, more preferably 1 from the viewpoint of forming an uneven shape on the surface of the metal thin film layer 2 and exhibiting an appropriate metallic luster. It is about 5 μm, more preferably about 2 to 4 μm.

From the viewpoint of forming an uneven shape on the surface of the metal thin film layer 2 and exhibiting an appropriate metallic luster, the portion of the fine particle-containing layer 3 where the fine particles 30 are located (corresponding to the shape of the fine particles, the fine particle-containing layer). The thickness of the protruding portion of the surface of the fine particles 30 is preferably 1.2 times or more the thickness of the portion where the fine particles 30 are not located (the protruding portion of the surface of the fine particle-containing layer), and is preferably 1.2 to It is more preferably about 5.0 times, and further preferably about 2.5 to 4.0 times. For these thicknesses, the maximum and minimum values of the thickness are measured by observing the cross section in the thickness direction in five different regions of the fine particle-containing layer 3, and the fine particles 30 position the average value of the five maximum values. The average value of the minimum value of 5 points is calculated as the thickness of the portion where the fine particles 30 are not located.

From the viewpoint of forming an uneven shape on the surface of the metal thin film layer 2 and exhibiting an appropriate metallic luster, the portion of the fine particle-containing layer 3 where the fine particles 30 are located and the portion of the metal thin film layer 2 on the fine particle-containing layer 3 side. The shortest distance x from the surface is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. As shown in FIGS. 1 and 4, for example, the fine particle-containing layer 3 and the metal thin film layer 2 may be adjacent to each other, and the shortest distance x may be substantially 0.

On the other hand, from the viewpoint of suppressing excessive reduction of metallic luster and deterioration of adhesion between the metal thin film layer 2 and the metal thin film layer 2, the fine particle-containing layer 3 and the metal thin film layer 2 should not be directly adjacent to each other. It is preferable to have at least one resin layer between the fine particle-containing layer 3 and the metal thin film layer 2 that does not substantially contain fine particles. Further, from the viewpoint of adhesion between the fine particle-containing layer 3 and the surface protective layer 4, the fine particle-containing layer 3 and the metal thin film layer 4 are arranged so that the fine particle-containing layer 3 and the metal thin film layer 4 are not directly adjacent to each other. It is preferable to have at least one resin layer between the two, which is substantially free of fine particles. From the above viewpoint, for example, the base material layer 1 / the metal thin film layer 2 / the second primer layer 7 / the second resin layer 9 / the color clear layer 5 / the first primer layer 6 / the surface protection layer 4 are laminated in this order. In the case of the decorative sheet of the embodiment, the second primer layer 7 directly adjacent to the metal thin film layer 2 is a layer that does not substantially contain fine particles, and the second resin is located between the second primer layer 7 and the surface protective layer 4. It is preferable that at least one layer of the layer 9, the color clear layer 5, and the first primer layer 6 is a fine particle-containing layer 3, and the first primer layer 6 directly adjacent to the surface protection layer 4 also does not substantially contain fine particles. As a layer, it is more preferable that at least one layer of the second resin layer 9 located between the second primer layer 7 and the first primer layer 6 and the color clear layer 5 is the fine particle-containing layer 3. The fact that the resin layer does not substantially contain fine particles means that the surface of the resin layer does not have a protruding portion due to the shape of the fine particles.

The thickness of the fine particle-containing layer 3 is not particularly limited, but is preferably about 0.1 to 5 μm, more preferably about 0.5 to 2.5 μm, and further preferably about 1 to 2 μm. The thickness of the fine particle-containing layer 3 means the thickness of the portion where the fine particles 30 are not located (the portion where the surface of the fine particle-containing layer does not protrude).

[Color clear layer 5]
The color clear layer 5 is provided between the metal thin film layer 2 and the surface protective layer 4 as necessary for the purpose of enhancing the metallic tone of the metal thin film layer 2 and coloring the decorative sheet. It is a transparent layer. The color clear layer 5 is, for example, between the surface protection layer 4 and the metal thin film layer 2, between the first primer layer 6 and the metal thin film layer 2, and between the first primer layer 6 and the second primer layer 7. It is provided between the first resin layer and the metal thin film layer 2, between the first resin layer 8 and the second primer layer 7, and the like.

Further, as described above, the color clear layer 5 can form the fine particle-containing layer 3 as shown in FIGS. 1 and 2, for example. When the color clear layer 5 constitutes the fine particle-containing layer 3, the color clear layer 5 contains the fine particles 30 as described in the above-mentioned column of [fine particle-containing layer 3], and the other configurations also include [fine particles]. It will be the one described in the column of [Containing layer 3].

The material forming the color clear layer 5 is not particularly limited, and examples thereof include a transparent resin colored with a colorant or the like. The colorant is not particularly limited, and examples thereof include color pigments and dyes. The transparent resin is not particularly limited, and examples thereof include acrylic resins, polyurethane resins, acrylic-urethane copolymer resins, and polyester resins. When the color clear layer 5 constitutes the fine particle-containing layer 3, the fine particles 30 are dispersed in these resins.

The thickness of the color clear layer 5 is not particularly limited, but is usually about 0.5 to 2.5 μm, preferably about 1 to 2 μm when the fine particle-containing layer 3 is not formed. The thickness when the color clear layer 5 constitutes the fine particle-containing layer 3 is as described in the above-mentioned fine particle-containing layer 3.

The method for forming the color clear layer 5 is not particularly limited, and examples thereof include a method of applying the above resin on the surface of a layer adjacent to the color clear layer 5. As the application method, gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, wire bar coat, flow coat, comma coat, hang Examples thereof include a normal coating method such as a sink coat, a brush coat, and a spray coat, and a transfer coating method.

[First primer layer 6]
The first primer layer 6 is a layer provided under the surface protective layer 4 as necessary for the purpose of enhancing the adhesion between the surface protective layer 4 and the layer located below the surface protective layer 4. The first primer layer 6 is, for example, between the surface protective layer 4 and the metal thin film layer 2, between the surface protective layer 4 and the color clear layer 5, between the surface protective layer 4 and the first resin layer 8, and the like. It will be provided.

Further, as described above, the first primer layer 6 can form the fine particle-containing layer 3 as shown in FIG. 3, for example. When the first primer layer 6 constitutes the fine particle-containing layer 3, the first primer layer 6 contains the fine particles 30 as described in the above-mentioned column of [fine particle-containing layer 3], and other configurations are also included. It will be the one described in the column of [Particle-containing layer 3].

The material forming the first primer layer 6 is not particularly limited as long as it can improve the adhesion between these layers, and is, for example, an acrylic resin, a polyurethane resin, an acrylic-urethane copolymer resin, or a polyester. Examples thereof include resins such as based resins. These resins may be used alone or in combination of two or more. When the first primer layer 6 constitutes the fine particle-containing layer 3, the fine particles 30 are dispersed in these resins.

The thickness of the first primer layer 6 is not particularly limited, but is usually about 0.5 to 2.5 μm, preferably about 1 to 2 μm when the fine particle-containing layer 3 is not formed.

A colorant can be mixed with the first primer layer 6 to adjust the color and improve the design, and further, a pattern can be formed from a design point of view. The method for forming the first primer layer 6 is not particularly limited, and examples thereof include a method of applying the above resin on the surface of a layer adjacent to the first primer layer 6 by the above-mentioned coating method.

[Second primer layer 7]
The second primer layer 7 is placed on the metal thin film layer 2 as necessary for the purpose of enhancing the adhesion between the metal thin film layer 2 and the layer located on the metal thin film layer 2 (on the surface protection layer 4 side). It is a layer to be provided. The second primer layer 7 is, for example, between the metal thin film layer 2 and the surface protective layer 4, between the metal thin film layer 2 and the color clear layer 5, between the metal thin film layer 2 and the second resin layer 8, and the like. It will be provided.

Further, as described above, the second primer layer 7 can form the fine particle-containing layer 3 as shown in FIG. 4, for example. When the second primer layer 7 constitutes the fine particle-containing layer 3, the second primer layer 7 contains the fine particles 30 as described in the above-mentioned column of [fine particle-containing layer 3], and other configurations are also included. It will be the one described in the column of [Particle-containing layer 3].

The material forming the second primer layer 7 is not particularly limited as long as it can improve the adhesion between these layers, and is, for example, an acrylic resin, a polyurethane resin, an acrylic-urethane copolymer resin, or a polyester. Examples thereof include resins such as based resins. These resins may be used alone or in combination of two or more. When the second primer layer 7 constitutes the fine particle-containing layer 3, the fine particles 30 are dispersed in these resins.

The thickness of the second primer layer 7 is not particularly limited, but is usually about 0.5 to 2.5 μm, preferably about 1 to 2 μm when the fine particle-containing layer 3 is not formed.

The method for forming the second primer layer 7 is not particularly limited, and examples thereof include a method of applying the above resin on the surface of a layer adjacent to the second primer layer 7 by the above-mentioned coating method.

[First resin layer 8]
The first resin layer 8 is usually provided under the first primer layer 6 (on the base material layer 1 side), and is mainly provided for forming the fine particle-containing layer 3. That is, when the first resin layer 8 is provided in the decorative sheet of the present invention, for example, as shown in FIG. 5, the first resin layer 8 usually constitutes the fine particle-containing layer 3. .. Since the above-mentioned first primer layer 6 does not form the fine particle-containing layer 3 and the first resin layer 8 constitutes the fine particle-containing layer 3, the adhesion of the surface protective layer 4 is improved by the first primer layer 6. By the first resin layer 8, an uneven shape is suitably formed on the surface of the metal thin film layer 2, and an appropriate metallic luster can be exhibited.

When the first resin layer 8 constitutes the fine particle-containing layer 3, the first resin layer 8 contains the fine particles 30 as described in the above-mentioned column of [fine particle-containing layer 3], and other configurations are also included. It will be the one described in the column of [Particle-containing layer 3].

The material forming the first resin layer 8 is not particularly limited, and examples thereof include resins such as acrylic resins, polyurethane resins, acrylic-urethane copolymer resins, and polyester resins. These resins may be used alone or in combination of two or more. When the first resin layer 8 constitutes the fine particle-containing layer 3, the fine particles 30 are dispersed in these resins.

The thickness of the first resin layer 8 is not particularly limited, but is usually about 0.5 to 2.5 μm, preferably about 1 to 2 μm when the fine particle-containing layer 3 is not formed.

The method for forming the first resin layer 8 is not particularly limited, and examples thereof include a method of applying the above resin on the surface of a layer adjacent to the first resin layer 8 by the above-mentioned coating method.

[Second resin layer 9]
The second resin layer 9 is usually provided on the second primer layer 7 (on the surface protective layer 4 side), and is mainly provided for forming the fine particle-containing layer 3. That is, when the second resin layer 9 is provided in the decorative sheet of the present invention, for example, as shown in FIG. 6, the second resin layer 9 usually constitutes the fine particle-containing layer 3. .. Since the above-mentioned second primer layer 7 does not form the fine particle-containing layer 3 and the second resin layer 9 constitutes the fine particle-containing layer 3, the adhesion of the metal thin film layer 2 is improved by the second primer layer 7. The second resin layer 9 preferably forms an uneven shape on the surface of the metal thin film layer, and can exhibit an appropriate metallic luster.

When the second resin layer 9 constitutes the fine particle-containing layer 3, the second resin layer 9 contains the fine particles 30 as described in the above-mentioned column of [fine particle-containing layer 3], and other configurations are also included. It will be the one described in the column of [Particle-containing layer 3].

The material forming the second resin layer 9 is not particularly limited, and examples thereof include resins such as acrylic resins, polyurethane resins, acrylic-urethane copolymer resins, and polyester resins. These resins may be used alone or in combination of two or more. When the second resin layer 9 constitutes the fine particle-containing layer 3, the fine particles 30 are dispersed in these resins.

The thickness of the second resin layer 9 is not particularly limited, but is usually about 0.5 to 2.5 μm, preferably about 1 to 2 μm when the fine particle-containing layer 3 is not formed.

The method for forming the second resin layer 9 is not particularly limited, and examples thereof include a method of applying the above resin on the surface of a layer adjacent to the second resin layer 9 by the above-mentioned coating method.

[Base material layer 1]
The base material layer 1 is formed of a resin sheet (resin film) that serves as a support in the decorative sheet of the present invention. The resin component used for the base material layer 1 is not particularly limited and may be appropriately selected depending on the three-dimensional moldability, compatibility with the molding resin layer and the like, but a thermoplastic resin is preferable. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"); acrylonitrile-styrene-acrylic acid ester resin; acrylic resin; polyolefin-based resins such as polypropylene and polyethylene. Examples thereof include resin; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET) resin and the like. Among these, ABS resin is preferable from the viewpoint of three-dimensional moldability. As the resin component forming the base material layer 1, only one kind may be used, or two or more kinds may be mixed and used. Further, the base material 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. It should be noted that a method of improving the three-dimensional formability of the decorative sheet by using the base material layer 1 as a multi-layer sheet can be considered, but since the decorative sheet of the present invention has a specific primer layer 3 described later. Even if the base material layer 1 is a single-layer sheet, it has high three-dimensional moldability.

The base material layer 1 is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides as necessary in order to improve the adhesion to the metal thin film layer 2, the adhesive layer and the like. It may have been done. Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, an ozone ultraviolet treatment method and the like. In addition, examples of the unevenness method performed as the surface treatment of the base material layer 1 include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of resin component constituting the base material layer 1, and a corona discharge treatment method is preferable from the viewpoint of effectiveness and operability.

Further, the base material layer 1 may be colored by blending a colorant or the like, painted to adjust the color, or formed a pattern to impart designability.

The thickness of the base material layer 1 is not particularly limited and is appropriately set according to the intended use of the decorative sheet, but is usually about 50 to 800 μm, preferably about 100 to 600 μm, and more preferably about 200 to 500 μm. Will be. When the thickness of the base material layer 1 is within the above range, the decorative sheet can be provided with even better three-dimensional moldability, designability, and the like.

[Metallic thin film layer 2]
The metal thin film layer 2 is provided on the base material layer 1 and is a layer that imparts an appropriate metallic luster to the decorative sheet. In the decorative sheet of the present invention, the surface of the fine particle-containing layer 3 has an uneven shape, so that the surface of the metal thin film layer 2 also has an uneven shape. That is, the surface of the metal thin film layer 2 on the fine particle-containing layer 3 side has an uneven shape corresponding to the uneven shape of the surface of the fine particle-containing layer 3.

The metal forming the metal thin film layer 2 is not particularly limited as long as it is a metal that can give a metallic design to the decorative sheet, but for example, tin, indium, chromium, aluminum, nickel, copper, silver, gold, and platinum. , Zinc, and alloys containing at least one of these. Among these, tin, indium, and chromium are preferably mentioned from the viewpoint of being rich in extensibility. Since the metal thin film layer 2 is formed of a metal having a high extensibility, it has an advantage that cracks are less likely to occur when the decorative sheet is three-dimensionally formed. The metal thin film layer 2 may be formed of one kind of metal or may be formed of two or more kinds of metals.

The method for forming the metal thin film layer 2 is not particularly limited, but from the viewpoint of forming an uneven shape corresponding to the uneven shape of the surface of the fine particle-containing layer 3 on the surface of the metal thin film layer 2 and exhibiting an appropriate metallic luster. For example, a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or the like using the above metal is preferable. In particular, the vacuum vapor deposition method is preferable in that it is low in cost and causes less damage to the object to be deposited. The vapor deposition conditions may be appropriately set according to the melting temperature or evaporation temperature of the metal to be used. In addition to the above-mentioned forming method, a method of applying a paste containing the above-mentioned metal, a plating method using the above-mentioned metal, or the like can also be used.

The thickness of the metal thin film layer 2 is not particularly limited, but is preferably 200 nm or less, more preferably about 10 to 100 nm, and further preferably about 20 to 60 nm from the viewpoint of improving the design and moldability of the decorative sheet. Can be mentioned.

[Surface protection layer 4]
The surface protective layer 4 is a layer provided on the outermost surface of the decorative sheet for the purpose of enhancing scratch resistance, weather resistance, and the like of the decorative sheet. In the decorative sheet of the present invention, the surface of the surface protective layer 4 is preferably a flat surface from the viewpoint of obtaining excellent image mapping, but it is fine for the purpose of decoration as long as the effect of the present invention is not impaired. It may have an uneven shape (for example, a hairline shape).

The material forming the surface protective layer 4 is not particularly limited, but a resin is usually used, and an ionizing radiation curable resin is preferably used. Further, it is also preferable that the surface protective layer 4 is formed of, for example, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or a resin film such as an acrylic resin. The surface protective layer 4 may be formed of, for example, an ionizing radiation curable resin or one layer of the resin film, or may be formed of two or more of these layers. Hereinafter, the ionizing radiation curable resin used for forming the surface protective layer 4 will be described in detail.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the surface protective layer 4 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. Examples thereof include those obtained by appropriately mixing at least one of a prepolymer, an oligomer, a monomer, and the like having the above. Here, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet (UV) or electron beam (EB) is used, but in addition, X It also includes electromagnetic waves such as rays and γ-rays, and charged particle beams such as α-rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin is suitable for forming the surface protective layer 4 because it can be made solvent-free, does not require a photopolymerization initiator, and stable curing characteristics can be obtained. Used for.

As the above-mentioned monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more (bifunctional or more), preferably three or more (trifunctional or more) polymerizable unsaturated bonds in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (). Meta) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, caprolactone-modified dicyclopentenyldi (meth) Meta) acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylol propanetri (meth) acrylate, ethylene oxide-modified trimethylol propanetri (meth) acrylate , Dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propanetri (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 alone or in combination of two or more.

Further, as the above-mentioned oligomer used as an 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 (bifunctional or higher) is preferable. Examples of the polyfunctional (meth) acrylate oligomer 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 cationically polymerizable functional group in the molecule (for example, novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) and the like. .. Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and has a (meth) acrylate group in the terminal or side chain, and for example, a polycarbonate polyol (meth) is used. It can be obtained by esterifying with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. Urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol with a polyhydric isocyanate compound and a hydroxy (meth) acrylate. Acrylic silicone (meth) acrylate can be obtained by radically copolymerizing a silicone macromonomer with a (meth) acrylate monomer. The urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or a 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 oxylan ring of a relatively low molecular weight bisphenol type epoxy resin or a novolak type epoxy resin to esterify it. Further, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can also be used. The polyester (meth) acrylate can be obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or to a polyvalent carboxylic acid. It can be obtained by esterifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. The silicone (meth) acrylate can be obtained by adding (meth) acrylic acid to the terminal or side chain of a silicone having a polysiloxane bond in the main chain. These oligomers may be used alone or in combination of two or more.

Among the above-mentioned ionizing radiation curable resins, it is preferable to use polycarbonate (meth) acrylate from the viewpoint of obtaining excellent three-dimensional moldability. Further, from the viewpoint of achieving both three-dimensional moldability and scratch resistance, it is more preferable to use a combination of polycarbonate (meth) acrylate and urethane (meth) acrylate.

(Other additive ingredients)
Various additives can be added to the surface protective layer 4 according to the desired physical properties to be provided in the surface protective layer 4. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesiveness improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a coloring agent. These additives can be appropriately selected and used from those commonly used. Further, 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.

On the other hand, when a matting agent is added to the surface protective layer 4, the surface smoothness of the surface protective layer 4 may be impaired and the image quality may be deteriorated. Further, even if the surface smoothness of the surface protective layer 4 is ensured in the state of the decorative sheet, the matting agent in the surface protective layer 4 is surfaced in the process of forming the decorative sheet, particularly in the vacuum forming process. In the state of the decorative resin molded product, the surface smoothness may be impaired and the imageability may be deteriorated. From the above viewpoint, it is preferable that the surface protective layer 4 does not substantially contain a matting agent.

In the case of a decorative sheet for transfer, the transfer base material is the surface of the surface protective layer (decorative resin molded product) through the process of manufacturing the decorative sheet and the process of obtaining the decorative resin molded product using the decorative sheet. Since it is laminated on the surface that becomes the outermost surface in the above-mentioned state, the phenomenon that the matting agent contained in the surface protective layer emerges on the surface is unlikely to occur. Therefore, by using a matting agent for the surface protective layer, it can be considered that it is relatively easy to achieve both a design having an appropriate metallic luster and a mapability. On the other hand, in the case of a so-called decorative sheet for laminating in which the base material layer is incorporated into the decorative resin molded product as in the present invention, molding is usually performed with the surface of the surface protective layer exposed. Since the above-mentioned phenomenon occurs, it is difficult to achieve both appropriate metallic luster and reproducibility. Therefore, the decorative sheet of the present invention has excellent technical significance in that it makes it possible to achieve both an appropriate metallic luster and a mapability, which was difficult with a decorative sheet for laminating.

(Thickness of surface protective layer 4)
The thickness of the surface protective layer 4 after curing is not particularly limited, and examples thereof include about 1 to 1000 μm, preferably about 1 to 50 μm, and more preferably about 1 to 30 μm. When the thickness in such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance and weather resistance can be obtained, and when the surface protective layer 4 is formed by using an ionizing radiation curable resin, it is ionized. Since it is possible to uniformly irradiate the radiation, it is possible to cure the radiation uniformly, which is economically advantageous. Further, when the thickness of the surface protective layer 4 after curing satisfies the above range, the three-dimensional moldability of the decorative sheet is further improved, so that high followability to a complicated three-dimensional shape such as an automobile interior application can be achieved. Obtainable. As described above, even if the decorative sheet of the present invention has a thicker surface protective layer 4 than the conventional one, sufficiently high three-dimensional moldability can be obtained. Therefore, the surface protective layer 4 has a particularly high film thickness. It is also useful as a decorative sheet for required members such as vehicle exterior parts.

(Formation of surface protective layer 4 when ionizing radiation curable resin is used)
The surface protective layer 4 is formed, for example, by preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, applying the same, and cross-linking and curing the composition. The viscosity of the ionizing radiation curable resin composition may be any viscosity that can form an uncured resin layer by the coating method described later.

In the present invention, the prepared coating liquid is applied by a known method such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat, preferably gravure coat so as to have the above thickness, and is uncured. Form a resin layer.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer to form the surface protective layer 4. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface protection layer 4, the electron beam transmission depth and surface protection are used. The acceleration voltage is selected so that the thicknesses of the layers 4 are substantially equal. As a result, it is possible to suppress the irradiation of the layer located below the surface protective layer 4 with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam.

The irradiation dose is preferably an amount at which the crosslink density of the surface protective layer 4 is saturated, 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).

Further, the electron beam source is not particularly limited, and various electron beam accelerators such as a cockloft Walton type, a van de Graaff type, a resonance transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Can be used.

When ultraviolet rays are used as ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

By adding various additives to the surface protective layer 4 thus formed, a hard coat function, an anti-fog coat function, an anti-fouling coat function, an anti-glare coat function, an anti-reflection coat function, an ultraviolet ray shielding coat function, A process for imparting a function such as an infrared shielding coat function may be performed.

When the surface protective layer 4 is formed of a resin film, the resin film may be laminated on the surface of the layer located below the surface protective layer 4.

[Adhesive layer]
An adhesive layer can be provided on the back surface of the base material layer 1 as needed for the purpose of improving the adhesiveness and adhesion between the decorative sheet and the molded resin layer 10 (not shown). The resin forming the adhesive layer is not particularly limited as long as it can improve the adhesiveness and adhesion between the decorative sheet and the molding resin, and for example, a thermoplastic resin or a thermosetting resin can be used. Used. Examples of the thermoplastic resin include acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, rubber resin and the like. .. One type of thermoplastic resin may be used alone, or two or more types may be used in combination. Examples of the thermosetting resin include urethane resin and epoxy resin. One type of thermosetting resin may be used alone, or two or more types may be used in combination. This adhesive layer is not necessarily a necessary layer, but when it is assumed that the decorative sheet of the present invention is applied to a decorative method by sticking on a resin molded body prepared in advance, such as a vacuum crimping method described later. Is preferably provided. When used in the vacuum crimping method, it is preferable to form an adhesive layer by using a conventional resin that develops adhesiveness by pressurization or heating among the various resins described above. The thickness of the adhesive layer is not particularly limited, and examples thereof include about 0.1 to 30 μm, preferably about 0.5 to 20 μm, and more preferably about 1 to 8 μm.

Further, in order to improve the adhesion between the base material layer 1 and the metal thin film layer 2, an adhesive layer may be provided between the base material layer 1 and the metal thin film layer 2 as necessary (not shown). ). The resin forming the adhesive layer is not particularly limited as long as it can improve the adhesion between the base material layer 1 and the metal thin film layer 2, and examples thereof include thermoplastic resins. The thermoplastic resin is not particularly limited, but for example, acrylic resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; ABS resin; polyester resin such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyvinyl chloride. , Polyvinyl chloride resin such as chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate- (meth) acrylic copolymer, polyvinyl chloride , Chlorine-based resins such as chlorinated polypropylene and the like. As the resin forming the adhesive layer 5, an acrylic resin or a chlorine-based resin is preferably used from the viewpoint of enhancing the adhesion between the base material layer 1 and the metal thin film layer 2. Examples of the chlorine-based resin include vinyl chloride resin and vinyl chloride-vinyl acetate copolymer, more preferably vinyl chloride, from the viewpoint of enhancing the adhesion between the base material layer 1 and the metal thin film layer 2 and the like. -A vinyl acetate copolymer can be mentioned. As the resin forming the adhesive layer, one type may be used alone, or two or more types may be mixed and used. In the present invention, "(meth) acrylic" is a general term for "acrylic" and "methacrylic", and other similar substances with (meth) have the same meaning. When this adhesive layer is provided, the thickness of the adhesive layer is not particularly limited, but from the viewpoint of improving the adhesion between the base material layer 1 and the metal thin film layer 2, it is about 0.6 to 3.5 μm, preferably 1. It can be about 2 μm.

These adhesive layers can be formed by applying the above resin on the surface of a layer adjacent to the adhesive layer, and as a coating method, for example, a dry laminating method or the like can be used.

2. 2. Decorative Resin Molded Product The decorative resin molded product of the present invention is formed by integrating the decorative sheet of the present invention with a molding resin. That is, in the decorative resin molded product of the present invention, at least the molding resin layer 10, the base material layer 1, the metal thin film layer 2, the fine particle-containing layer 3, and the surface protection layer 4 are laminated in this order. The surface of the fine particle-containing layer 3 on the metal thin film layer 2 side, which is made of a body, is characterized by having an uneven shape due to the fine particles 30 contained in the fine particle-containing layer 3. As described above, the color clear layer 5, the first primer layer 6, the second primer layer 7, the first resin layer 8, the second resin layer 9, and the like constitute the fine particle-containing layer 3.

The decorative resin molded product of the present invention 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, for example, using the decorative sheet of the present invention. To. Among these injection molding methods, an insert molding method and an injection molding simultaneous decoration method are preferably mentioned. Further, the decorative resin molded product of the present invention is a decorative method such as a vacuum crimping method in which a decorative sheet of the present invention is attached onto a three-dimensional resin molded body (molded resin layer 10) prepared in advance. It can also be produced by.

In the insert molding method, first, in the vacuum forming step, the decorative sheet of the present invention is vacuum-formed (offline pre-molding) into the surface shape of the molded product in advance by a vacuum forming mold, and then the excess portion is trimmed if necessary. Obtain a molded sheet. This molding sheet is inserted into an injection molding mold, the injection molding mold is molded, the fluid resin is injected into the mold and solidified, and the decorative sheet is integrated on the outer surface of the resin molded product at the same time as the injection molding. By making it a decorative resin molded product, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance using a vacuum forming mold.
The trimming process to obtain a molded sheet by trimming the excess part of the vacuum-formed decorative sheet, and the molding sheet is inserted into the injection molding mold, the injection molding mold is closed, and the fluid resin is injected into the injection molding mold. An integration process that integrates the resin and the molded sheet.

In the vacuum forming step in the insert molding method, the decorative sheet may be heated and molded. 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, the thickness of the decorative sheet, and the like. For example, when an ABS resin film is used as the base material layer. For example, it can be usually about 100 to 250 ° C, preferably about 130 to 200 ° C. Further, in the integration step, the temperature of the resin in the fluid state is not particularly limited, but can be usually about 180 to 320 ° C, preferably about 220 to 280 ° C.

Further, in the injection molding simultaneous decoration method, the decoration sheet of the present invention is placed in a female mold that also serves as a vacuum molding mold provided with a suction hole for injection molding, and pre-molding (in-line pre-molding) is performed with this female mold. After that, the injection molding mold is molded, the fluid resin is injection-filled in the mold and solidified, and at the same time as the injection molding, the decorative sheet of the present invention is integrated on the outer surface of the resin molded product. As a result, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is produced by an injection molding simultaneous decoration method including the following steps.
After installing the decorative sheet of the present invention so that the surface of the base material layer of the decorative sheet faces the molded surface of the movable mold having a molded surface of a predetermined shape, the decorative sheet is heated. Pre-molding step of pre-molding a decorative sheet by softening and vacuum suctioning from the movable mold side to bring the softened decorative sheet into close contact with the molding surface of the movable mold.
After the movable mold having the decorative sheet adhered along the molding surface and the fixed mold are molded, a fluid resin is injected, filled and solidified in the cavity formed by both molds. As a result, a resin molded body is formed, and an integration step of laminating and integrating the resin molded body and the decorative sheet, and resin molding in which all layers of the decorative sheet are laminated by separating the movable mold from the fixed mold. Extraction process to take out the body.

In the preforming process of the injection molding simultaneous decoration 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 usually be about 70 to 130 ° C. Further, in the injection molding step, the temperature of the resin in the fluid state is not particularly limited, but can be usually about 180 to 320 ° C, preferably about 220 to 280 ° C.

In the vacuum crimping method, first, the decorative sheet and the resin molded body of the present invention 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. Installed in the vacuum crimping machine so that the vacuum chamber side and the resin molded body are on the second vacuum chamber side and the base material layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state. do. The resin molded body is installed on an elevating table that can be raised and lowered up and down, which is provided on the second vacuum chamber side. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using an elevating table, and the resin molded body is stretched while stretching the decorative sheet by utilizing the pressure difference between the two vacuum chambers. Stick on the surface of. Finally, the decorative resin molded product of the present invention can be obtained by opening the two vacuum chambers to atmospheric pressure and trimming the excess portion of the decorative sheet as needed.

In the vacuum crimping method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve the moldability before the step of pressing the molded body against the decorative sheet. The vacuum crimping method including this step may be particularly called a vacuum heating crimping method. The heating temperature in the step may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, but when a polyester resin film or an acrylic resin film is used as the base material layer, it may be selected. Usually, the temperature can be about 60 to 200 ° C.

In the decorative resin molded product of the present invention, the molded resin layer 10 may be formed by selecting a resin according to the intended use. The resin forming the molding resin layer 10 may be a thermoplastic resin or a thermosetting resin.

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

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

The decorative resin molded product of the present invention is, for example, an interior or exterior material of a vehicle such as an automobile; a fitting such as a window frame or a door frame; an interior material of a building such as a wall, a floor, or a ceiling; a television receiver, an air conditioner. Housing for home appliances such as machines; can be used as containers and the like.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

<Making decorative sheets>
(Example 1)
A hairline design was applied to the surface of a biaxially stretched polyethylene terephthalate film (PET film, thickness 38 μm). Next, an ionizing radioactive curable resin composition (including polycarbonate (meth) acrylate and urethane (meth) acrylate as the resin) is applied to the surface on which the hairline design is applied so that the thickness after curing is 10 μm. , Printed by gravure coat. The uncured resin layer was cured by irradiating the uncured resin layer with an electron beam having an acceleration voltage of 165 kV and an irradiation intensity of 50 kGy (5Mrad) to form a surface protective layer. Next, an acrylic resin was printed on the surface of the surface protective layer by a gravure coat to form a first primer layer (thickness 1 μm). Next, a color clear layer (brown) made of an acrylic resin containing 5% by mass of silica particles having a particle size of 3 to 4 μm was printed by a gravure coat (thickness of the portion not containing the silica particles was 1 μm). Next, the acrylic resin was printed by a gravure coat to form a second primer layer (thickness 1 μm). Next, tin (Sn) was laminated by about 50 nm using a vacuum vapor deposition machine to form a metal thin film layer. Next, an adhesive layer made of polyester is printed on the metal thin film layer by a gravure coat (thickness 1 μm), and then bonded to a base material layer made of an ABS resin film (thickness 400 μm) by thermal lamination to peel off the PET film. As a result, a decorative sheet having a laminated structure as shown in FIG. 2 was obtained.

(Example 2)
A first primer layer made of an acrylic resin containing 5% by mass of silica particles having a particle size of 3 to 4 μm was formed (thickness of a portion not containing silica particles was 1 μm), and a color clear made of an acrylic resin containing no silica particles. A decorative sheet having a laminated structure as shown in FIG. 3 was obtained in the same manner as in Example 1 except that the layer (brown) was printed by gravure coating (thickness 1 μm).

(Example 3)
A color clear layer (brown) made of an acrylic resin containing no silica particles was printed by a gravure coat (thickness 1 μm), and a second primer layer made of an acrylic resin containing 5% by mass of silica particles having a particle size of 3 to 4 μm. A decorative sheet having a laminated structure as shown in FIG. 4 was obtained in the same manner as in Example 1 except that the resin particles were formed (thickness of the portion not containing silica particles was 1 μm).

(Example 4)
After forming the first primer layer and before forming the color clear layer, a first resin layer made of an acrylic resin containing 5% by mass of silica particles having a particle size of 3 to 4 μm was formed (a portion not containing silica particles). As shown in FIG. 5, in the same manner as in Example 1, except that the color clear layer (brown) made of acrylic resin containing no silica particles was printed by a gravure coat (thickness 1 μm). A decorative sheet having a various laminated structure was obtained.

(Example 5)
A color clear layer (brown) made of an acrylic resin containing no silica particles was printed by a gravure coat (thickness 1 μm), and the particle size was changed after the color clear layer was formed and before the second primer layer was formed. It is shown in FIG. 6 in the same manner as in Example 1 except that the first resin layer made of an acrylic resin containing 5% by mass of silica particles of 3 to 4 μm was formed (thickness of the portion not containing silica particles was 1 μm). A decorative sheet having such a laminated structure was obtained.

(Example 6)
A decorative sheet having a laminated structure as shown in FIG. 2 was obtained in the same manner as in Example 1 except that the content of silica particles in the color clear layer was 2.5% by mass.

(Comparative Example 1)
A surface protective layer was formed by adding 5% by mass of silica particles having a particle size of 3 to 4 μm to the ionizing radiation curable resin composition, and a color clear layer (brown) made of an acrylic resin containing no silica particles. Was printed by a gravure coat (thickness 1 μm), and a decorative sheet was obtained in the same manner as in Example 1.

(Comparative Example 2)
A decorative sheet was obtained in the same manner as in Example 1 except that a color clear layer (brown) made of an acrylic resin containing no silica particles was printed by a gravure coat (thickness 1 μm).

(Metallic luster of decorative sheet before molding)
The surface of each decorative sheet obtained above on the surface protective layer side was visually observed, and the metallic luster was evaluated according to the following criteria. The results are shown in Table 1.
○: Has moderate metallic luster △: Metallic luster is a little strong or metallic luster is a little weak, so it is not a little beautiful as a metallic design ×: Metallic luster is too strong and distracting or metallic luster Is too weak to look like metal

(Metallic luster of decorative sheet after molding)
Each decorative sheet obtained above was heated to 180 ° C. with an infrared heater to soften it. Next, using a vacuum forming mold, vacuum forming was performed under the condition that the maximum draw ratio was 50%, and the decorative sheet was formed so as to have the internal shape of the vacuum forming mold. The surface of the decorative sheet after molding on the surface protective layer side was visually observed, and the metallic luster was evaluated according to the following criteria. The results are shown in Table 1. ○: Has moderate metallic luster △: Metallic luster is a little strong or metallic luster is a little weak, so it is not a little beautiful as a metallic design ×: Metallic luster is too strong and distracting or metallic luster Is too weak to look like metal

(Mapping property of decorative sheet before molding)
In a room brightened with a fluorescent lamp, the surface of each decorative sheet obtained above on the surface protective layer side was visually observed, and the image quality of the decorative sheet was evaluated according to the following criteria. The results are shown in Table 1.
○: The end of the fluorescent light is clearly reflected △: The end of the fluorescent light is slightly blurred ×: The end of the fluorescent light is reflected considerably blurred Are

(Mapping property of decorative sheet after molding)
Each decorative sheet obtained above was heated to 180 ° C. with an infrared heater to soften it. Next, using a vacuum forming mold, vacuum forming was performed under the condition that the maximum draw ratio was 50%, and the decorative sheet was formed so as to have the internal shape of the vacuum forming mold. Next, in a room brightened with a fluorescent lamp, the surface of each decorative sheet after molding on the surface protective layer side was visually observed, and the image quality of the decorative sheet was evaluated according to the following criteria. The results are shown in Table 1.
○: The end of the fluorescent light is clearly reflected △: The end of the fluorescent light is slightly blurred ×: The end of the fluorescent light is reflected considerably blurred Are

(Adhesion evaluation)
On the surface of each decorative sheet obtained above, cut 11 vertical and 11 horizontal cuts with a cutter with a length of 5 mm and an interval of 2 mm, and make a total of 100 squares of 10 squares x 10 squares. Formed a notch. After crimping cellophane tape (registered trademark) (No. 405-1P) manufactured by Nichiban Co., Ltd. from above this notch, the adhesiveness of the surface protective layer was evaluated by rapidly peeling off in the 90 degree direction (initial adhesion). Sex test). Further, for each of the decorative sheets obtained above, a condition of leaving the decorative sheet at 100 ° C. for 500 hours (heat resistance test), a condition of leaving the decorative sheet at a temperature of 50 ° C. and a humidity of 100% for 500 hours (moisture and heat adhesion test). And the adhesion under the condition (weather resistance adhesion test) using a xenon weather meter (1000 kJ, 340 nm) was evaluated. The evaluation criteria are as follows. The results are shown in Table 1.
◯: No peeling is seen △: No peeling is seen in the initial adhesion, but peeling is seen in any of the heat resistance test, moisture heat adhesion test, or weather resistance test ×: Initial adhesion Peeling is seen in the test

As is clear from the results shown in Table 1, in the decorative sheets of Examples 1 to 6 in which the fine particle-containing layer containing fine particles is provided between the metal thin film layer and the surface protective layer, both before and after molding. It showed an appropriate metallic luster and was excellent in image quality. In particular, the decorative sheets of Examples 1, 4, and 5 in which the color ink layer, the first resin layer, or the second resin layer is a fine particle-containing layer have an appropriate metallic luster and excellent imageability. It was also excellent in adhesion.
On the other hand, in Comparative Example 1 in which fine particles were blended in the surface protective layer to adjust the metallic luster, the surface protective layer had an appropriate metallic luster, but the imageability was inferior. On the other hand, in Comparative Example 2 in which the layer containing the fine particles was not provided, the image quality was excellent, but the metallic luster was too high to express a high-quality texture.

1 ... Base material layer 2 ... Metal thin film layer 3 ... Fine particle-containing layer 4 ... Surface protection layer 5 ... Color clear layer 6 ... First primer layer 7 ... Second primer layer 8 ... First resin layer 9 ... Second resin layer 10 ... Molded resin layer 30 ... Fine particles

Claims (8)

At least, it is composed of a laminate in which a base material layer, a metal thin film layer, a fine particle-containing layer, and a surface protection layer are laminated in this order.
The surface of the fine particle-containing layer on the metal thin film layer side has an uneven shape due to the fine particles contained in the fine particle-containing layer.
The surface of the metal thin film layer on the fine particle-containing layer side has an uneven shape corresponding to the uneven shape of the surface of the fine particle-containing layer.
The surface of the surface protective layer on the fine particle-containing layer side is a flat surface.
The colored transparent color clear layer constitutes the fine particle-containing layer.
A decorative sheet provided with a second primer layer between the metal thin film layer and the color clear layer . In the fine particle-containing layer, the thickness of the portion where the fine particles are located is 1.2 times or more and 5.0 times or less the thickness of the portion where the fine particles are not located.
The decorative sheet according to claim 1, wherein the shortest distance x between the portion of the fine particle-containing layer where the fine particles are located and the surface of the metal thin film layer on the fine particle-containing layer side is 10 μm or less. The decorative sheet according to claim 1 or 2, wherein the shortest distance between the portion of the fine particle-containing layer where the fine particles are located and the surface of the metal thin film layer on the fine particle-containing layer side is 10 μm or less. The decorative sheet according to any one of claims 1 to 3, wherein the metal thin film layer is a layer formed by a vapor deposition method, a sputtering method, or an ion plating method. The metal thin film layer is formed of at least one metal selected from the group consisting of tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and an alloy containing at least one of these. The decorative sheet according to any one of claims 1 to 4. The decorative sheet according to any one of claims 1 to 5, wherein the thickness of the metal thin film layer is 200 nm or less. The surface protective layer is formed of an ionizing radiation curable resin or a resin film.
The decorative sheet according to any one of claims 1 to 6. At least, it is composed of a laminate in which a molding resin layer, a base material layer, a metal thin film layer, a fine particle-containing layer, and a surface protection layer are laminated in this order.
The surface of the fine particle-containing layer on the metal thin film layer side has an uneven shape due to the fine particles contained in the fine particle-containing layer.
The surface of the metal thin film layer on the fine particle-containing layer side has an uneven shape corresponding to the uneven shape of the surface of the fine particle-containing layer.
The surface of the surface protective layer on the fine particle-containing layer side is a flat surface.
The colored transparent color clear layer constitutes the fine particle-containing layer.
A decorative resin molded product provided with a second primer layer between the metal thin film layer and the color clear layer .

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