JP2020062860A - Decorative sheet for molding decoration - Google Patents

Abstract

To provide a molding decoration decorative sheet that does not impair the design of a blight-colored pattern even if a black color substrate sheet is used.SOLUTION: Provided is a molding decoration decorative sheet 1 having a transparent film layer 3, a pattern print layer 4, an adhesive layer 5, and a substrate sheet layer 8 in this order, in which the substrate sheet layer 8 is a black color acrylonitrile/butadiene/styrene copolymer resin sheet, and the adhesive layer 5 is a heat-sensitive adhesive layer containing a white pigment.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet, and more particularly, to a decorative sheet for molding and decorating, which is used by being attached to the surface of a plastic molded product for decoration.

  Various techniques have been proposed regarding a method of decorating the surface of a three-dimensional product used for interiors of shops, houses, vehicles, etc., houses, and exteriors of furniture. For example, a three-dimensional molded product can be painted by post-processing using a method such as hydraulic transfer, a method of vacuum-pressure molding a thick decorative sheet, and a preliminary method using this method. An in-mold molding method in which a molded product is set in a molding die and integrated by injection molding, or an in-mold transfer method in which a pattern is transferred simultaneously with molding in the mold during injection molding is known.

  Various decorative sheets suitable for such various decoration methods have been proposed. The decorative sheet described in Patent Document 1 is a decorative sheet having good secondary processability such as bending and sticking to a complicated shape. This decorative sheet has a tensile modulus of elasticity of 300 to 2000 MPa and a tensile elongation at break of 30 to 500% both in the direction of flow of the film and in the direction perpendicular to the direction of the film. A decorative sheet using a polyolefin film having no yield point in at least one direction.

  In addition, the printed decorative laminated material described in Patent Document 2 is a decorative material intended for the above-mentioned use, and is a decorative material having an improved deep feeling of a printed pattern. This decorative material is a printed decorative laminated material in which a printed layer and a transparent resin layer are laminated on a base material, and a colored layer is interposed between the printed layer and the transparent resin layer. It is a characteristic cosmetic material.

  Further, the decorative sheet described in Patent Document 3 is a decorative sheet used for decorating an ABS resin molded product used for interior parts of automobiles, etc., and it is not necessary to peel off the decorative sheet at the time of recycling, which is recyclable. It is an excellent decorative sheet.

  Conventionally, ABS resin (acrylonitrile / butadiene / styrene copolymer resin) has been widely used as a synthetic resin used for automobile parts, but it is often used by mixing recycled materials for the purpose of cost reduction. For this reason, a compound colored in black is often used in order to prevent the color tone of the resin compound from varying.

  Therefore, as for the decorative sheet used for the surface of the molded product, it is common to use a black ABS substrate sheet on the back surface in order to prevent variations in color tone, scratches and defects generated during molding, and to make it inconspicuous. Has become.

  On the other hand, in recent years, there has been a movement to develop light-colored wood grain patterns and geometric patterns used in living spaces for interior sheets for automobiles in order to improve the design. The decorative base sheet used in the living space is generally a colored base sheet with a brown or cream color tone, so the black base sheet for automobile interior is used in the living space. It has been an obstacle to developing light-colored designs in car interiors.

JP, 10-67081, A Japanese Patent Laid-Open No. 8-52759 JP 2001-334609 A

  The problem to be solved by the present invention is to propose a decorative sheet for molding decoration in which the design of a light-colored pattern is not impaired even if a black base sheet is used.

  As a means for solving the above problems, the invention according to claim 1 is a decorative sheet for molding and decorating, which has a transparent film layer, a pattern printing layer, an adhesive layer, and a base sheet layer in this order, In the decorative decorative sheet for molding, the base sheet layer is a black acrylonitrile / butadiene / styrene copolymer resin sheet, and the adhesive layer is a heat-sensitive adhesive layer containing a white pigment.

  The decorative sheet for molding decoration according to the present invention, by adding a white pigment to the adhesive layer for bonding the printed transparent film layer and the black base sheet layer, the design of the light-colored pattern is Damage is reduced.

  The invention according to claim 2 is characterized in that the white pigment contained in the adhesive layer is titanium oxide, and the content is 5% or more and 30% or less. It is a decorative decorative sheet.

  Further, the invention according to claim 3 is characterized in that the adhesive layer is composed of two layers, and the white pigment is contained only in the layer in contact with the pattern printing layer. It is a decorative decorative sheet.

  The invention according to claim 4 is the decorative sheet for molding and decorating according to any one of claims 1 to 3, which has a surface protective layer on the surface of the transparent film layer.

  The decorative decorative sheet for molding according to the present invention, by adding a white pigment to the adhesive layer for bonding the printed transparent film layer and the black base sheet layer, the black color of the base sheet layer is hidden. As a result, the deterioration of the design of the light-colored pattern was reduced.

  When the white pigment contained in the adhesive layer is titanium oxide and the content of titanium oxide is 5% or more and 30% or less, the hiding property and the adhesive property are high. Can be compatible at both levels.

  As in the invention according to claim 3, when the adhesive layer is composed of two layers and the white pigment is contained only in the layer in contact with the pattern printing layer, the hiding property and the adhesive property are highly balanced. Can be made.

FIG. 1 is a sectional explanatory view schematically showing a basic embodiment of a sheet for forming and decorating according to the present invention. FIG. 2 is a cross-sectional explanatory view schematically showing another embodiment of the molded decorative sheet according to the present invention, which is an example in which the adhesive layer is composed of two layers. FIG. 3 is a cross-sectional explanatory view schematically showing another embodiment of the molded decorative sheet according to the present invention, which is an example having a surface protective layer. FIG. 4 is a cross-sectional explanatory view showing an example of a decorative molded product produced using the molded decorative sheet according to the present invention.

  Hereinafter, the decorative sheet for molding and decorating according to the present invention will be described in detail with reference to the drawings. FIG. 1 is a sectional explanatory view schematically showing a basic embodiment of a sheet for forming and decorating according to the present invention. FIG. 4 is a cross-sectional explanatory view showing an example of a decorative molded product produced using the molded decorative sheet according to the present invention. The sheet for forming and decorating 1 according to the present invention is a decorative sheet used for decorating the surface of a molded product. As a basic structure, the transparent film layer 3, the pattern print layer 4, the adhesive layer 5, and the base sheet layer 8 are provided in this order. The base sheet layer 8 is a black acrylonitrile / butadiene / styrene copolymer resin (hereinafter abbreviated as ABS resin) sheet, and the adhesive layer 5 is a heat-sensitive adhesive layer containing a white pigment.

  The decorative decorative sheet 1 for molding and decorating according to the present invention is used as a surface decorative material for a molded article 10 having a three-dimensional shape as shown in FIG. The molded product 10 has a structure in which the sheet for molding decoration 1 is attached to the surface of the molding substrate 9. As described above, the molding base material 9 is often made of a black ABS resin containing a recycled material. As a method for adhering the sheet for forming and decorating 1 to the surface of the forming substrate 9, the sheet for forming and decorating 1 is preformed by a method such as a vacuum forming method or a vacuum pressure forming method in advance, and cut into a predetermined outer shape. An in-mold molding method or the like in which the molded product is placed in a molding die and a molding substrate is injection-molded to be integrated is used.

  In the decorative sheet 1 for molding and decorating according to the present invention, the pattern printing layer 4 is formed by printing on the back surface of the transparent film layer 3, and the printed surface is attached to the surface of the base material sheet layer 8 via the adhesive layer 5. The adhesive layer 5 is a heat-sensitive adhesive layer containing a white pigment.

  In many cases, the transparent film layer 3 serving as a printed material is required to have not only transparency and printability but also light resistance, weather resistance, scratch resistance, moldability, and the like. Acrylic resin films are most suitable in view of satisfying these required qualities in a well-balanced manner and considering the cost. As the acrylic resin film, the most common polymethylmethacrylate (PMMA) resin film can be used.

  As the transparent film layer 3, a film made of another material may be used depending on the degree of the required quality. For example, polyvinyl chloride resin film, polyvinylidene chloride resin film, polyethylene terephthalate (PET) resin film, polypropylene resin film, polystyrene resin film, polycarbonate resin film, ethylene-vinyl alcohol copolymer film or other single film or , A multi-layer film that combines these. You may combine these films with an acrylic resin film.

  The material of the ink used for printing the pattern print layer 5 is selected according to the material of the transparent film layer 3. If the transparent film layer 3 is an acrylic resin film, the same acrylic resin type ink is most suitable. In order to improve printability, a vinyl chloride-vinyl acetate copolymer resin can be added to the acrylic resin, or urethane modified.

  The base material sheet layer 8 has a thickness for the decorative sheet for forming and decorating, and ensures formability for preliminary preforming and the like for integrating with the forming base material 9 shown in FIG. It is not always necessary to use the same resin as the resin used for the molding substrate 9, but it is common to use the same type of resin.

  In the decorative molded decorative sheet according to the present invention, a black acrylonitrile / butadiene / styrene copolymer resin (ABS resin) sheet is used as the base sheet layer 8. The ABS resin sheet has a good balance between moldability and heat resistance and is optimal for the application of the present invention. In addition, by using a black-colored material, the black recycled resin, which is often used as the molding base material 9, has an effect of making defects during molding inconspicuous. As the ABS resin used as the ABS resin sheet, a general ABS resin obtained by copolymerizing acrylonitrile, butadiene and styrene, or a polymer blend type ABS resin obtained by mechanically kneading each polymer is used. Is also good.

  The resin system of the adhesive used for the adhesive layer 5 used for bonding the printed transparent film layer 3 and the base sheet layer 8 is not particularly limited, but the transparent film layer 3 which is an adherend, Since the base sheet layer 8 is also bonded in a state where the air permeability is low, a thermal laminating method or a dry laminating method in which a solvent is not used at the time of bonding is suitable as the bonding method. Therefore, it is essential to use a heat-sensitive adhesive as the adhesive layer 5.

  Examples of the binder resin used for the adhesive layer 5 include acrylic resin, acrylic polyol resin, polyester resin, polyester polyol resin, vinyl chloride vinyl acetate copolymer resin, vinyl acetate resin, ethylene vinyl acetate copolymer resin, epoxy resin, butyral resin, A single substance or a mixture of silicone resin, synthetic rubber type and polyurethane resin can be used. You may use together polyisocyanate as a hardening | curing agent to these. A white pigment dispersed in these binder resins is used as an adhesive. When the adhesive contains a solvent, the adhesive is attached and dried to remove the solvent before being bonded. In the case of a hot melt type that does not contain a solvent, it is pasted and cooled immediately after coating.

  The white pigment used in the adhesive layer 5 is not particularly limited, and white pigments such as titanium oxide, zinc white, lithopone, and lead white can be used, but titanium oxide is the most common. In the case of titanium oxide, the addition amount thereof is appropriately 5% or more and 30% or less as the solid content of the adhesive layer. If it is less than 5%, the hiding property may be insufficient, and if it exceeds 30%, the adhesive strength may be insufficient.

FIG. 2 is a cross-sectional explanatory view schematically showing another embodiment of the sheet for molding and decorating 1 according to the present invention, which is an example in which the adhesive layer 5 is composed of two layers. In this example, the adhesive layer 5 is composed of two layers, an adhesive layer A in contact with the pattern printing layer 4 and an adhesive layer B in contact with the base sheet layer 8, and a white pigment is dispersed only in the adhesive layer A. ing. By doing so, the amount of the white pigment dispersed in the adhesive layer A can be increased to the limit, and the decrease in the adhesive force due to this can be complemented by the adhesive layer B. The total weight of the adhesive layer 5 is preferably about ² g / m ² (dry) in both cases of a single layer and two layers.

  FIG. 3 is a cross-sectional explanatory view schematically showing another embodiment of the sheet for decorative molding according to the present invention, which is an example having the surface protective layer 2. The surface protective layer 2 is provided for the purpose of improving the surface performance of the molded product 10, and in addition to improving scratch resistance and stain resistance, light resistance, weather resistance, and hand oil proof (fingerprint resistance). It is provided for the purpose of improving the design and improving the texture, luster, and texture.

  As the surface protective layer 2, a transparent resin coating is prepared by appropriately adding necessary additives such as a matting agent, a wax, an ultraviolet absorber and a leveling agent to a resin varnish such as an acrylic resin type, a fluororesin type or a silicone resin type. Can be formed. The surface protective layer may be formed by painting after forming a molded product. Hereinafter, the decorative sheet for molding and decorating according to the present invention will be specifically described based on Examples.

<Example 1>
As a transparent film layer, a pattern printing layer was formed on the back surface of an acrylic resin film (Acryprene (registered trademark) manufactured by Mitsubishi Chemical Co., Ltd.) having a thickness of 125 μm using an acrylic ink (manufactured by Toyo Ink Co., Ltd.) by a gravure printing method. A heat-sensitive adhesive having the following composition was applied to the printed surface as an adhesive layer.
(Composition of heat-sensitive adhesive)
Acrylic resin (Acrynal LS # 3002 manufactured by Toei Kasei Co., Ltd.) and acrylic / vinyl chloride resin (V424 PVC primer manufactured by Toyo Ink Co., Ltd.) were mixed at 68:32 to prepare a resin liquid 1. Titanium oxide was dispersed and mixed in the resin liquid 1 so that the solid content ratio was 80:20.
The adhesive was applied with a bar coater at 2 g / m ² (dry), dried at 40 ° C. for 30 seconds, and then laminated on a black ABS substrate having a thickness of 380 μm at a speed of 2 m / min by a heat roll heated to 140 ° C. Then, it was used as a decorative sheet for molding and decoration.

<Example 2>
A decorative sheet for molding and decorating was prepared in the same manner as in Example 1 except that the composition of the heat-sensitive adhesive was changed to resin solution 1: titanium oxide = 90:10.

<Example 3>
Two adhesive layers were used, the first layer was coated with 1 g / m ² (dry) of a resin solution 1: titanium oxide = 70: 30, and the second layer was coated with the resin solution 1 at 1 g / m 2. ^A decorative sheet for molding and decorating was prepared in the same manner as in Example 1 except that ² (dry) coating was performed.

<Comparative Example 1>
A decorative decorative sheet for molding and decoration was prepared in the same manner as in Example 1 except that the resin liquid 1 was applied as the adhesive layer in an amount of 2 g / m ² (dry).

<Comparative example 2>
A decorative sheet for molding and decorating was prepared in the same manner as in Example 1 except that the composition of the heat-sensitive adhesive was changed to resin solution 1: titanium oxide = 95: 5.

The following evaluations were performed on the obtained decorative sheet for molding and decoration.
<Appearance (picture reproducibility)>
It was confirmed visually that the expected pattern was reproduced.
○: The expected pattern has been reproduced.
×: The expected pattern has not been reproduced.
<Appearance (air biting)>
The heat seal layer was observed using a laser microscope.
○: No air biting or solvent foaming.
×: Air biting or solvent foaming.
<Adhesiveness>
The printed surface and the ABS substrate are peeled off by hand to evaluate whether or not they are peeled off.
○: No interfacial peeling or cohesive peeling.
X: Interface peeling or cohesive peeling occurred.

  The above results are summarized in Table 1.

  From the results of Table 1, the superiority of the decorative sheet for molding and decorating according to the present invention can be seen.

DESCRIPTION OF SYMBOLS 1 ... Decorative sheet for molding and decoration 2 ... Surface protective layer 3 ... Transparent film layer 4 ... Picture printing layer 5 ... Adhesive layer 6 ... Adhesive layer A
7 ... Adhesive layer B
8 ... Base material sheet layer 9 ... Molded base material 10 ... Molded product

Claims (4)

  A decorative sheet for forming and decorating, comprising a transparent film layer, a pattern printing layer, an adhesive layer, and a base material sheet layer in this order, wherein the base material sheet layer is a black acrylonitrile / butadiene / styrene copolymer resin sheet, and an adhesive agent. A decorative sheet for molding and decorating, wherein the layer is a heat-sensitive adhesive layer containing a white pigment.   The white decorative pigment contained in the adhesive layer is titanium oxide, and the content thereof is 5% or more and 30% or less, and the decorative sheet for molding and decorating according to claim 1.   The decorative sheet for molding and decorating according to claim 1 or 2, wherein the adhesive layer is composed of two layers, and the white pigment is contained only in the layer in contact with the pattern printing layer.   The decorative sheet for molding and decorating according to any one of claims 1 to 3, wherein the transparent film layer has a surface protective layer on its surface.

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