JP6064495B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

  The present invention relates to a decorative sheet having a design property in which a rich and low gloss feeling with a texture is expressed, and having an excellent moldability. Furthermore, the present invention relates to a decorative resin molded product using the decorative sheet.

  A decorative resin molded product in which a decorative sheet is laminated on the surface of a resin molded product is used for a vehicle interior part, a building material interior material, a home appliance housing, and the like. Conventionally, in the production of a decorative resin molded product, a molding method is used in which a decorative sheet to which design properties have been imparted in advance is integrated with a resin by injection molding. As typical examples of such a method for producing a decorated resin molded product, an insert molding method and an injection molding simultaneous decoration method are known. In the insert molding method, a decorative sheet is molded into a three-dimensional shape in advance using a vacuum mold, the decorative sheet is inserted into an injection mold, and a resin in a flow state is injected into the mold to decorate the resin. This is a molding method that integrates the sheet. The injection molding simultaneous decoration method decorates the surface of the resin molded body by integrating the decorative sheet inserted into the mold during injection molding with the molten resin injected and injected into the cavity. Is a molding method.

  Some decorative resin molded products have a complicated surface shape such as a three-dimensional curved surface, and the decorative sheet is required to have three-dimensional formability that can sufficiently follow the shape of the decorative resin molded product. Yes. In addition, since the decorative sheet is used as a surface material of a decorative resin molded product, it is also required to have surface characteristics such as scratch resistance. In addition, with the recent trend toward high-class consumers, decorative resin molded products are required to express high-quality and high-quality designs.

  So far, several techniques have been reported for decorative sheets having excellent formability and scratch resistance, high texture, and excellent design. For example, Patent Document 1 discloses a low-gloss pattern ink layer that is provided at least partially on a substrate, and is present on and in contact with the low-gloss pattern ink layer. In the decorative sheet having the surface protective layer covering the entire surface including the region where the low gloss design ink layer is not formed, the composition and thickness of the surface protective layer are set to a specific range Thus, it has been reported that excellent moldability, scratch resistance, and design properties can be provided. Further, for example, in Patent Document 2, in a decorative sheet for insert molding having, in this order, a low gloss pattern ink layer and a surface protective layer partially provided on a support, the surface protective layer is thickened. An area where the low gloss pattern ink layer is formed and the low gloss pattern ink layer are formed in the surface protective layer while forming the ionizing radiation curable resin composition having a thickness of 1 to 30 μm by crosslinking and curing. It has been reported that excellent formability, scratch resistance, and design can be provided by covering the uncoated regions.

  Although the decorative sheet described in Patent Documents 1 and 2 can express a visual concavo-convex pattern from the surface with a low-gloss pattern ink layer, in response to the demands of consumers to appeal for an unprecedented and realistic design There is no limit to enumeration, and it is considered that the design expression of a conventional decorative sheet cannot always sufficiently follow the diversifying consumer preferences. Further, in recent years, there is a tendency that a design with a rich and low gloss feeling is desired. The use of a matting agent is effective to make the decorative sheet have a low glossiness. However, simply adding a matting agent to the surface protective layer of the decorative sheet will produce a rich, low-gloss texture. There is a problem that the design of the feeling cannot be expressed or the moldability is impaired.

  Against the background of such a conventional technique, it is desired to establish a technique that makes the decorative sheet have both a design property that expresses a rich and low gloss feeling with a texture and an excellent moldability.

JP 2009-132145 A JP 2010-30277 A

  The object of the present invention is to provide a decorative sheet having a design that expresses a rich and low gloss feeling with a texture and has an excellent moldability, and a decorative resin molded product using the decorative sheet It is to be.

  The inventors of the present invention have made extensive studies to solve the above problems, and in the decorative sheet in which at least a primer layer and a surface protective layer are sequentially laminated on the base material layer, the surface protective layer is provided. Formed from a cured product of an ionizing radiation curable resin composition containing a matting agent and an ionizing radiation curable resin, and by blending synthetic resin particles in the primer layer, a rich low gloss feeling with a texture is revealed. The present inventors have found that it is possible to combine the improved design and excellent formability. The present invention has been completed by further studies based on this finding.

That is, this invention provides the invention of the aspect hung up below.
Item 1. On the base material layer, it has at least a primer layer and a surface protective layer in order,
The surface protective layer is formed from a cured product of an ionizing radiation curable resin composition containing a matting agent and an ionizing radiation curable resin, and the primer layer contains synthetic resin particles;
A decorative sheet characterized by that.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the ionizing radiation curable resin is polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate.
Item 3. Item 3. The decorative sheet according to Item 1 or 2, wherein a pattern layer is provided between the base material layer and the primer layer.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein a low-gloss pattern layer that expresses a low-gloss region by interaction with the surface protective layer is provided between the primer layer and the surface protective layer.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein a transparent resin layer is provided between the base material layer and the primer layer.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the synthetic resin particles are at least one selected from the group consisting of acrylic beads, urethane beads, silicone beads, silicone rubber beads, and polyolefin waxes.
Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, wherein the synthetic resin particles have an average particle size of 0.1 to 10 µm.
Item 8. Item 8. The decorative sheet according to any one of Items 1 to 7, wherein the matting agent is at least one selected from the group consisting of acrylic beads, silicone rubber beads, and urethane beads.
Item 9. Item 9. The decorative sheet according to any one of Items 1 to 8, wherein the matting agent has an average particle size of 0.1 to 25 µm.
Item 10. Item 10. The decorative sheet according to any one of Items 1 to 9, wherein the content of the matting agent in the surface protective layer is 1 to 70 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.
Item 11. It has at least an injection resin layer, a base material layer, a primer layer, and a surface protective layer in order,
The surface protective layer is formed from a cured product of an ionizing radiation curable resin composition containing a matting agent and an ionizing radiation curable resin, and the primer layer contains synthetic resin particles,
This is a decorative resin molded product.
Item 12. A method for producing a decorative resin molded product including the following steps:
The vacuum forming process which shape | molds the decorating sheet in any one of claim | item 1 -10 in a solid shape beforehand with a vacuum forming die,
Trimming excess portions of the vacuum-decorated decorative sheet to obtain a molded sheet, and inserting the molded sheet obtained in the above process into an injection mold, closing the injection mold, and molding the fluid resin The process of injecting the resin and the molded sheet.
Item 13. A method for producing a decorative resin molded product including the following steps:
After the decorative sheet according to any one of Items 1 to 10 is installed so that the base material of the decorative sheet faces the molding surface of the movable mold having a molding surface of a predetermined shape, Heating and softening the decorative sheet, vacuum sucking from the movable mold side, and preliminarily molding the decorative sheet by adhering the softened decorative sheet along the molding surface of the movable mold,
After clamping the movable mold and the fixed mold having the decorative sheet adhered along the molding surface, the resin molding material in a fluid state is injected and filled into the cavity formed by both molds. An injection molding process in which the formed resin molded body and the decorative sheet are laminated and integrated by solidification, and a movable molded mold is separated from the fixed mold, and the entire decorative sheet is laminated. The process of taking out.

  The decorative sheet of the present invention can express a rich and low gloss feeling with a texture, and can have a novel and high-quality design that has never been seen before. In addition, the decorative sheet of the present invention has excellent moldability, and even when subjected to injection molding of a decorative resin molded product, it is possible to suppress the occurrence of cracks and the like. It can contribute to the improvement of production efficiency.

  Furthermore, the decorative sheet of the present invention also has excellent scratch resistance, and can be suitably used as a surface material for decorative resin products that are easily damaged such as vehicle interior parts.

It is a figure which shows the cross-section of one form of the decorating sheet of this invention. It is a figure which shows the cross-section of one form of the decorating sheet of this invention. It is a figure which shows the cross-section of one form of the decorating sheet of this invention.

1. Decorative sheet The decorative sheet of the present invention is formed by laminating at least a primer layer and a surface protective layer in order on a base material layer, and the surface protective layer contains a matting agent and an ionizing radiation curable resin. It is formed from a cured product of an ionizing radiation curable resin composition, and the primer layer contains synthetic resin particles. Hereinafter, the decorative sheet of the present invention will be described in detail.

Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure in which at least a primer layer and a surface protective layer are sequentially laminated on a base material layer.

  In the decorative sheet of the present invention, a pattern layer may be provided between the base material layer and the primer layer as necessary for the purpose of imparting decorative properties. Moreover, you may provide a low gloss pattern layer between a primer layer and a surface protective layer for the purpose of improving a low gloss feeling as needed. From the viewpoint of imparting decorativeness, it is desirable that at least one of the pattern layer and the low gloss pattern layer is provided.

  In the decorative sheet of the present invention, a concealing layer may be provided between the base material layer and the primer layer for the purpose of suppressing color change and variation of the base material layer. In the case of providing a picture layer, the concealing layer is provided between the base material layer and the picture layer.

  Furthermore, the decorative sheet of the present invention may be provided with a transparent resin layer between the base material layer and the primer layer as necessary for the purpose of improving chemical resistance and scratch resistance. In addition, what is necessary is just to provide a transparent resin layer between a pattern layer and a primer layer, when providing a pattern layer between a base material layer and a primer layer.

  Furthermore, in the decorative sheet of the present invention, the back surface of the base material layer (the surface opposite to the surface protective layer) is used for the purpose of improving the adhesion with the injection resin during the molding of the decorative resin product. If necessary, an adhesive layer may be provided

  As an example of the laminated structure of the decorative sheet of the present invention, a laminated structure in which a base material layer / picture layer / primer layer / surface protective layer are laminated in order; a base material layer / primer layer / low glossy picture layer / surface protective layer Laminated structure laminated in order; base layer / picture layer / primer layer / low gloss picture layer / surface protective layer laminated structure in order; base material layer / picture layer / transparent resin layer / primer layer / surface protective layer And a laminated structure in which a base material layer / picture layer / transparent resin layer / primer layer / low glossy picture layer / surface protective layer are laminated in order. FIG. 1 shows a cross-sectional view of a decorative sheet in which a base material layer / picture layer / primer layer / surface protective layer are sequentially laminated as an embodiment of the laminated structure of the decorative sheet of the present invention. In FIG. 2, sectional drawing of the decorating sheet | seat on which the base material layer / picture layer / transparent resin layer / primer layer / surface protective layer was laminated | stacked in order as one aspect | mode of the laminated structure of the decorating sheet of this invention is shown. FIG. 3 shows a cross-sectional view of a decorative sheet in which a base material layer / picture layer / primer layer / low glossy picture layer / surface protective layer are sequentially laminated as an embodiment of the laminated structure of the decorative sheet of the present invention.

Each layer composition that forms a decorative sheet [base material layer]
The base material layer plays a role as a support in the decorative sheet of the present invention. The resin film used for the base material layer is not particularly limited and may be appropriately selected according to the three-dimensional moldability, compatibility with the injection resin, and the like, preferably a resin film made of a thermoplastic resin. It is done. Specific examples of the thermoplastic resin include acrylonitrile / butadiene / styrene resin (hereinafter sometimes referred to as “ABS resin”), acrylonitrile / styrene / acrylic ester resin (hereinafter referred to as “ASA resin”). A), polyolefin resins such as acrylic resin, polypropylene and polyethylene, polycarbonate resin, vinyl chloride resin, polyethylene terephthalate (PET) and the like. Among these, ABS resin is preferable from the viewpoint of three-dimensional moldability. Moreover, the base material layer may be formed with the single layer sheet | seat of these resin, and may be formed with the multilayer sheet | seat by the same kind or different resin.

  Although it does not restrict | limit especially about the bending elastic modulus of a base material layer, For example, the bending elastic modulus in 25 degreeC is 500-4,000 MPa, Preferably 750-3,000 MPa is mentioned. Here, the flexural modulus at 25 ° C. is a value measured according to JIS K7171. When the flexural modulus at 25 ° C. is 500 MPa or more, the decorative sheet has sufficient rigidity, and the surface characteristics and moldability are further improved. In addition, when the bending elastic modulus at 25 ° C. is 3,000 MPa or less, sufficient tension can be applied when manufacturing by roll-to-roll, and sagging does not easily occur. So that the so-called pattern registration is good.

  The base material layer is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one or both sides as necessary in order to improve the adhesion with the layer provided on the base material layer. Also good. Examples of the oxidation method performed as the surface treatment of the substrate layer include a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method. Moreover, as the uneven | corrugated method performed as surface treatment of a base material layer, a sandblasting method, a solvent processing method, etc. are mentioned, for example. These surface treatments are appropriately selected according to the type of the resin component constituting the base material layer. From the viewpoints of effects and operability, a corona discharge treatment method is preferable.

  The base material layer may be subjected to a treatment such as forming a known adhesive layer.

  Furthermore, the base material layer may be colored with a colorant or may not be colored. Further, the base material layer may be any of colorless and transparent, colored and transparent. Although it does not restrict | limit especially as a coloring agent used for a base material layer, Preferably the coloring agent which does not discolor also at 150 degreeC or more temperature conditions is mentioned, Specifically, the existing dry color, paste color, masterbatch resin composition Thing etc. are mentioned.

  Although the thickness of a base material layer is suitably set according to the use etc. of a decorating sheet, it is about 50-1000 micrometers normally, Preferably it is 100-700 micrometers, More preferably, 100-500 micrometers is mentioned. When the thickness of the base material layer is within the above range, it is possible to provide more excellent surface properties, three-dimensional formability, and design properties, and the printing workability (productivity) is also improved. It becomes advantageous from.

[Hidden layer]
The concealing layer is used between the base material layer and the primer layer, or between the base material layer and the picture layer, if necessary, for the purpose of suppressing color change and variation of the base material layer. It is a layer provided.

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

  The concealing layer is formed using an ink composition in which a binder, a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed. The ink composition for forming the hiding layer is appropriately selected from those used for the pattern layer described later.

  The concealing layer is usually set to a thickness of about 1 to 20 μm and is desirably formed as a so-called solid printing layer.

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

[Picture layer]
The pattern layer is a layer provided as necessary between the base material layer and the primer layer, or between the concealing layer and the primer layer when providing the concealing layer, for the purpose of imparting decorativeness to the decorative sheet. .

  The pattern layer is a layer in which a desired pattern is formed using the ink composition. As the ink composition used for forming the pattern layer, a binder and a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed.

  The binder used in the ink composition is not particularly limited. For example, polyurethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin , Polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin and the like. These binders may be used individually by 1 type, and may be used in combination of 2 or more type.

  The colorant used in the ink composition is not particularly limited. For example, carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue Inorganic pigments such as: organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue; metal pigments composed of scaly foils such as aluminum and brass; scaly foils such as titanium dioxide-coated mica and basic lead carbonate Examples include pearlescent (pearl) pigments composed of pieces.

  The pattern formed by the pattern layer is not particularly limited, but, for example, a wood pattern, a marble pattern (for example, a travertine marble pattern), a stone pattern that simulates the surface of a rock, or a cloth that simulates a texture or cloth pattern Patterns, tiled patterns, brickwork patterns, and the like may be mentioned, and patterns such as marquetry and patchwork that combine these may be used. These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, but also by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. Can be formed.

  Although the thickness in particular of a pattern layer is not restrict | limited, For example, 1-30 micrometers, Preferably 1-20 micrometers is mentioned.

  A picture layer is formed by printing so that it may become a desired picture using an ink composition. The printing method for forming the pattern layer is not particularly limited, and examples thereof include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and ink jet printing.

[Transparent resin layer]
The transparent resin layer is a layer provided as necessary between the base layer and the primer layer, or between the base layer and the primer layer when providing the base layer, for the purpose of improving chemical resistance and scratch resistance. It is.

  The resin component for forming the transparent resin layer is appropriately selected according to transparency, three-dimensional moldability, shape stability, chemical resistance, etc., but a thermoplastic resin is usually used. The thermoplastic resin is not particularly limited, and examples thereof include acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, ABS resins, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and vinyl chloride resins. Etc. are used. Among these thermoplastic resins, from the viewpoint of chemical resistance, scratch resistance, etc., preferably acrylic resins, polyolefin resins, polycarbonate resins, polyester resins; more preferably acrylic resins, polyester resins; more preferably polyesters. Resin.

  The transparent resin layer 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 with other layers that come into contact with the transparent resin layer. Also good. These physical or chemical surface treatments are the same as the surface treatments applied to the base material layer.

  Although it does not restrict | limit especially about the thickness of a transparent resin layer, For example, 10-200 micrometers, Preferably 15-150 micrometers is mentioned.

  The transparent resin layer may be laminated via an adhesive, or may be laminated directly without using an adhesive. When laminating via an adhesive, examples of the adhesive used include polyester resin, polyether resin, urethane resin, epoxy resin, phenol resin, polyamide resin, polyolefin resin, polyvinyl acetate resin, cellulose resin, and acrylic resin. Resins, polyimide resins, amino resins, rubbers, silicon resins, and the like can be given. Moreover, when laminating | stacking without using an adhesive agent, it can carry out by methods, such as an extrusion method, a sand lamination method, and a thermal lamination method.

[Primer layer]
The primer layer is a layer containing synthetic resin particles, and between the base material layer and the surface protective layer, when providing a picture layer, between the picture layer and the surface protective layer, and when providing a low gloss picture layer, the base material layer and Between the low gloss pattern layer, when providing a pattern layer and a low gloss pattern layer, between the pattern layer and the low gloss pattern layer, when providing a transparent resin layer, between the transparent resin layer and the surface protective layer, or transparent resin When the layer and the low gloss pattern layer are provided, they are provided between the transparent resin layer and the low gloss pattern layer. When the low gloss pattern layer is provided, the primer layer may contact both the low gloss pattern layer and the surface protective layer as shown in FIGS.

  The primer layer is formed using a primer composition containing synthetic resin particles and a binder resin. By selecting synthetic resin particles in this way and blending them into the primer layer, fine cracks and whitening occur in the stretched portion of the surface protective layer based on the interaction with the surface protective layer having a specific composition described later. The effect is made difficult, and a rich, low-gloss appearance with a texture is possible. In addition, the synthetic resin particles contained in the primer layer also have advantageous effects such as suppression of cracking during molding, improved adhesion with other layers in contact, and improved blocking resistance in the case of off-line printing. Can be played.

  The synthetic resin particles contained in the primer layer may be either a thermosetting resin or a thermoplastic resin. The type of synthetic resin particles is not particularly limited, and examples thereof include acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, and polyolefin waxes. Specific examples of the polyolefin wax include polyethylene wax and polypropylene wax. Among these synthetic resin particles, acrylic beads, urethane beads, silicone beads, silicone rubber beads, polyolefin waxes, and more preferably acrylic beads are preferable from the viewpoint of further improving the low gloss to be expressed. These synthetic resin particles may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although it does not restrict | limit especially about the average particle diameter of a synthetic resin particle, For example, 0.1-10 micrometers is mentioned. In particular, the average particle diameter of the synthetic resin particles is preferably 0.5 to 5 μm from the viewpoint of further improving the rich low gloss feeling and the moldability with a texture. Here, the average particle size of the synthetic resin particles is determined by using the Shimadzu laser diffraction particle size distribution analyzer SALD-2100-WJA1 and using compressed air to inject the powder to be measured from the nozzle and into the air. It is a value measured by a spray-type dry measurement method that is measured by dispersing.

The specific gravity of the synthetic resin particles is not particularly limited, but is, for example, 0.7 to 1.5 g / cm ³ , preferably 0.8 to 1.3 g / cm ³ , and more preferably 0.85 to 1. 2 g / cm ³ is mentioned.

  Further, the content of the synthetic resin particles in the primer layer is appropriately set according to the low gloss feeling to be exposed on the decorative sheet, for example, 1 to 100 parts by mass of the binder resin in the primer layer. 70 mass parts, Preferably it is 10-50 mass parts, More preferably, 15-50 mass parts is mentioned.

  The binder resin used in the primer composition is not particularly limited, but may be a mutual relationship between a thermoplastic resin used in a low-gloss pattern layer provided as necessary and an ionizing radiation curable resin that forms a surface protective layer. A resin having a property that hardly causes an action is preferable, and examples of such a resin include a thermosetting resin. Specific examples include urethane resins, (meth) acrylic resins, (meth) acrylic / urethane copolymer resins, vinyl chloride / vinyl acetate copolymers, polyester resins, butyral resins, chlorinated polypropylene, and chlorinated polyethylene. It is done. These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type. Among these binder resins, urethane resins, (meth) acrylic resins, and (meth) acrylic / urethane copolymer resins are preferable. In addition, the primer layer is preferably formed using a cross-linking agent from the viewpoint of more prominently exhibiting the effect of developing a gloss difference between the low gloss pattern layer and the surface protective layer provided as necessary.

  As the urethane resin, polyurethane having a polyol (polyhydric alcohol) as a main ingredient and an isocyanate as a crosslinking agent (curing agent) can be used. The polyol may be any compound having two or more hydroxyl groups in the molecule, and specific examples include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like. Specific examples of the isocyanate include polyvalent isocyanate having two or more isocyanate groups in the molecule; aromatic isocyanate such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, Examples include aliphatic (or alicyclic) isocyanates such as hydrogenated diphenylmethane diisocyanate.

  Among the urethane resins, acrylic is preferably used as a polyol from the viewpoints of improving adhesion to the surface protective layer after crosslinking, reducing interaction after laminating the surface protective layer, improving physical properties, and improving moldability. A combination of a polyol or polyester polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a cross-linking material; more preferably, a combination of acrylic polyol and hexamethylene diisocyanate.

  Although it does not restrict | limit especially as said (meth) acrylic resin, For example, the homopolymer of (meth) acrylic acid ester, the copolymer of 2 or more types of different (meth) acrylic acid ester monomers, or (meth) acrylic acid Examples include copolymers of esters and other monomers. More specifically, as a (meth) acrylic resin, poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, (meth) acrylic acid Methyl / (meth) butyl acrylate copolymer, (meth) ethyl acrylate / (meth) butyl acrylate copolymer, ethylene / (meth) methyl acrylate copolymer, styrene / methyl (meth) acrylate copolymer Examples include (meth) acrylic acid esters such as polymers. These (meth) acrylic resins may be used alone or in combination of two or more.

  Although it does not restrict | limit especially as (meth) acryl / urethane copolymer resin, For example, acrylic / urethane (polyester urethane) block copolymer resin is mentioned. Further, as the curing agent, the above-described various isocyanates are used. The ratio of the acrylic to urethane ratio in the acrylic-urethane (polyester urethane) block copolymer resin is not particularly limited. For example, the acrylic / urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8 / 2 to 2/8.

In addition, as a physical property of the primer layer, the elongation at break at 120 ° C. measured under the following measurement conditions from the viewpoint of making fine cracks and whitening hardly occur in the stretched portion of the surface protective layer during vacuum forming of the decorative sheet, Preferably it is 50% or more, more preferably 200% or more.
(Measurement conditions for measuring elongation at break)
In accordance with JIS K 7127: 1999, a primer composition constituting the primer layer was crosslinked and cured (heated at 50 ° C. for 72 hours) to form a film having a width of 25 mm × length (distance between chucks) of 50 mm × thickness of 40 ± 10 μm. After putting the sample in an oven at 120 ° C. and leaving it for 120 seconds, the elongation at break is measured at a tensile speed of 50 mm / min.

  Although it does not restrict | limit especially about the thickness of a primer layer, For example, 0.1-10 micrometers, Preferably 1-10 micrometers is mentioned. By satisfying such a thickness, the primer layer can effectively express a rich and low gloss feeling and can effectively suppress cracking, breakage, whitening and the like of the surface protective layer.

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

[Low gloss pattern layer]
The low gloss pattern layer is a layer provided as necessary between the primer layer and the surface protective layer for the purpose of satisfactorily expressing the uneven surface pattern and enhancing the low gloss feeling.

  The low gloss pattern layer is an elution, dispersion, and mixing that occurs between the resin composition forming the low gloss pattern layer and the ionizing radiation curable resin forming the surface protective layer provided on the low gloss pattern layer. It is a layer that forms a low gloss region exhibiting low gloss in the vicinity including the immediate upper part or the immediate upper part of the low gloss pattern layer (hereinafter sometimes referred to simply as “directly above and its vicinity”) by the interaction of . This interaction is inevitably caused, and the range in the vicinity cannot be controlled. The low gloss pattern layer expresses low gloss by interaction with the ionizing radiation curable resin composition, and even if the gloss value of the low gloss pattern layer alone is high, the low gloss pattern layer By the interaction of the surface protective layer, the decorative sheet having a low gloss feeling can be exhibited.

  As described above, the low-gloss pattern layer forms a low-gloss region immediately above and in the vicinity thereof (see FIG. 3). Therefore, when the decorative sheet is viewed from the surface protective layer side, the portion where the relatively low gloss region is expressed is visually recognized as a concave portion, and the other region is visually recognized as a convex portion. Therefore, it is visually recognized as an uneven pattern as a whole. Therefore, on the outermost surface of the surface protective layer corresponding to the immediate upper portion where the low gloss pattern layer is formed and the vicinity thereof, the visual effect of irregularities can be obtained without providing a convex shape due to the low gloss pattern layer. However, a physical uneven shape may be formed in a portion where the visual effect of the unevenness is obtained. When a convex shape is formed around the low-gloss pattern layer, the surface area scattered by the convex shape increases, the glossiness decreases further, and the viewing angle for recognizing low-glossiness also increases. In addition to the effect of the glossy pattern layer, the visual unevenness is further emphasized. In addition, although it does not restrict | limit especially about the height of the convex shape in the case of providing the said uneven | corrugated shape, Usually, 2-3 micrometers is mentioned. The design of the low gloss pattern layer may be formed in a pattern pattern, or may be a uniform pattern, that is, a solid pattern.

  The ink used for the low gloss pattern layer needs to be a binder resin having the property of allowing interaction with the ionizing radiation curable resin forming the surface protective layer, and as such a binder resin Is a resin usually used without using a crosslinking agent such as isocyanate, preferably a thermoplastic resin not using a crosslinking agent.

  Specific examples of the thermoplastic resin used in the low gloss pattern layer include acrylic resins, polyester resins, unsaturated polyester resins, nitrocellulose resins such as nitrified cotton, thermoplastic urethane resins, and polyvinyl acetal resins such as polyvinyl butyral. Etc. Among these thermoplastic resins, compatibility with polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate employed as an ionizing radiation curable resin of an ionizing radiation curable resin composition for forming a surface protective layer to be described later That is, from the viewpoint of making whitening and the like difficult to occur, nitrocellulose resins such as urethane resins, acrylic resins, and nitrified cotton are preferable, and acrylic resins are more preferable.

  The molecular weight of the acrylic resin is not particularly limited. For example, the weight average molecular weight is 10,000 to 1,000,000, preferably 50,000 to 700,000, and more preferably 70,000 to 500,000. Can be mentioned. By satisfying such a weight average molecular weight, the thixotropy is good and the unevenness of the low gloss pattern layer is easily exposed, and the film forming property and transferability during printing are also improved.

  In addition, for the low gloss pattern layer, an unsaturated polyester resin, acrylic resin, or vinyl chloride is used to adjust the degree of expression of the low gloss region and the contrast of the gloss difference between the low gloss layer and its surroundings as necessary. / Vinyl acetate copolymer may be contained.

  Further, the low gloss pattern layer may contain porous particles such as silica as necessary. By including porous particles such as silica in the low gloss pattern layer, large irregularities are formed immediately above and near the low gloss pattern layer so that light is greatly scattered. Low gloss can be further promoted. The silica used for the low gloss pattern layer preferably has an oil absorption of 180 to 220 ml / 100 g and an average particle size of 1 to 8 μm. The average particle size of silica is measured by using the Shimadzu laser diffraction particle size distribution analyzer SALD-2100-WJA1 and using compressed air to inject the powder to be measured from the nozzle and dispersing it in the air. It is a value measured by the jet type dry measurement method to be measured.

  When porous particles are contained in the low gloss pattern layer, the content is not particularly limited, but for example, 20 to 150 parts by mass, preferably 20 to 100 parts by mass with respect to 100 parts by mass of the resin in the low gloss pattern layer. 120 parts by mass can be mentioned. When the content of the porous particles satisfies the above range, the design property by the low gloss pattern layer can be expressed more effectively, and the moldability is improved by providing the low gloss pattern layer with desired flexibility. It becomes possible to do.

  Although it does not restrict | limit especially about the thickness of a low gloss pattern layer, For example, 0.1-10 micrometers, Preferably it is 0.6-7 micrometers. By satisfying such a thickness, the interaction with the surface protective layer is sufficient, a low gloss area that exhibits low gloss can be sufficiently formed, and there are no mechanical restrictions when printing ink, and it is economical. Also advantageous.

[Surface protective layer]
The surface protective layer is a layer formed from a cured product of an ionizing radiation curable resin composition containing a matting agent and an ionizing radiation curable resin, and is the outermost surface of the decorative sheet (on the primer layer or low gloss pattern layer) Is provided on the low gloss pattern layer).

  The surface protective layer is formed from a cured product of an ionizing radiation curable resin composition containing a matting agent and an ionizing radiation curable resin, so that, in combination with the action of the primer layer, a rich low quality with a texture. Glossy feeling can be expressed, and further, moldability can be improved. In addition, when the low gloss pattern layer is provided, a low gloss region expressing low gloss is formed by the interaction between the ionizing radiation curable resin forming the surface protective layer and the low gloss pattern layer, which is more excellent. A low gloss feeling can be exhibited.

(Matting agent)
The matting agent used in the surface protective layer is a component that diffuses or reflects light to cause the gloss to disappear or attenuate. The matting agent contained in the surface protective layer is not particularly limited, and those generally used in the field of paints and the like can be used, and any of synthetic resin particles or inorganic particles may be used. As the matting agent, specifically, synthetic resin particles such as acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, polyolefin wax (polypropylene wax, polyethylene wax, mixtures thereof, etc.); silica Inorganic particles such as alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, kaolin, and hydrophobic treated products thereof. These matting agents may be used individually by 1 type, and may be used in combination of 2 or more type. Among these matting agents, synthetic resin particles are preferable from the viewpoint of further improving moldability, further improving the low gloss feeling to be exposed, and suppressing glossiness after injection molding, and the like. Acrylic beads, silicone rubber beads, urethane beads, particularly preferably urethane beads.

Further, the specific gravity of the matting agent is not particularly limited, but is, for example, 0.7 to 1.5 g / cm ³ , preferably 0.8 to 1.3 g / cm ³ , and more preferably 0.85 to 1. 2 g / cm ³ is mentioned.

  The average particle size of the matting agent is not particularly limited, but is usually 0.1 to 25 μm, preferably 1 to 10 μm, more preferably from the viewpoint of better expressing a rich low gloss feeling with a texture. 1-5 micrometers is mentioned. Here, the average particle size of the matting agent is determined by using the Shimadzu laser diffraction particle size distribution analyzer SALD-2100-WJA1 and using compressed air to inject the powder to be measured from the nozzle and into the air. It is a value measured by an injection-type dry measurement method that is measured by dispersing.

  Further, the content of the matting agent in the surface protective layer is appropriately set depending on the low gloss feeling to be displayed on the decorative sheet, for example, 100 parts by mass of ionizing radiation curable resin in the surface protective layer 1 to 70 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 to 30 parts by mass.

  Part of the particles of the matting agent may protrude from the surface of the surface protective layer, or may be embedded in the surface protective layer. When some of the particles protrude from the surface protective layer, the matte effect tends to be improved.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used to form the surface protective layer is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group is present in the molecule. What mixed the prepolymer, oligomer, and / or monomer which it has suitably is mentioned. Here, ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. Among ionizing radiation curable resins, electron beam curable resins can be made solvent-free, do not require a photopolymerization initiator, and provide stable curing characteristics, which is suitable for forming a surface protective layer. used.

  As the monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (bifunctional or more), preferably three or more (trifunctional or more) 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 ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di ( (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri ( (Meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol Examples include hexa (meth) acrylate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The oligomer used as the ionizing radiation curable resin is preferably a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule, and more than two polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferred. 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, oligomer having a cationic polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) . Here, the polycarbonate (meth) acrylate can be obtained, for example, by esterifying a polycarbonate polyol with (meth) acrylic acid. The acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used. Polyester (meth) acrylate is obtained 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, for example, or It can be obtained by esterifying the terminal hydroxyl group of an 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. Silicone (meth) acrylate can be obtained by adding (meth) (meth) acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type. In the present specification, “(meth) acrylate” means “acrylate or methacrylate”, and other similar ones have the same meaning.

  These curable resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these curable resins, polycarbonate (meth) acrylate and acrylic silicone (meth) acrylate are preferably used from the viewpoint of further improving the expressive effect and rich formability of the texture and rich luster.

  When polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate is used for forming the surface protective layer, these may be used alone as an ionizing radiation curable resin, and polycarbonate (meth) acrylate and / or When using in combination with polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate and other ionizing radiation curable resin, which may contain a combination of acrylic silicone (meth) acrylate and other ionizing radiation curable resin, The combination mode is not particularly limited, but is preferably polycarbonate (meth) acrylate and / or acrylic silicone (meta) from the viewpoint of further improving the expression effect of rich and low gloss with a texture and the moldability. ) With acrylate The combination of polyfunctional (meth) acrylate is mentioned.

  The polyfunctional (meth) acrylate used in combination with the polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate may be any one of the above-mentioned polyfunctional (meth) acrylate monomers and oligomers, or both of them. However, a polyfunctional (meth) acrylate oligomer is preferable. In particular, a polyfunctional urethane (meth) acrylate oligomer is preferable, a trifunctional or higher functional urethane (meth) acrylate oligomer is particularly preferable, and a 3- to 8-functional urethane (meth) acrylate oligomer is particularly preferable.

  The molecular weight of the polyfunctional (meth) acrylate oligomer used in combination with the polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate is not particularly limited. For example, the weight average molecular weight is 1,000 to 20,000. , Preferably 1,000-10,000 are mentioned.

  Moreover, when combining a polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate and a polyfunctional (meth) acrylate, as these ratios, for example, polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate: The mass ratio of the polyfunctional (meth) acrylate is, for example, 98: 2 to 60:40, preferably 95: 5 to 65:35.

  Hereinafter, polycarbonate methacrylate and acrylic silicone (meth) acrylate that are suitably used as an ionizing radiation curable resin in the formation of the surface protective layer will be described.

<Polycarbonate (meth) acrylate>
The polycarbonate (meth) acrylate used as the ionizing radiation curable resin is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate in the terminal or side chain. Moreover, the said (meth) acrylate is 2 or more normally as a number of the functional groups per molecule from a viewpoint of making bridge | crosslinking and hardening favorable, Preferably 2-6 are mentioned.

  The polycarbonate (meth) acrylate is obtained, for example, by converting part or all of the hydroxyl groups of the polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be performed by a normal esterification reaction. For example, 1) a method of condensing polycarbonate polyol and acrylic acid halide or methacrylic acid halide in the presence of a base, 2) a method of condensing polycarbonate polyol and acrylic acid anhydride or methacrylic acid anhydride in the presence of a catalyst, Or 3) a method of condensing polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst.

  The polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain. A typical method for producing the polycarbonate polyol includes a method by a polycondensation reaction from a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component.

The diol compound (A) used as a raw material for the polycarbonate polyol is represented by the general formula HO—R ¹ —OH. Here, R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain an ether bond. For example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

  Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in combination of two or more.

  Examples of the trihydric or higher polyhydric alcohol (B) used as a raw material for polycarbonate polyol include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Is mentioned. The trihydric or higher polyhydric alcohol may be an alcohol having a hydroxyl group in which 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide is added to the hydroxyl group of the polyhydric alcohol. Good. These polyhydric alcohols may be used individually by 1 type, and may be used in combination of 2 or more type.

  The compound (C) used as a raw material of the polycarbonate polyol, which is a carbonyl component, is any compound selected from carbonic acid diesters, phosgene, and equivalents thereof. Specific examples of the compound include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate; phosgene; halogenated formic acid such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate. Examples include esters. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The polycarbonate polyol is synthesized by subjecting the diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component to a polycondensation reaction under general conditions. What is necessary is just to set the preparation molar ratio of a diol compound (A) and a polyhydric alcohol (B) in the range of 50: 50-99: 1, for example. Further, the charged molar ratio of the compound (C) serving as the carbonyl component to the diol compound (A) and the polyhydric alcohol (B) is, for example, 0.2 to 2 with respect to the hydroxyl group of the diol compound and the polyhydric alcohol. What is necessary is just to set to the range of an equivalent.

  The number of equivalents of hydroxyl groups (eq./mol) present in the polycarbonate polyol after the polycondensation reaction at the above-mentioned charge ratio is, for example, 3 or more on average in one molecule, preferably 3 to 50, more preferably 3-20 are mentioned. When such an equivalent number is satisfied, a necessary amount of (meth) acrylate groups are formed by an esterification reaction described later, and moderate flexibility is imparted to the polycarbonate (meth) acrylate resin. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.

  The method for producing the polycarbonate polyol described above is described in, for example, JP-A No. 64-1726. The polycarbonate polyol can also be produced by an ester exchange reaction between a polycarbonate diol and a trihydric or higher polyhydric alcohol as described in JP-A-3-181517.

  The molecular weight of the polycarbonate (meth) acrylate is not particularly limited. For example, the weight average molecular weight is 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but may be, for example, 100,000 or less, preferably 50,000 or less from the viewpoint of controlling the viscosity not to be too high. The weight average molecular weight of the polycarbonate (meth) acrylate is preferably more than 2,000 and not more than 50,000, and more preferably from the viewpoint of further improving the expression effect of rich luster with a texture and moldability. Is 5,000 to 20,000.

  In addition, the weight average molecular weight of the polycarbonate (meth) acrylate in the present specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

<Acrylic silicone (meth) acrylate>
The acrylic silicone (meth) acrylate used as the ionizing radiation curable resin is not particularly limited, and a part of the acrylic resin structure is substituted with a siloxane bond (Si—O) in one molecule, and Any functional group may be used as long as it has two or more (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) at the side chain and / or main chain terminal of the acrylic resin. As a suitable example of this acrylic silicone (meth) acrylate, the structure of the acrylic resin which has a siloxane bond in a side chain as disclosed by Unexamined-Japanese-Patent No. 2007-070544 is mentioned, for example. In addition, the acrylic silicone (meth) acrylate is usually 2 or more in terms of the number of functional groups per molecule from the viewpoint of further improving the expression effect and moldability of a rich and low gloss feeling with a texture. Preferably 3-8 pieces are mentioned.

  The acrylic silicone (meth) acrylate can be synthesized, for example, by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer in the presence of a radical polymerization initiator.

  Examples of the (meth) acrylate monomer used as a raw material for the acrylic silicone (meth) acrylate include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( Examples include meth) acrylate and glycidyl (meth) acrylate. These (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 types.

  The silicone macromonomer used as a raw material for the acrylic silicone (meth) acrylate is, for example, living anion polymerization of hexaalkylcyclotrisiloxane using n-butyllithium or lithium silanolate as a polymerization initiator, and further radical polymerizable unsaturated. It is synthesized by capping with a group-containing silane. As the silicone macromonomer, a compound represented by the following formula (1) is preferably used.

Here, in the formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, a methyl group or an n- butyl group are preferable. R ² represents a monovalent organic group, —CH═CH ₂ , —C ₆ H ₄ —CH═CH ₂ , — (CH ₂ ) ₃ O (CO) CH═CH ₂ , or — (CH ₂ ). ₃ O (CO) C (CH ₃ ) ═CH ₂ is preferred. R ^{3 s} may be the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, and more preferably a methyl group. N represents the number of repeating units-[Si (R ³ ) ₂ ]-, and the number is not particularly limited, but the number average molecular weight of the silicone macromonomer is 1,000 to 30,000, preferably 1 It is desirable that the range of 20,000 to 20,000 is satisfied.

  The acrylic silicone (meth) acrylate obtained using the above-mentioned raw materials has structural units represented by the following formulas (2), (3) and (4), for example.

In formulas (2), (3) and (4), R ¹ and R ³ have the same meanings as in formula (1), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents the (meth) acrylate. An alkyl group or glycidyl group in the monomer, or an alkyl group which may have a functional group such as an alkyl group or glycidyl group in the (meth) acrylate monomer, and R ⁶ is an organic compound having a (meth) acryloyloxy group. Represents a group, and n has the same meaning as in formula (1).

  The said acrylic silicone (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although there is no restriction | limiting in particular about the molecular weight of the said acrylic silicone (meth) acrylate, For example, the weight average molecular weight of standard polystyrene conversion by GPC analysis is 1,000 or more, Preferably 2,000 or more is mentioned. The upper limit of the weight average molecular weight of the acrylic silicone (meth) acrylate is not particularly limited, but may be, for example, 150,000 or less, preferably 100,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of further improving the expressive effect and moldability of a rich low gloss feeling with a texture, the weight average molecular weight in terms of standard polystyrene by GPC analysis of the acrylic silicone (meth) acrylate is preferably 2,000 to 100,000.

  Further, the average molecular weight between the crosslinking points of the acrylic silicone (meth) acrylate is not particularly limited, and examples thereof include 100 to 2,500, preferably 100 to 1,500, and more preferably 100 to 1,000. . By satisfying such an average molecular weight between cross-linking points, moldability can be further improved.

(Other additive ingredients)
Various additives can be blended in the ionizing radiation curable resin composition forming the surface protective layer according to desired physical properties to be provided in the surface protective layer. Examples of the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a colorant. These additives can be appropriately selected from those commonly used. In addition, 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 be used.

(Surface protective layer thickness)
Although there is no restriction | limiting in particular about the thickness after hardening of a surface protective layer, For example, 1-1000 micrometers, Preferably it is 1-50 micrometers, More preferably, 1-30 micrometers is mentioned. Satisfying a thickness in such a range can provide sufficient physical properties as a protective layer such as scratch resistance and weather resistance, and can be uniformly irradiated with ionizing radiation, so that it can be cured uniformly. It becomes possible, and it becomes economically advantageous. Furthermore, when the thickness of the surface protective layer after curing satisfies the above range, the three-dimensional formability of the decorative sheet is further improved, so that it has a high follow-up property for complicated three-dimensional shapes such as automobile interior applications. Can be obtained. As described above, the decorative sheet of the present invention requires a high film thickness especially for the surface protective layer because sufficiently high three-dimensional formability can be obtained even if the surface protective layer is made thicker than the conventional one. It is also useful as a decorative sheet for a member to be used, such as a vehicle exterior part.

(Formation of surface protective layer)
The surface protective layer is formed by preparing an ionizing radiation curable resin composition containing a matting agent and an ionizing radiation curable resin, applying it, and crosslinking and curing it. In addition, the viscosity of ionizing radiation curable resin composition should just be a viscosity which can form a non-hardened resin layer on the surface of a base material by the below-mentioned application system.

  In the present invention, the prepared coating solution is coated on the primer layer or a low-gloss pattern layer provided as necessary so as to have the above thickness, gravure coat, bar coat, roll coat, reverse roll coat, comma It coat | covers by well-known systems, such as a coat, Preferably gravure coat, and forms an uncured 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 a surface protective layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but usually includes an acceleration voltage of about 70 to 300 kV.

  In addition, in electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material layer, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material layer, and to minimize the deterioration of the base material due to the excess electron beam.

  The irradiation dose is preferably such that the crosslink density of the resin layer 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).

  Furthermore, there is no restriction | limiting in particular as an electron beam source, For example, various electron beam accelerators, such as a cock loft Walton type, a van de Graft type, a resonance transformer type, an insulated core transformer type, or a linear type, a dynamitron type, a high frequency type, etc. Can be used.

  When ultraviolet rays are used as the ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet ray 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 thus formed, a hard coat function, an antifogging coat function, an antifouling coating function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared ray You may perform the process which provides functions, such as a shielding coat function.

[Adhesive layer]
The adhesive layer is provided on the back surface (the surface opposite to the surface protective layer) of the base material layer as necessary for the purpose of enhancing the adhesion with the injection resin when molding a decorative resin product. Is a layer.

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

  Examples of the thermoplastic resin used for forming the adhesive layer include an acrylic resin, an acrylic-modified polyolefin resin, a chlorinated polyolefin resin, a vinyl chloride / vinyl acetate copolymer, a thermoplastic urethane resin, a thermoplastic polyester resin, and a polyamide resin. And rubber resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as a thermosetting resin used for formation of a contact bonding layer, a urethane resin, an epoxy resin, etc. are mentioned, for example. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

2. Decorative resin molded product The decorated resin molded product of the present invention is formed by integrating an injection resin with the decorative sheet of the present invention. That is, the decorative resin molded product of the present invention has at least an injection resin layer, a base material layer, a primer layer, and a surface protective layer in this order, and the surface protective layer includes a matting agent and an ionizing radiation curable resin. It is formed from the hardened | cured material of the ionizing radiation curable resin composition containing this, and the primer layer contains the synthetic resin particle, It is characterized by the above-mentioned.

  More specifically, the decorative resin molded product of the present invention uses the decorative sheet of the present invention, and various types of injection molding such as insert molding, simultaneous injection molding, blow molding, and gas injection molding. It is produced by the method. Among these injection molding methods, an insert molding method and an injection molding simultaneous decorating method are preferable.

  In the insert molding method, first, in the vacuum forming process, the decorative sheet of the present invention is vacuum formed (off-line pre-molding) into a molded product surface shape in advance by a vacuum forming die, and then an extra portion is trimmed as necessary. A molded sheet is obtained. This molded sheet is inserted into an injection mold, the injection mold is clamped, the resin in a fluid state is injected into the mold and solidified, and the decorative sheet is integrated on the outer surface of the resin molding simultaneously with the injection molding. By decorating, 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 by a vacuum forming die
Trimming excess portions of the vacuum-decorated decorative sheet to obtain a molded sheet, and inserting the molded sheet obtained in the above process into an injection mold, closing the injection mold, and molding the fluid resin The process of injecting the resin and the molded sheet.

  In addition, in the simultaneous injection molding decoration method, the decorative sheet of the present invention is placed in a female mold that also serves as a vacuum forming mold provided with a suction hole for injection molding, and preliminary molding (in-line preliminary molding) is performed with this female mold. After performing, the injection mold is clamped, the resin in a fluid state is injected into the mold, solidified, and the decorative sheet of the present invention is integrated on the outer surface of the resin molding simultaneously with the injection molding Thus, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is manufactured by the simultaneous injection molding method including the following steps.
After the decorative sheet of the present invention is installed so that the base material of the decorative sheet faces the molding surface of the movable mold having a molding surface of a predetermined shape, the decorative sheet is heated and softened. And vacuum suction from the movable mold side, the step of preforming the decorative sheet by adhering the softened decorative sheet along the molding surface of the movable mold,
After clamping the movable mold and the fixed mold having the decorative sheet adhered along the molding surface, the resin molding material in a fluid state is injected and filled into the cavity formed by both molds. An injection molding process in which the formed resin molded body and the decorative sheet are laminated and integrated by solidification, and a movable molded mold is separated from the fixed mold, and the entire decorative sheet is laminated. The process of taking out.

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

  Examples of the thermoplastic resin used as the injection resin include polyolefin resins such as polyethylene and polypropylene, ABS resin, styrene resin, polycarbonate resin, acrylic resin, and vinyl chloride resin. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as a thermosetting resin used as injection resin, a urethane resin, an epoxy resin, etc. are mentioned, for example. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The decorative resin molded product of the present invention has a design that expresses a rich and low gloss feeling with a texture, can be molded into complex shapes, and has excellent scratch resistance. , For example, interior materials or exterior materials of vehicles such as automobiles; construction members such as baseboards and rims; fittings such as window frames and door frames; interior materials of buildings such as walls, floors, and ceilings; television receivers; It can be used as a casing or container for home appliances such as an air conditioner.

  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.

Example 1
A colored ABS resin film (thickness: 400 μm) was used as the base material layer. A woodgrain pattern layer (thickness: 5 μm) was formed on the base material layer by gravure printing using an ink composition containing an acrylic resin. On the pattern layer, a primer layer having the composition shown in Table 1 was printed so that the thickness after drying was 2 μm. Next, an ionizing radiation curable resin composition having the composition shown in Table 1 was applied on the primer layer so that the thickness after curing was 3 μm. The ionizing radiation curable resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface protective layer. Thus, a decorative sheet having a laminated structure in which the base layer / the pattern layer / the primer layer / the surface protective layer was laminated in order was obtained.

Examples 2-12, Comparative Examples 1 and 2
A colored ABS resin film (thickness: 400 μm) was used as the base material layer. A woodgrain pattern layer (thickness: 5 μm) was formed on the base material layer by gravure printing using an ink composition containing an acrylic resin. On the pattern layer, a primer layer having the composition shown in Table 1 was printed so that the thickness after drying was 2 μm. Next, on the primer layer, using ink containing 100 parts by mass of nitrocellulose resin and 100 parts by mass of silica (oil absorption 200 ml / 100 g, average particle size 5 μm) so as to synchronize with the conduit part of the grain of the pattern layer A low gloss pattern layer (thickness: 1.0 μm) was formed by gravure printing. From the low gloss pattern layer, an ionizing radiation curable resin composition having the composition shown in Table 1 was applied so that the thickness after curing was 3 μm. The ionizing radiation curable resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface protective layer. Thus, a decorative sheet having a laminated structure in which a base material layer / picture layer / primer layer / low gloss pattern layer / surface protective layer were laminated in order was obtained.

Examples 13 and 14
As the transparent resin layer, a transparent acrylic film (thickness: 100 μm) was used in Example 13, and a transparent polyethylene terephthalate film (thickness: 100 μm) whose both surfaces were corona-treated was used in Example 14. A woodgrain pattern layer (thickness: 5 μm) was formed on one surface of the transparent resin layer by gravure printing using an ink composition containing an acrylic resin. Next, a primer layer (thickness 2 μm) having the composition shown in Table 1 was applied by gravure reverse on the surface of the transparent resin layer on the side where no pattern layer was formed. Furthermore, using the ink containing 100 parts by mass of nitrocellulose resin and 100 parts by mass of silica (oil absorption 200 ml / 100 g, average particle size 5 μm) on the primer layer, it is synchronized with the conduit part of the grain of the pattern layer. A low gloss pattern layer (thickness: 1.0 μm) was formed by gravure printing. From the low gloss pattern layer, an ionizing radiation curable resin composition having the composition shown in Table 1 was applied so that the thickness after curing was 3 μm. The ionizing radiation curable resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface protective layer. Next, an adhesive made of polyester resin is applied on the pattern layer laminated on the transparent resin layer by gravure reverse so as to have a thickness of 10 μm, and a colored ABS resin film (thickness of 350 μm is used as a base layer) ) Was laminated by dry lamination. Thus, a decorative sheet having a laminated structure in which the base layer / adhesive layer / design layer / transparent resin layer / primer layer / low gloss pattern layer / surface protective layer was laminated in order was obtained.

Comparative Example 3
A colored ABS resin film (thickness: 400 μm) was used as the base material layer. A woodgrain pattern layer (thickness: 5 μm) was formed on the base material layer by gravure printing using an ink composition containing an acrylic resin. Using an ink containing 100 parts by mass of nitrocellulose resin and 100 parts by mass of silica (oil absorption 200 ml / 100 g, average particle size 5 μm) on the pattern layer, the gloss is low-gloss so as to synchronize with the conduit part of the grain of the pattern layer A pattern layer (thickness: 1.0 μm) was formed by gravure printing. From the low gloss pattern layer, an ionizing radiation curable resin composition having the composition shown in Table 1 was applied so that the thickness after curing was 3 μm. The ionizing radiation curable resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface protective layer. Thus, a decorative sheet having a laminated structure in which a base material layer / picture layer / low gloss pattern layer / surface protective layer were laminated in order was obtained.

Performance evaluation of each decorative sheet The decorative sheet obtained in each Example and Comparative Example was evaluated for three-dimensional formability, scratch resistance, and low gloss effect by the following methods.

<Evaluation of three-dimensional formability>
Each decorative sheet was heated to 160 ° C. with an infrared heater and softened. Next, vacuum forming was performed using a vacuum forming die (maximum draw ratio: 150%) to form the internal shape of the die. After the molded decorative sheet was cooled, it was released from the mold, and the three-dimensional formability was evaluated according to the following criteria.
(Three-dimensional formability criteria)
A: No cracking or whitening was observed in the surface protective layer, and the shape of the mold was satisfactorily followed.
○: Although a fine coating crack or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion, there was no practical problem.
(Triangle | delta): Although only the largest extending | stretching part had a coating-film crack and whitening were seen in the surface protective layer, the other part was favorable and there was no problem practically.
X: Remarkable coating film cracking or whitening of the surface protective layer was observed in the three-dimensional shape portion or the maximum stretched portion.
Xx: The coating film crack and whitening were observed in the surface protective layer without being able to follow the shape of the mold.

<Scratch resistance>
Each decorative sheet was scratched 20 times with a nail, the appearance of each decorative sheet was measured, and scratch resistance was evaluated according to the following criteria.
(Criteria for scratch resistance)
A: There was no damage.
○: Although fine scratches were observed on the surface, the coating film was not scraped or whitened.
Δ: Scratches were observed on the surface, and glossiness of the damaged portions was observed.
X: Scratches were observed on the surface, and a slight scraped mark remained on the coating film.
XX: The surface was markedly scratched and the coating film was scraped.

<Low gloss effect>
About the non-conduit part of the grain pattern of each decorating sheet, the 60 degree gloss value was measured using a gloss meter in accordance with JIS K 7105.

<Evaluation results>
The results are shown in Table 1. From this result, in the decorative sheet in which the base material layer, the primer layer, and the surface protective layer are sequentially laminated, when the synthetic resin particles are blended in the primer layer and the matting agent is blended in the surface protective layer (implementation) Examples 1 to 14) had a design property in which a 60 ° gloss value was low and a rich low gloss feeling with a texture was expressed. In the decorative sheets of Examples 1 to 14, the three-dimensional formability also satisfied a practical level, and the scratch resistance was also good. On the other hand, when the matting agent is not blended in the primer layer and the matting agent is blended only in the surface protective layer (Comparative Examples 1 and 3), the 60 ° gloss value is high and sufficiently low gloss is felt. Could not be expressed. Moreover, in the decorative sheet of Comparative Example 3, the three-dimensional formability was insufficient. Further, when silica particles, which are matting agents for inorganic particles, are blended in the primer layer, and matting agents are blended in the surface protective layer (Comparative Example 2), the three-dimensional formability is poor and can be put to practical use. There wasn't.

[Footnotes in Table 1]
Surface protective layer The surface protective layer was formed using an ionizing radiation curable resin composition in which a matting agent was added to EB1 to EB1 shown below.
(EB1)
Bifunctional polycarbonate acrylate (weight average molecular weight; 10,000): 94 parts by mass Hexafunctional urethane acrylate oligomer (weight average molecular weight; 6,000): 6 parts by mass Polyolefin wax: 6 parts by mass Matting agent: Predetermined amount shown in Table 1 (EB2)
Bifunctional polycarbonate acrylate (weight average molecular weight; 10,000): 100 parts by mass polyolefin wax: 6 parts by mass matting agent: predetermined amount shown in Table 1 (EB3)
Trifunctional acrylic silicone acrylate (weight average molecular weight; 20,000): 70 parts by mass Hexafunctional urethane acrylate oligomer (weight average molecular weight; 5,000): 30 parts by mass Polyolefin wax: 6 parts by mass Matting agent: Predetermined amounts shown in Table 1 The abbreviations of the matting agent added to the surface protective layer are as follows.
Urethane: Urethane resin beads (specific gravity 1.1-1.2g / cm ³ , glass transition point -20-30 ° C)
Silicone: Silicone beads Silica: Silica particles (no surface treatment)
In Table 1, the addition amount of the matting agent in the surface protective layer is a ratio (part by mass) to 100 parts by mass of the ionizing radiation curable resin in the ionizing radiation curable resin composition.

Primer layer The primer layer is a mixture of a binder resin in which acrylic polyol and hexamethylene diisocyanate are mixed so that the equivalent ratio of the hydroxyl group of acrylic polyol and hexamethylene diisocyanate is 1: 1, and the matting agent shown in Table 1. The primer composition was used.
In Table 1, the addition amount of the matting agent in the primer layer is a ratio (parts by mass) to 100 parts by mass of the binder resin (total amount of acrylic polyol and hexamethylene diisocyanate).
In Table 1, the abbreviations of the matting agent added to the primer layer are as follows.
Acrylic: Cross-linked acrylic beads Silicone: Silicone beads PP + PE wax :: A mixture of polypropylene wax and polyethylene wax (specific gravity 1.0-1.1 g / cm ³ , melting point 130-140 ° C.)
Silica: Silica particles (no surface treatment)

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Picture pattern layer 3 Primer layer 4 Low gloss pattern layer 5 Surface protective layer 6 Low gloss area 7 Transparent resin layer

Claims (12)

On the base material layer, it has at least a primer layer and a surface protective layer in order,
The surface protective layer is formed from a cured product of an ionizing radiation curable resin composition containing a matting agent and an ionizing radiation curable resin, and the primer layer is a synthetic having an average particle size of 0.1 to 3 μm. Contains resin particles,
A decorative sheet for three-dimensional molding, characterized in that.   The decorative sheet according to claim 1, wherein the ionizing radiation curable resin is polycarbonate (meth) acrylate and / or acrylic silicone (meth) acrylate.   The decorative sheet according to claim 1, wherein a pattern layer is provided between the base material layer and the primer layer.   The decorative sheet according to any one of claims 1 to 3, wherein a low-gloss pattern layer that expresses a low-gloss region by an interaction with the surface protective layer is provided between the primer layer and the surface protective layer.   The decorative sheet according to any one of claims 1 to 4, wherein a transparent resin layer is provided between the base material layer and the primer layer.   The decorative sheet according to any one of claims 1 to 5, wherein the synthetic resin particles are at least one selected from the group consisting of acrylic beads, urethane beads, silicone beads, silicone rubber beads, and polyolefin waxes.   The decorative sheet according to any one of claims 1 to 6, wherein the matting agent is at least one selected from the group consisting of acrylic beads, silicone rubber beads, and urethane beads.   The decorative sheet according to any one of claims 1 to 7, wherein the matting agent has an average particle size of 0.1 to 25 µm.   The decorating sheet according to any one of claims 1 to 8, wherein the content of the matting agent in the surface protective layer is 1 to 70 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. It has at least an injection resin layer, a base material layer, a primer layer, and a surface protective layer in order,
The surface protective layer is formed from a cured product of an ionizing radiation curable resin composition containing a matting agent and an ionizing radiation curable resin, and the primer layer is a synthetic having an average particle size of 0.1 to 3 μm. Contains resin particles,
This is a decorative resin molded product. A method for producing a decorative resin molded product including the following steps:
A vacuum forming step in which the decorative sheet according to any one of claims 1 to 9 is previously formed into a three-dimensional shape by a vacuum forming die,
Trimming excess portions of the vacuum-decorated decorative sheet to obtain a molded sheet, and inserting the molded sheet obtained in the above process into an injection mold, closing the injection mold, and molding the fluid resin The process of injecting the resin and the molded sheet. A method for producing a decorative resin molded product including the following steps:
After installing the decorating sheet according to any one of claims 1 to 9 so that the base material of the decorating sheet faces the molding surface of the movable mold having a molding surface of a predetermined shape, The process of pre-molding the decorative sheet by heating and softening the decorative sheet, and vacuum-sucking the decorative sheet from the movable mold side to bring the softened decorative sheet into close contact with the molding surface of the movable mold ,
After clamping the movable mold and the fixed mold having the decorative sheet adhered along the molding surface, the resin molding material in a fluid state is injected and filled into the cavity formed by both molds. An injection molding process in which the formed resin molded body and the decorative sheet are laminated and integrated by solidification, and a movable molded mold is separated from the fixed mold, and the entire decorative sheet is laminated. The process of taking out.