JP2018058222A - Decorative sheet, decorative resin molding, and methods for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of suitably imparting an excellent design to a decorative resin molding.SOLUTION: The decorative sheet includes at least a substrate layer 1 and a surface protective layer 2 formed of a cured product of an ionizing radiation-curable resin composition. A first surface 2a on the substrate layer side of the surface protective layer 2 is provided with a first uneven shape 11. A second surface 2b opposite to the first surface 2a of the surface protective layer 2 is provided with a second uneven shape 12. The first uneven shape 11 and the second uneven shape 12 are different from each other.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet, a decorative resin molded product, and a method for producing them.

  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. As a molding method of such a decorative resin molded product, the decorative sheet is formed into a three-dimensional shape in advance by a vacuum mold, the molded sheet is inserted into an injection mold, and the resin in a fluid state is placed in the mold. An insert molding method in which a resin and a molded sheet are integrated by injection (see, for example, Patent Document 1), a decorative sheet inserted into a mold at the time of injection molding, and a molten resin injected and injected into a cavity An injection molding simultaneous decorating method (see, for example, Patent Document 2 and Patent Document 3) that integrates and decorates the surface of a resin molded body is known.

  Conventionally, a technique for improving the texture of a decorative sheet by providing a concave-convex shape on the surface of the decorative sheet is known. As a method of providing a concavo-convex shape on the surface of the decorative sheet, for example, a colored layer is provided on a transparent resin film, and embossing is performed thereon, thereby providing a concavo-convex shape in which the colored layer protrudes toward the transparent resin film. The method is known.

  In recent years, with the diversification of consumer needs, decorative resin molded products having various designs have been demanded. In order to follow such diversifying consumer needs, there is a demand for the development of a decorative resin molded product having not only an appearance design feeling based on the uneven shape of the surface but also a touch feeling.

JP 2004-322501 A Japanese Patent Publication No. 50-19132 Japanese Examined Patent Publication No. 61-17255

  In recent years, there has been a demand for the development of decorative resin molded products that have not only the appearance of a design based on the uneven shape of the surface, but also the feel of touch, and various decorative sheets have been proposed. There are restrictions on the design that can be imparted to a decorative resin molded product, such as a sheet that can only express a design that matches the appearance and feel of the hand.

  Moreover, the uneven | corrugated shape of a decorating sheet is easy to deform | transform or lose | disappear with the heat and pressure at the time of shaping | molding, and the design feeling and touch feeling which were excellent by the uneven | corrugated shape may be unable to be provided with respect to a decorative resin molded product.

  Under such circumstances, an object of the present invention is to provide a decorative sheet capable of suitably imparting an excellent design to a decorative resin molded product, for example, the design feeling and the touch feeling are different. And Furthermore, this invention also makes it the objective to provide the manufacturing method of the said decorating sheet, the decorative resin molded product using the said decorating sheet, and its manufacturing method.

  The present inventors have intensively studied to solve the above problems. As a result, it is a decorative sheet comprising at least a base material layer and a surface protective layer made of a cured product of an ionizing radiation curable resin composition, and on the first surface of the surface protective layer on the base material layer side, A first concavo-convex shape is provided, and a second concavo-convex shape is provided on the second surface opposite to the first surface of the surface protective layer, and the first concavo-convex shape and the second shape are different from each other. It has been found that an excellent design can be suitably imparted to a decorative resin molded product, for example, such that the design feeling and the touch feeling are different from each other, for example. 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. At least a decorative sheet comprising a base material layer and a surface protective layer made of a cured product of an ionizing radiation curable resin composition,
A first concavo-convex shape is provided on the first surface of the surface protective layer on the base material layer side,
A second concavo-convex shape is provided on the second surface opposite to the first surface of the surface protective layer,
The decorative sheet in which the first uneven shape and the second shape are different from each other.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the surface protective layer is a single layer or a multilayer.
Item 3. Item 3. The decorative sheet according to item 1 or 2, wherein a peelable film layer is provided on the second surface of the surface protective layer.
Item 4. A decorative layer is provided between the base material layer and the surface protective layer,
Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the decorative layer is provided along the first uneven shape.
Item 5. A primer layer is provided directly under the surface protective layer,
The said primer layer is a decorating sheet in any one of claim | item 1 -4 provided along the said 1st uneven | corrugated shape.
Item 6. Forming a first concavo-convex shape on the surface of the base material layer;
Applying an ionizing radiation curable resin composition to the surface side where the first concavo-convex shape of the base material layer is formed and curing to form a surface protective layer;
Forming a second concavo-convex shape different from the first concavo-convex shape on the surface of the surface protective layer opposite to the base material layer;
A method for producing a decorative sheet.
Item 7. At least a decorative resin molded product comprising a molded resin layer, a base material layer, and a surface protective layer made of a cured product of an ionizing radiation curable resin composition,
A first concavo-convex shape is provided on the first surface of the surface protective layer on the base material layer side,
A second concavo-convex shape is provided on the second surface opposite to the first surface of the surface protective layer,
A decorative resin molded product in which the first uneven shape and the second shape are different from each other.
Item 8. The manufacturing method of a decorative resin molded product provided with the process of laminating | stacking a molded resin layer by injecting resin to the said base material layer side of the decorating sheet in any one of claim | items 1-6.

  ADVANTAGE OF THE INVENTION According to this invention, the decorating sheet which can provide the outstanding design suitably to a decorating resin molded product can be provided. Moreover, according to this invention, the manufacturing method of the said decorating sheet, the decorating resin molded product using the said decorating sheet, and its manufacturing method can also be provided.

It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the present invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the present invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the present invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded product of the present invention.

1. The decorative sheet of the present invention is a decorative sheet comprising at least a base material layer and a surface protective layer made of a cured product of an ionizing radiation curable resin composition, the base material layer of the surface protective layer The first concavo-convex shape is provided on the first surface on the side, and the second concavo-convex shape is provided on the second surface opposite to the first surface of the surface protective layer. And the second shape are different from each other. By providing such a specific configuration, the decorative sheet of the present invention can suitably impart an excellent design to the decorative resin molded product, for example, the design feeling and the touch feeling are different. It is possible.

  Hereinafter, the decorative sheet of the present invention will be described in detail. In the present specification, the numerical range indicated by “to” means “above” or “below”, except for the portions specified as “above” or “below”. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, in this specification, “(meth) acrylate” means “acrylate or methacrylate”, and other similar things have the same meaning.

As shown in FIGS. 1 to 3, the decorative sheet of the present invention has a laminated structure in which at least a base material layer 1 and a surface protective layer 2 are laminated. As will be described later, the surface protective layer 2 is composed of a cured product of an ionizing radiation curable resin composition.

  In the decorative sheet of the present invention, a decorative layer 3 may be provided between the base material layer 1 and the surface protective layer 2 as necessary for the purpose of enhancing the appearance of the design. Moreover, you may provide the primer layer 4 directly under the surface protective layer 2 as needed, for the purpose of improving the adhesiveness of the surface protective layer 2 and the layer located under it. As will be described later, the decorative layer 3 and the primer layer 4 are respectively provided along the first concavo-convex shape 11 provided on the first surface 2a of the surface protective layer 2 on the base material layer 1 side.

  As shown in FIG. 2, in the decorative sheet of the present invention, the surface protective layer 2 may be a multilayer. FIG. 2 shows an example in which the surface protective layer 2 has a two-layer structure of a first surface protective layer 21 constituting the first surface 2a and a second surface protective layer 22 constituting the second surface 2b. Is shown.

  Furthermore, as shown in FIG. 3, the decorative sheet of the present invention is necessary for the purpose of protecting the uneven shape (particularly, the second uneven shape) of the surface protective layer 2 during injection molding or the like. Accordingly, a peelable film layer 5 may be provided on the second surface 2 b of the surface protective layer 2. Note that a release layer (not shown) may be provided between the surface protective layer 2 and the peelable film layer 5 for the purpose of enhancing the peelability between these layers.

  In addition, a concealing layer (not shown) is provided between the base material layer 1 and the surface protective layer 2 as needed for the purpose of suppressing color change and variation of the base material layer 1. Also good. If the primer layer 4 is provided, the concealing layer may be provided between the base material layer 1 and the primer layer 4, and if the decorative layer 3 is provided, the concealing layer is a base material layer. What is necessary is just to provide between 1 and the decoration layer 3. FIG.

  Furthermore, in the decorative sheet of the present invention, the back surface of the base material layer 1 (the surface opposite to the surface protective layer 2) is used for the purpose of enhancing the adhesion with the molding resin during the molding of the decorative resin molded product. ) May be provided with a back surface adhesive layer (not shown) as required.

  As an example of the laminated structure of the decorative sheet of the present invention, a laminated structure in which the substrate layer 1 / surface protective layer 2 is laminated; a laminated structure in which the substrate layer 1 / decorative layer 3 / surface protective layer 2 is laminated in order; Laminated structure in which base material layer 1 / primer layer 4 / surface protective layer 2 are laminated in order; Laminated structure in which base material layer 1 / decoration layer 3 / primer layer 4 / surface protective layer 2 are laminated in order; / Laminated structure in which surface protective layer 2 / film layer 5 are laminated in order; base material layer 1 / surface protective layer 2 / release layer / laminated structure in which film layer 5 is laminated in order; base material layer 1 / decoration layer 3 / Laminated structure in which surface protective layer 2 / film layer 5 are laminated in sequence; Base material layer 1 / decoration layer 3 / primer layer 4 / surface protective layer 2 / laminated structure in which film layer 5 is laminated in sequence; Laminated structure in which / decoration layer 3 / primer layer 4 / surface protective layer 2 / release layer / film layer 5 are laminated in order Such as a multilayer structure in which the base material layer 1 / decorative layer 3 / primer layer 4 / first surface protective layer 21 / a second surface protective layer 22 / the film layer 5 are laminated in this order and the like.

  FIG. 1 shows a cross-sectional view of a decorative sheet in which base layer 1 / decoration layer 3 / primer layer 4 / surface protective layer 2 are laminated as an embodiment of the laminated structure of the decorative sheet of the present invention. FIG. 2 shows a decorative structure in which a base layer 1 / decoration layer 3 / primer layer 4 / first surface protective layer 21 / second surface protective layer 22 are sequentially laminated as an embodiment of the laminated structure of the decorative sheet of the present invention. Sectional drawing of a sheet | seat is shown. In FIG. 3, as one aspect of the laminated structure of the decorative sheet of the present invention, base layer 1 / decoration layer 3 / primer layer 4 / first surface protective layer 21 / second surface protective layer 22 / film layer 5 are in this order. Sectional drawing of the laminated decorating sheet is shown.

Composition of each layer of the decorative sheet [base material layer 1]
The base material layer 1 is a resin sheet (resin film) that plays a role as a support in the decorative sheet of the present invention. The resin component used for the base material layer 1 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the molding resin, and the like. Preferably, a resin film made of a thermoplastic resin is used. Can be mentioned. Specifically, as the thermoplastic resin, acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”), acrylonitrile-styrene-acrylate resin (hereinafter referred to as “ASA resin”). And acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, vinyl chloride resins, and polyethylene terephthalate (PET). Among these, ABS resin and acrylic resin are preferable from the viewpoint of three-dimensional moldability. Moreover, the base material layer 1 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 kind | species resin.

  The bending elastic modulus of the base material layer 1 is not particularly limited. For example, when the decorative sheet of the present invention is integrated with a molding resin by an insert molding method, the flexural modulus at 25 ° C. of the base material layer 1 in the decorative sheet of the present invention is 500 to 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 even when subjected to the insert molding method, 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 1 is subjected to physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one side or both sides as necessary in order to improve adhesion with a layer provided thereon. May be. Examples of the oxidation method performed as the surface treatment of the base material layer 1 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 the base material layer 1, 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 1, and preferably a corona discharge treatment method from the viewpoints of effects and operability.

  The base material layer 1 may be subjected to a treatment such as forming a known adhesive layer.

  Furthermore, the base material layer 1 may be colored with a coloring agent or may not be colored. Moreover, the base material layer 1 may be any of colorless and transparent, colored and transparent, and translucent. Although it does not restrict | limit especially as a coloring agent used for the base material layer 1, Preferably the coloring agent which does not discolor also under the temperature conditions of 150 degreeC or more is mentioned, Specifically, the existing dry color, paste color, masterbatch resin Examples thereof include compositions.

  Although the thickness of the base material layer 1 is suitably set according to the use of the decorative sheet, the molding method to be integrated with the molding resin, etc., usually about 25 to 1000 μm and about 50 to 700 μm are mentioned. More specifically, if the decorative sheet of the present invention is used for the insert molding method, the thickness of the base material layer 1 is usually about 50 to 1000 μm, preferably about 100 to 700 μm, more preferably 100 to 500 μm. Degree. If the decorative sheet of the present invention is subjected to the simultaneous injection molding method, the thickness of the base material layer 1 is usually about 25 to 200 μm, preferably about 50 to 200 μm, more preferably about 70 to 200 μm. Is mentioned. In addition, the thickness of the base material layer 1 is the thickness in the position where the recessed part by the 1st uneven | corrugated shape 11 is not formed.

[Surface protective layer 2]
A surface protective layer is a layer provided in order to provide the design which was excellent in the decorative resin molded product by uneven | corrugated shape, protecting the surface of a decorative resin molded product. A first concavo-convex shape 11 is provided on the first surface 2 a of the surface protective layer 2 on the base material layer 1 side. Furthermore, a second concavo-convex shape 12 is provided on the second surface 2 b opposite to the first surface 2 a of the surface protective layer 2. In the present invention, the first uneven shape 11 and the second shape 12 are different from each other. More specifically, when the decorative sheet of the present invention is viewed in plan, the design expressed by the first uneven shape 11 and the design expressed by the second shape 12 are preferably different. Thereby, it can be set as the outstanding design, for example, the design feeling and the touch feeling by appearance differ. In addition, it can confirm from the cross-sectional shape of the thickness direction of a decorating sheet that the 1st uneven | corrugated shape 11 and the 2nd shape 11 mutually differ.

<Uneven shape>
The specific shapes of the first concavo-convex shape 11 and the second shape 12 are not particularly limited as long as they are different from each other, and may be appropriately set according to the design feeling to be imparted. Examples of the concavo-convex shape include a hairline pattern, a wood grain pattern, a geometric pattern (dots, stripes, woven fabric, carbon, etc.) and the like.

  In the decorative sheet of the present invention, the first concavo-convex shape 11 and the second shape 12 have, for example, the same pattern (for example, hairline pattern, wood grain pattern, geometric pattern (dot, stripe, woven fabric, carbon, etc.)). However, if the height of the convex portion, the width of the convex portion, the pitch between adjacent convex portions, the width of the concave portion, the depth of the concave portion, and the like are different, the shape becomes different and an excellent design can be exhibited.

  For example, from the viewpoint of suitably imparting a decorative resin molded product with a design having a different design and feel to the appearance, the first uneven shape 11 and the second shape 12 have the same pattern, and the convex portion It is preferable that any one of height, the width of a convex part, the pitch between adjacent convex parts, the width | variety of a recessed part, and the depth of a recessed part differs. From the viewpoint of more suitably applying the design, it is more preferable that the first uneven shape 11 and the second shape 12 represent different patterns.

  In the decorative sheet of the present invention, each of the first concavo-convex shape 11 and the second concavo-convex shape 12 is formed in at least a part of the region in order to exhibit excellent design properties due to the concavo-convex shape on the decorative sheet. That's fine. As will be described later, the first uneven shape 11 is formed by ionizing, for example, on the surface side of the base layer 1 where the first uneven shape 11 is formed after the first uneven shape 11 is formed on the surface of the base layer 1. The surface protective layer 2 can be formed by applying and curing a radiation curable resin composition. Therefore, when the base material layer 1 and the surface protective layer 2 are in contact with each other, the first uneven shape 11 is constituted by the interface between the base material layer 1 and the surface protective layer 2. On the other hand, after forming the first concavo-convex shape 11 on the surface of the base material layer 1, the decoration layer 3 and the primer layer 4 are provided on the surface side of the base material layer 1 on which the first concavo-convex shape 11 is formed. When the surface protective layer 2 is formed by applying and curing the radiation curable resin composition, the decorative layer 3 or primer is interposed between the base material layer 1 and the surface protective layer 2 in the first concavo-convex shape 11. Layer 4 is located.

  For example, as shown in FIGS. 2 and 3, the surface protective layer 2 may be composed of a plurality of layers. As described above, in FIG. 2, the surface protective layer 2 includes two layers of the first surface protective layer 21 constituting the first surface 2 a and the second surface protective layer 22 constituting the second surface 2 b. Although the example which is a structure is shown, it is good also as a structure of 3 or more layers in which another surface protective layer was further provided between the 1st surface protective layer 21 and the 2nd surface protective layer 22. FIG.

  The surface protective layer 2 is composed of a cured product of an ionizing radiation curable resin composition. That is, in the decorative sheet of the present invention, the first uneven shape 11 and the second uneven shape 12 are constituted by the surface protective layer 2 made of a cured product of the ionizing radiation curable resin composition. The change of the uneven shape due to the heat pressure is effectively suppressed, and an excellent design can be imparted to the decorative resin molded product. Hereinafter, the ionizing radiation curable resin used for forming the surface protective layer 2 will be described in detail. In addition, when the surface protective layer 2 is comprised by the multilayer, the ionizing radiation curable resin composition which comprises each layer may be the same, and may differ.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the surface protective layer 2 is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. And a mixture of at least one of prepolymers, oligomers, monomers, and the like, as appropriate. 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. Therefore, they are suitable for forming the surface protective layer 2. Used for.

  As the monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more 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 is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate. 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 a polyisocyanate compound with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or 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) 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.

  Among the ionizing radiation curable resins described above, polycarbonate (meth) acrylate is preferably used from the viewpoint of obtaining excellent three-dimensional formability. It is also preferable to use a combination of polycarbonate (meth) acrylate and urethane (meth) acrylate.

(Other additive ingredients)
Various additives can be blended in the surface protective layer 2 in accordance with desired physical properties to be provided in the surface protective layer 2. 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.

(Thickness of the surface protective layer 2)
The thickness of the surface protective layer 2 (the total thickness in the case of multiple layers) is preferably about 0.01 to 20 μm, more preferably about 0.01 to 15 μm, and still more preferably about 0.01 to 12 μm. . When the surface protective layer 2 is a multilayer, the thickness of each layer is preferably about 0.01 to 15 μm, more preferably about 0.01 to 12 μm, and still more preferably about 0.01 to 10 μm. . In the present invention, the thickness of the surface protective layer is such that the convex portions of the first concavo-convex shape 11 (portions not protruding toward the base material layer 1 side, the same applies hereinafter) and the concave portions of the second concavo-convex shape 12 (base material layer 1). The thickness of the portion located between the portion protruding to the side and the same applies hereinafter).

(Formation of surface protective layer 2)
The surface protective layer 2 is formed, for example, by preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, applying it, and crosslinking and curing it. In addition, the viscosity of an ionizing radiation curable resin composition should just be a viscosity which can form a non-hardened resin layer with the below-mentioned coating system.

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

  The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer to form the surface protective layer 2. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the 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 the electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface protective layer 2, the electron beam transmission depth and the surface protection are used. The acceleration voltage is selected so that the thicknesses of the layers 2 are substantially equal. Thereby, irradiation of the extra electron beam to the layer located under the surface protective layer 2 can be suppressed, and deterioration of each layer due to the excess electron beam can be minimized.

  The irradiation dose is preferably such that the crosslinking density of the surface protective layer 2 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, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type 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 2 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, You may perform the process which provides functions, such as an infrared shielding coat function.

[Decorative layer 3]
The decorative layer 3 is provided between the base material layer 1 and the surface protective layer 2 for the purpose of imparting a decorative property to the decorative sheet. When providing a layer, it is a layer provided as needed, such as between the concealing layer and the surface protective layer 2. The decorative layer 3 is provided along the first uneven shape 11 of the surface protective layer 2.

  For example, the decorative layer 3 can be a layer in which a desired pattern is formed using an ink composition. As the ink composition used for forming the decoration layer 3, 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 decorative layer 3 is also not particularly limited, but for example, a grain pattern, a texture pattern or a cloth-like pattern imitating the surface of a rock such as a grain pattern, a marble pattern (for example, travertine marble pattern) Examples include fabric patterns, tiled patterns, brickwork patterns, and the like, which may be a pattern such as a parquet or patchwork that is a combination of these, or may be a solid color (so-called solid solid). These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, but also by multicolor printing with special colors performed by preparing individual color plates constituting the pattern. Can be formed.

  Although the thickness in particular of a decoration layer is not restrict | limited, For example, 1-30 micrometers, Preferably it is 1-20 micrometers. In addition, the thickness of the decoration layer is a thickness at a position where the concave portion due to the first concavo-convex shape 11 is not formed in the base material layer 1.

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

  When the decoration layer 3 is a metal thin film layer, the thickness is not particularly limited, but the optical density (OD value) is preferably 0.6 to 1.8 from the viewpoint of improving the designability of the decorative sheet. Degree, more preferably about 0.8 to 1.4. In addition, the thickness of the metal thin film layer is a thickness at a position where the concave portion due to the first concavo-convex shape 11 is not formed in the base material layer 1.

[Primer layer 4]
The primer layer 4 is a layer provided directly under the surface protective layer 2 as necessary for the purpose of improving the adhesion between the surface protective layer 2 and the layer located therebelow. The primer layer 4 is provided along the first uneven shape 11 of the surface protective layer 2.

  Primer compositions constituting the primer layer 4 include urethane resin, (meth) acrylic resin, (meth) acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, chlorinated polypropylene. Those using chlorinated polyethylene as a binder resin are preferably used, and these resins can be used alone or in combination of two or more. Among these, urethane resin, (meth) acrylic resin, and (meth) acrylic-urethane copolymer resin are preferable.

  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. As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used. Examples of the isocyanate include 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, hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as are used. It is also possible to mix urethane resin and butyral resin.

  From the viewpoints of adhesion to the surface protective layer 2 after crosslinking, difficulty of interaction after laminating the surface protective layer 2, physical properties, and moldability, acrylic polyol or polyester polyol as a polyol and hexamethylene as a crosslinking agent A combination of diisocyanate and 4,4-diphenylmethane diisocyanate is preferable, and an acrylic polyol and hexamethylene diisocyanate are particularly preferably used in combination.

  (Meth) acrylic resins include (meth) acrylic acid ester homopolymers, copolymers of two or more different (meth) acrylic acid ester monomers, or (meth) acrylic acid esters and other monomers. Polymers, specifically, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate- (Meth) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene- (meth) methyl acrylate copolymer A (meth) acrylic resin made of a homopolymer or a copolymer containing a (meth) acrylic acid ester such as the above is preferably used.

  As the (meth) acryl-urethane copolymer resin, for example, an acrylic-urethane (polyester urethane) block copolymer resin is preferable. As the curing agent, the above-mentioned various isocyanates are used. The acrylic-urethane (polyester urethane) block copolymer resin adjusts the acrylic / urethane ratio (mass ratio) in the range of preferably 9/1 to 1/9, more preferably 8/2 to 2/8, if desired. It is preferable.

  Although it does not restrict | limit especially about the thickness of the primer layer 4, For example, it is about 0.5-20 micrometers, Preferably, 1-5 micrometers is mentioned. In addition, the thickness of a primer layer is a thickness in the position in which the recessed part by the 1st uneven | corrugated shape 11 is not formed in the base material layer 1. FIG.

  The primer layer 4 is a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, a solid coat with a silk screen, a wire bar coat, It is formed by a normal coating method such as flow coating, comma coating, flow coating, brush coating, spray coating, or 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.

[Peelable film layer 5]
In this invention, the film layer 5 is provided as needed in order to suppress the deformation | transformation and disappearance of the uneven | corrugated shape (especially 2nd uneven | corrugated shape 12) of the surface protective layer 2 at the time of vacuum forming and injection molding of a decorative sheet. Is a layer. The film layer 5 is provided on the surface of the surface protective layer 2 opposite to the base material layer 1 side. The film layer 5 is laminated so as to be peelable from the decorative sheet (surface protective layer 2), and is a layer that is peeled off from the decorative resin molded product after being integrally formed with the molding resin.

  The film layer 5 and the surface protective layer 2 may be directly laminated, or other layers may be laminated between these layers.

  When the surface protective layer 2 and the film layer 5 are directly laminated, it is preferable that the film layer 5 fills at least part of the concave portions of the second concavo-convex shape 12 of the surface protective layer 2. Since the film layer 5 fills the concave portions of the second uneven shape 12 of the surface protective layer 2, the protective function of the second uneven shape 12 of the surface protective layer 2 by the film layer 5 can be further enhanced.

  As a method for filling the concave portions of the second uneven shape 12 of the surface protective layer 2 with the film layer 5, for example, the film layer 5 is laminated so as to fill the concave portions of the second uneven shape 12 by extrusion molding or thermal lamination. A method is mentioned.

  In the decorative sheet of the present invention, the surface protective layer 2 is formed of a cured product of an ionizing radiation curable resin composition. For this reason, the deformation | transformation of the uneven | corrugated shape by the heating at the time of laminating | stacking the film layer 5 by heat lamination or extrusion molding is suppressed. Furthermore, in the decorative sheet of the present invention, when the film layer 5 is provided, since the second uneven shape 12 of the surface protective layer 2 is protected by the film layer 5, injection molding or preliminary molding (vacuum prior to that) It is particularly excellent in moldability during molding. Further, in order to sufficiently suppress the deformation of the concavo-convex shape and to improve the workability at the time of peeling, it is difficult to impair the moldability even when the thickness of the film layer 5 is increased. For this reason, the decorating sheet of this invention can be used conveniently also as a decorating sheet in which high three-dimensionality formation is calculated | required.

  From the viewpoint of adjusting the adhesive strength so that the film layer 5 and the surface protective layer 2 are in close contact with each other in the form of a decorative sheet and can be easily peeled after being integrally formed with the molding resin, the film layer 5 is formed by extrusion molding. It is preferable that they are laminated.

  The thermoplastic resin constituting the film layer 5 is not particularly limited, and acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”); acrylonitrile-styrene-acrylate resin; acrylic resin; polypropylene And polyolefin resins such as polyethylene; polycarbonate resins; vinyl chloride resins; polyester resins such as polyethylene terephthalate (PET) resins and polybutylene terephthalate (PBT) resins. One kind of thermoplastic resin may be contained alone, or two or more kinds may be contained.

  From the viewpoint of effectively improving the moldability of the decorative sheet and imparting excellent chemical resistance, wear resistance, and excellent design feeling based on the uneven shape to the decorative resin molded product, these Especially, it is preferable that the film layer 5 is comprised by polyolefin resin or polyester resin. As the polyester resin, it is preferable to use amorphous polyethylene terephthalate (PET). As non-crystalline PET, a resin generally known as A-PET or PET-G can be used.

  Although it does not restrict | limit especially as thickness of the film layer 5, Preferably it is about 5-300 micrometers, More preferably, about 5-100 micrometers is mentioned. The film layer 5 may consist of multiple layers. In addition, the thickness of the film layer 5 is a thickness at a position where the concave portion of the second uneven shape 12 of the surface protective layer 2 is not filled.

(Release layer)
The release layer is a layer provided as necessary for the purpose of improving the peelability between the film layer 5 and the surface protective layer 2. The release layer is also provided so as to be in contact with the surface protective layer 2.

  As a material for forming the release layer, any material that can be applied so as to fill the second uneven shape 12 of the surface protective layer 2 and can be peeled off from the surface of the surface protective layer 2 together with the film layer 5 can be used. Although not particularly limited, the release layer is preferably formed of a cured product of an ionizing radiation curable resin composition. This makes it possible to more effectively suppress deformation and disappearance of the uneven shape of the surface protective layer 2 during vacuum molding or injection molding, and to impart a superior design feeling to the decorative resin molded product.

<Ionizing radiation curable resin in release layer>
The types and preferred ones of the ionizing radiation curable resin used for forming the release layer are the same as those used for forming the surface protective layer 2. The ionizing radiation curable resin used for forming the release layer and the ionizing radiation curable resin used for forming the surface protective layer 2 may be of the same type or different types.

<Other additive components>
The ionizing radiation curable resin composition used for forming the release layer contains, in addition to the ionizing radiation curable resin, other resin components as necessary for improving the moldability. Also good. Examples of the resin component other than the ionizing radiation curable resin include acrylic resin; polyvinyl acetal (butyral resin) such as polyvinyl butyral; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; vinyl chloride resin; urethane resin; Polyolefin such as polypropylene, styrene resin such as polystyrene and α-methylstyrene, polyamide, polycarbonate, acetal resin such as polyoxymethylene, fluorine resin such as ethylene-4 fluoroethylene copolymer, polyimide, polylactic acid, polyvinyl Acetal resin; thermoplastic resin such as liquid crystalline polyester resin. These resin components may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition to the ionizing radiation curable resin composition, the release layer includes a silicone resin, a fluorine resin, an acrylic resin (for example, an acrylic-melamine resin), a polyester resin, a polyolefin resin, and a polystyrene resin. Resin, polyurethane resin, cellulose resin, vinyl chloride-vinyl acetate copolymer resin, thermoplastic resin such as nitrified cotton, copolymer of monomers forming the thermoplastic resin, or these resins (meth) What modified | denatured with acrylic acid or urethane can be formed using the resin composition which mixed single or multiple. Among these, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers that form these resins, and those obtained by urethane modification thereof are more preferable. More specifically, acrylic-melamine Resin, acrylic-melamine resin-containing composition, polyester resin and ethylene / acrylic acid copolymer modified with urethane, acrylic resin / styrene / acrylic copolymer And a resin composition mixed with the above emulsion. Among these, it is particularly preferable that the release layer is composed of an acrylic-melamine resin alone or a composition containing 50% by mass or more of the acrylic-melamine resin.

  Various additives can be blended with the resin composition forming the release layer in consideration of desired physical properties to be provided in the release 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.

  Although it does not restrict | limit especially as thickness of a mold release layer, Preferably it is about 1-40 micrometers, More preferably, about 5-15 micrometers is mentioned. In addition, the thickness of a mold release layer is a thickness in the position in which the recessed part by the 2nd uneven | corrugated shape 12 is not formed in the base material layer 1. FIG.

  The release layer can be formed by applying the above-described resin composition on the surface protective layer 2. Specifically, the resin composition may be applied to the surface of the surface protective layer 2 by a method such as gravure coating, bar coating, roll coating, reverse roll coating, or comma coating.

[Hidden layer]
For the purpose of suppressing the color change and variation of the base material layer 1, the concealing layer is provided between the base material layer 1 and the surface protective layer 2 and between the base material layer 1 and the primer layer 4 if a primer layer 4 is provided. It is a layer provided as needed between the base material layer 1 and the decoration layer 3 if the space or the decoration layer 3 is 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 decorative layer described above.

  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 thickness of the masking layer is a thickness at a position where the concave portion of the second concave-convex shape 12 of the surface protective layer 2 is not filled.

  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.

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

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

  Examples of the thermoplastic resin used for forming the back surface 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. Examples thereof include resins 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 back surface adhesive 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.

The decorative sheet manufacturing method The decorative sheet of the present invention can be manufactured, for example, by a method including the following steps 1 to 3.
Step 1: Forming the first uneven shape 11 on the surface of the base material layer 1 Step 2: Applying the ionizing radiation curable resin composition to the surface side of the base material layer 1 where the first uneven shape 11 is formed, Step 3 of forming the surface protective layer 2 by curing: Step of forming a second concavo-convex shape 12 different from the first concavo-convex shape 11 on the surface of the surface protective layer 2 opposite to the base material layer 1.

  According to the method for producing a decorative sheet of the present invention, when the surface protective layer 2 is formed of a cured product of an ionizing radiation curable resin composition, the second uneven shape 12 is formed by embossing, for example. Since it is suppressed that the 1st uneven | corrugated shape 11 lose | disappears by the heat and pressure of this, it becomes easy to visually recognize the 1st uneven | corrugated shape 11 in the obtained decorating sheet.

  In the method for producing a decorative sheet of the present invention, details of the base material layer 1, the surface protective layer 2, the first uneven shape 11, and the second uneven shape 12 are as described above.

  In step 1, before providing the first uneven shape 11 on the surface of the base material layer 1, the decorative layer 3, the primer layer 4 and the like are laminated as necessary, and then the first surface is formed on the surface of the base material layer 1. The uneven shape 11 may be formed. When laminating the decorative layer 3, the primer layer 4, etc., the first uneven shape 11 can be formed on the surface of the base material layer 1 by embossing from the side where these layers are laminated, And the decoration layer 3 and the primer layer 4 along the 1st uneven | corrugated shape 11 can be formed.

  Further, in step 1, before laminating the above-described decoration layer 3, primer layer 4 and the like, the first concavo-convex shape 11 is provided on the surface of the base layer 1, and thereafter, the above-described decoration layer 3, primer layer 4 and the like are provided. May be laminated. Also in this case, the first concavo-convex shape 11 can be formed on the surface of the base material layer 1 by laminating the decoration layer 3 and the primer layer 4 so that all the concave portions of the first concavo-convex shape 11 are not filled. The decorative layer 3 and the primer layer 4 can be formed along the first concavo-convex shape 11.

  Moreover, although it does not restrict | limit especially as the method of providing the 1st uneven | corrugated shape 11 and the 2nd uneven | corrugated shape 12 in the process 2 and the process 3, Preferably, an embossing is mentioned, respectively. Embossing is a well-known method, after heating and softening the surface of the embossing object, pressurizing with the embossing plate, shaping the uneven shape formed on the embossing plate on the surface of the embossing object, It is a method of cooling and fixing. For embossing, a known single-wafer or rotary embossing machine can be used. By using an embossed plate corresponding to the first uneven shape 11 and the second uneven shape 12, the first uneven shape 11 and the second uneven shape 12 can be formed.

Furthermore, when the peelable film layer 5 is formed on the decorative sheet of the present invention, the following process is provided after the process 3.
The process of forming the peelable film layer 5 on the 2nd uneven | corrugated shape 12 of the surface protection layer 2 of the laminated body obtained at the process 3. FIG.

  The details of the peelable film layer 5 are as described above.

2. Decorated resin molded product The decorated resin molded product of the present invention is formed by integrating a molded resin with the decorated sheet of the present invention. That is, the decorative resin molded product of the present invention is a decorative resin molded product comprising at least a base material layer 1 and a surface protective layer 2 made of a cured product of an ionizing radiation curable resin composition, The first surface 2a on the base material layer 1 side of the layer 2 is provided with a first uneven shape 11, and the second surface 2b opposite to the first surface 2a of the surface protective layer 2 has a second surface 2b. An uneven shape 12 is provided, and the first uneven shape 11 and the second shape 12 are different from each other. In FIG. 4, about the one aspect | mode of the decorative resin molded product of this invention, the cross-sectional structure is shown. FIG. 4 is a schematic cross-sectional view of a decorative resin molded product in which the decorative sheet having the laminated configuration shown in FIG. 1 and the molded resin layer 6 are integrated.

  The decorative resin molded product of the present invention can be produced by a method including a step of forming a molded resin layer by injecting a resin on the base material layer side of the decorative sheet of the present invention. Specifically, the decorative sheet of the present invention is used to produce various injection molding methods such as insert molding, simultaneous injection molding, blow molding, and gas injection molding.

  When the decorative sheet of the present invention is provided with a film layer, the decorative sheet of the present invention is subjected to various injection molding methods to produce a decorative resin molded product with a film layer. It is possible to suitably exhibit the effect of suppressing damage to the surface. A suitable example of the molded resin layer 6 constituting the decorative resin molded product of the present invention is an injection resin layer formed by injection molding. Among these injection molding methods, an insert molding method and an injection molding simultaneous decorating method are preferable. That is, the decorating sheet of the present invention is suitably used for the insert molding method or the injection molding simultaneous decorating method.

  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, a resin in a fluid state is injected into the mold and solidified, and at the same time as the injection molding, a decorative sheet is formed on the outer surface of the resin molded product. A decorative resin molded product is manufactured by integrating the material layer 1 side.

  More specifically, the decorative resin molded product (or the decorative resin molded product with a film layer) 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 the vacuum forming step in the insert molding method, the decorative sheet may be heated and molded. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, for example, when an ABS resin film is used as the base material layer. For example, the temperature is usually about 100 to 250 ° C, preferably about 130 to 200 ° C. Moreover, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but is usually about 180 to 320 ° C, preferably about 220 to 280 ° C.

  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 the injection mold is clamped, the resin in a fluid state is injected and filled into the mold and solidified, and the base material layer of the decorative sheet of the present invention is formed on the outer surface of the resin molding simultaneously with the injection molding A decorative resin molded product is manufactured by integrating the one side.

  More specifically, the decorative resin molded product (or the decorative resin molded product with a film layer) of the present invention is manufactured by an injection molding simultaneous decorating 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 preforming step of the simultaneous injection molding method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, etc. If a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can usually be about 70 to 130 ° C. In the injection molding process, the temperature of the resin in the fluidized state is not particularly limited, but is usually about 180 to 320 ° C, preferably about 220 to 280 ° C.

  In addition, the decorative resin molded product of the present invention can be obtained by a decorative method of sticking the decorative sheet of the present invention on a three-dimensional resin molded body (molded resin layer) prepared in advance, such as a vacuum pressure bonding method. Can also be made.

  In the vacuum bonding method, first, the decorative sheet and the resin molded body of the first pressure chamber located on the upper side and the second vacuum chamber located on the lower side in the vacuum pressure bonding machine, the decorative sheet is the first. The vacuum chamber side is placed in a vacuum press so that the resin molded body is on the second vacuum chamber side, and the base material layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state. To do. The resin molding is installed on a lifting platform that is provided on the second vacuum chamber side and can be moved up and down. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using an elevator, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Adhere to the surface. Finally, the two vacuum chambers are opened to the atmospheric pressure, and the decorative resin molded product of the present invention can be obtained by trimming the excess portion of the decorative sheet as necessary.

  In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve the formability before the step of pressing the molded body against the decorative sheet. The vacuum pressure bonding method provided with the said process may be especially called a vacuum thermocompression bonding method. Although the heating temperature in the said process should just be suitably selected with the kind of resin which comprises a decorating sheet, the thickness of a decorating sheet, etc., if it is a case where a polyester resin film or an acrylic resin film is used as a base material layer Usually, it can be about 60-200 degreeC.

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

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

  Examples of the thermosetting resin used as the molding resin include urethane resins and epoxy resins. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  When the decorative sheet of the present invention includes a film layer, the decorative resin molded product can be obtained by peeling and removing the film layer from the decorative resin molded product with a film layer of the present invention. In addition, in the decorative resin molded product with a film layer, the film layer plays a role as a protective sheet for the decorative resin molded product, so it is stored as it is without being peeled after production, and the film layer is peeled off at the time of use. Also good. By using in such a mode, it is possible to prevent the decorative resin molded product from being damaged due to rubbing during transportation.

  Since the decorative resin molded product of the present invention has an excellent design, for example, an interior material or exterior material of a vehicle such as an automobile; a construction member such as a baseboard or a rim; a window frame, a door frame, etc. Joinery; interior materials for buildings such as walls, floors, ceilings; housings for home appliances such as television receivers and air conditioners; containers and the like.

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

[Example 1]
An ABS resin film (thickness 400 μm) was used as the base material layer. On the base material layer, an ink composition containing an acrylic resin was used to form a woodgrain decorative layer (thickness 5 μm) by gravure printing. A resin composition for a primer layer comprising a binder resin composed of a two-part curable resin containing 100 parts by mass of a main agent (acrylic polyol / urethane, mass ratio 9/1) and 7 parts by mass of a curing agent (hexamethylene diisocyanate) on a decorative layer. The product was applied and dried to form a primer layer having a thickness of 2 μm, and a laminate in which the base layer / decoration layer / primer layer was laminated in order was obtained. Next, embossing was performed on the primer layer using an embossed plate having a plate depth of 20 μm (provided with an uneven shape on which a carbon mesh pattern is formed) to form a first uneven shape. Next, an electron beam curable resin composition having the following composition is applied by bar coating so that the thickness after curing is 10 μm from above the first uneven shape, and the electron beam curable resin composition is used. An uncured resin layer filling the first uneven shape was formed. This uncured resin layer was irradiated with an electron beam having an acceleration voltage of 165 kV and a radiation dose of 50 kGy (5 Mrad) to provide a surface protective layer. Furthermore, embossing is performed from above the surface protective layer using an embossed plate having a plate depth of 20 μm (having an uneven shape on which a hairline pattern is formed) to form a second uneven shape of the surface protective layer, A decorative sheet having a laminated structure as shown in FIG. 1 was obtained.

(Ionizing radiation curable resin composition)
Trifunctional pentaerythritol acrylate (molecular weight 300): 30 parts by mass Acrylic polymer (weight average molecular weight 120,000): 70 parts by mass

[Example 2]
In Example 1, after forming the 2nd uneven | corrugated shape of a surface protective layer (here 1st surface protective layer), the thickness after hardening becomes 10 micrometers in the electron beam curable resin composition which has the following composition. As in Example 1, except that the uncured resin layer was coated with a bar coat and irradiated with an electron beam with an acceleration voltage of 165 kV and a radiation dose of 50 kGy (5 Mrad) to provide a second surface protective layer. Thus, a decorative sheet having a laminated structure as shown in FIG. 2 was obtained.

[Example 3]
In the same manner as in Example 2, a laminate as shown in FIG. 2 was formed, and then a peelable film layer was formed by laminating a polyethylene film (thickness 40 μm) on the second surface protective layer by extrusion. And a decorative sheet having a laminated structure as shown in FIG. 3 was obtained.

[Comparative Example 1]
A decorative sheet was obtained in the same manner as in Example 2 except that the first surface protective layer was not provided.

<Vacuum molding of decorative sheets and production of decorative resin molded products>
Each decorative sheet obtained above was heated with an infrared heater and softened until the sheet temperature reached 160 ° C. Subsequently, vacuum forming was performed using a vacuum forming die (maximum draw ratio: 100%) to form the inner shape of the mold. The decorative sheet after vacuum forming was cooled and then released from the mold. Next, the vacuum-decorated decorative sheet is placed in a mold, the injection resin is injected into the mold cavity, the decorative sheet and the injection resin are integrally molded, and the decorative resin is removed from the mold at the same time. A molded product was obtained.

<Evaluation of design feeling and feel by uneven shape>
Each decorative sheet obtained above, each decorative sheet obtained by vacuum forming these decorative sheets as described above, and each decorative resin molded product obtained from the vacuum-formed decorative sheet, the surface Were visually observed and further touched by hand, and the design feeling and touch feeling were visually evaluated according to the following criteria. The results are shown in Table 1.

(Evaluation of visual design feeling)
◎: The first concavo-convex shape was clearly visible, and the design feeling by visual observation was excellent. ◯: The first concavo-convex shape was sufficiently visible, and felt as a design by visual observation. Δ: It was difficult to visually recognize, but the first concavo-convex shape. It was confirmed that the design was expressed by X: The first uneven shape could not be visually recognized.

(Feel)
◎: The second uneven shape can be clearly felt, and the design is excellent in touch feeling. ○: The touch feeling due to the second uneven shape can be sufficiently felt. △: The second unevenness is somewhat difficult to understand. I was able to feel the hand feeling due to the shape ×: I could not feel the second uneven shape with my hand

DESCRIPTION OF SYMBOLS 1 Base material layer 11 1st uneven | corrugated shape 12 2nd uneven | corrugated shape 2 Surface protective layer 2a 1st surface 2b 2nd surface 21 1st surface protective layer 22 2nd surface protective layer 3 Decoration layer 4 Primer layer 5 Film layer 6 Molding resin layer

Claims (8)

At least a decorative sheet comprising a base material layer and a surface protective layer made of a cured product of an ionizing radiation curable resin composition,
A first concavo-convex shape is provided on the first surface of the surface protective layer on the base material layer side,
A second concavo-convex shape is provided on the second surface opposite to the first surface of the surface protective layer,
The decorative sheet in which the first uneven shape and the second shape are different from each other.   The decorative sheet according to claim 1, wherein the surface protective layer is a single layer or a multilayer.   The decorative sheet according to claim 1 or 2, wherein a peelable film layer is provided on the second surface of the surface protective layer. A decorative layer is provided between the base material layer and the surface protective layer,
The said decoration layer is a decorating sheet in any one of Claims 1-3 provided along the said 1st uneven | corrugated shape. A primer layer is provided directly under the surface protective layer,
The said primer layer is a decorating sheet in any one of Claims 1-4 provided along the said 1st uneven | corrugated shape. Forming a first concavo-convex shape on the surface of the base material layer;
Applying an ionizing radiation curable resin composition to the surface side where the first concavo-convex shape of the base material layer is formed and curing to form a surface protective layer;
Forming a second concavo-convex shape different from the first concavo-convex shape on the surface of the surface protective layer opposite to the base material layer;
A method for producing a decorative sheet. At least a decorative resin molded product comprising a molded resin layer, a base material layer, and a surface protective layer made of a cured product of an ionizing radiation curable resin composition,
A first concavo-convex shape is provided on the first surface of the surface protective layer on the base material layer side,
A second concavo-convex shape is provided on the second surface opposite to the first surface of the surface protective layer,
A decorative resin molded product in which the first uneven shape and the second shape are different from each other.   The manufacturing method of a decorative resin molded product provided with the process of laminating | stacking a molded resin layer by injecting resin to the said base material layer side of the decorating sheet in any one of Claims 1-6.