JP6657599B2 - Decorative sheet - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a decorative sheet that can impart an excellent design feeling and a feeling of touch due to an uneven shape.

  2. Description of the Related Art A decorative resin molded product obtained by laminating a decorative sheet on the surface of a resin molded product is used for a vehicle interior component, a building material interior material, a home appliance housing, and the like. In recent years, with the diversification of consumer needs, decorative resin molded products having various design properties 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 an uneven shape on the surface and having not only a good design feeling but also a good touch.

  Conventionally, in the production of decorative resin molded products, a molding method of integrating a decorative sheet, which has been given a design property in advance, with a resin by injection molding has been used, and a decorative resin molded product having an uneven shape is formed. In the production of, a decorative sheet having an uneven shape on the surface is used.

  However, when manufacturing a decorative resin molded product using a decorative sheet having an uneven shape, the uneven shape is deformed by heat or pressure when the decorative sheet is subjected to injection molding or preliminary forming (vacuum forming) prior thereto. Because of this, the decorative sheet after injection molding cannot maintain the initial uneven shape, and thus has a drawback that the design and feel due to the uneven shape cannot be sufficiently imparted.

  In order to overcome such a drawback, by laminating a cushion layer made of a thermoplastic resin by extrusion or hot melt coating on the surface of a decorative sheet having irregularities formed by embossing a thermoplastic base sheet, A method has been reported in which deformation or disappearance of the uneven shape generated during vacuum molding or injection molding is suppressed, and the cushion layer is removed after injection molding (for example, see Patent Document 1).

  However, in the method disclosed in Patent Literature 1, the cushion layer provided for suppressing deformation and disappearance of the uneven shape is formed by extrusion molding of a thermoplastic resin or hot melt coating, so that the molten thermoplastic resin There is a problem that fine irregularities on the surface of the thermoplastic base sheet are easily deformed or lost due to the heat of the resin.

JP 2008-137216 A

  The main object of the present invention is to provide a decorative sheet that can provide a resin molded product with an excellent design and feel due to the uneven shape. Further, another object of the present invention is to provide a decorative resin molded product using the decorative sheet, and a method for producing the same.

  The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, at least, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated, and the uneven protective layer is, in order from the surface layer side, an adhesive layer that fills the concave portion of the uneven shape of the surface layer. It has been found that the decorative sheet having the release film layer can effectively protect the unevenness of the surface layer by the unevenness protection layer. Then, by using the decorative sheet, deformation and disappearance of the uneven shape generated during vacuum molding or injection molding can be suppressed, and the decorative resin molded product can be given an excellent design feeling and a feeling of touch due to the uneven shape. Was found. The present invention has been completed by further study based on such knowledge.

That is, the present invention provides the following aspects of the invention.
Item 1. At least, a surface layer having an uneven shape, and a peelable unevenness protective layer are laminated,
The decorative sheet, wherein the unevenness protective layer includes, in order from the surface layer side, an adhesive layer filling a concave portion of the unevenness of the surface layer, and a release film layer.
Item 2. Item 4. The decorative sheet according to Item 1, wherein the adhesive layer is formed of a cured product of a curable resin.
Item 3. The unevenness protective layer includes, in order from the surface layer side, a release layer, the adhesive layer, and the release film layer,
Item 3. The decorative sheet according to Item 1 or 2, wherein the release layer and the adhesive layer fill the concaves and convexes of the surface layer.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the release layer is formed of a cured product of the ionizing radiation-curable resin composition.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the surface layer is formed of a cured product of a curable resin composition or a resin film.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein a primer layer is laminated immediately below the surface layer.
Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, wherein a picture layer is laminated on a side of the surface layer opposite to the unevenness protective layer.
Item 8. A first step of preparing a surface layer having an uneven shape,
A second step of applying an adhesive on the surface layer so as to fill the concaves and convexes of the surface layer, and laminating the adhesive layer,
A third step of laminating a release film layer on the adhesive layer;
A method for manufacturing a decorative sheet, comprising:
Item 9. Item 9. The method for manufacturing a decorative sheet according to Item 8, wherein the first step includes the following steps.
A step of laminating a pattern layer and a primer layer in this order on the base material layer,
Performing an embossing process on the primer layer, and forming an uneven shape on the surface of the primer layer,
A step of applying a curable resin composition over the primer layer, curing the composition, and laminating a surface layer having an uneven shape.
Item 10. Item 9. The method for manufacturing a decorative sheet according to Item 8, wherein the first step includes the following steps.
A step of preparing a surface layer made of a resin film,
A step of performing embossing from above the surface layer to form irregularities on the surface of the surface layer.
Item 11. Item 9. The method for manufacturing a decorative sheet according to Item 8, wherein the first step includes the following steps.
A step of laminating a pattern layer and a primer layer in this order on the base material layer,
A step of laminating a resin film on the primer layer and laminating a surface layer,
A step of performing embossing from above the surface layer to form irregularities on the surface of the surface layer.
Item 12. At least, a molded resin layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order,
A decorative resin molded article with a concavo-convex protective layer, comprising, in order from the surface layer side, the concavo-convex protective layer, which includes an adhesive layer filling a concave portion of the concavo-convex shape of the surface layer, and a release film layer.
Item 13. Item 13. A method for producing a decorative resin molded product, comprising a step of peeling off the concave-convex protective layer from the decorative resin molded product with the concave-convex protective layer according to Item 12.
Item 14. Item 8. A method for producing a decorative resin molded article with a concavo-convex protective layer, comprising a step of injecting a resin to form a molded resin layer on the surface layer side of the decorative sheet according to any one of Items 1 to 7.

  According to the present invention, it is possible to provide a decorative sheet capable of imparting an excellent design feeling and a feeling of touch to a resin molded product due to an uneven shape. Further, according to the present invention, it is also possible to provide a decorative resin molded product using the decorative sheet, and a method for producing the same.

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. FIG. 1 is a schematic view of a cross-sectional structure of one embodiment of a decorative resin molded product having an unevenness protective layer according to 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. Decorative sheet The decorative sheet of the present invention has at least a surface layer having an uneven shape and a peelable uneven protective layer laminated thereon, and the uneven protective layer is, in order from the surface layer side, the surface layer. It is characterized by comprising an adhesive layer filling the concave portion of the concave and convex shape and a release film layer. Hereinafter, the decorative sheet of the present invention will be described in detail. In this specification, unless otherwise specified, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”, and other similar notations have the same meaning. Further, the decorative sheet of the present invention does not have to have a pattern layer or the like, and may be, for example, transparent.

Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure in which at least a surface layer 2 having an uneven shape and a peelable uneven protective layer 3 are stacked.

  The unevenness protective layer 3 includes, in order from the surface layer 2 side, an adhesive layer 31 filling the concave portions of the unevenness of the surface layer 2 and a release film layer 30. For the purpose of enhancing the releasability between the surface layer 2 and the concavo-convex protection layer 3, the release layer 32, the adhesive layer 31, and the release film layer 30 of the concavo-convex protection layer 3 are arranged in this order from the surface layer 2 side. May be laminated. In the case where the unevenness protective layer 3 has the release layer 32, in the decorative sheet of the present invention, the release layer 32 and the adhesive layer 31 fill the unevenness of the surface layer 2.

  In the decorative sheet of the present invention, a base layer 1 may be provided on the surface layer 2 on the side opposite to the unevenness protective layer 3 as a support for the decorative sheet or the like.

  In the decorative sheet of the present invention, a primer layer 4 may be provided on the side of the surface layer 2 opposite to the unevenness protective layer 3 as needed for the purpose of increasing the adhesion between the layers.

  Further, a picture layer 5 may be provided on the side of the surface layer 2 opposite to the concavo-convex protection layer 3 as needed for the purpose of providing decorativeness. When the base layer 1 and the primer layer 4 are provided, the picture layer 5 may be provided between the base layer 1 and the primer layer 4.

  When the base material layer 1 is provided, a concealing layer (not shown) may be provided between the base material layer 1 and the surface layer 2 as needed for the purpose of suppressing a change or variation in color of the base material layer 1. May be provided. When the primer layer 4 is provided, the concealing layer may be provided between the base material layer 1 and the primer layer 4, and when the picture layer 5 is provided, the concealing layer is provided by the base material layer It may be provided between 1 and the pattern layer 5.

  Further, a transparent resin layer 6 may be provided on the side of the surface layer 2 opposite to the unevenness protective layer 3 as needed for the purpose of improving the scratch resistance. When the primer layer 4 is provided, the transparent resin layer 6 may be provided between the picture layer 5 and the primer layer 4.

  Further, in the decorative sheet of the present invention, the surface of the surface layer 2 on the side opposite to the concave-convex protective layer 3 is provided for the purpose of enhancing the adhesiveness with the molding resin when molding the decorative resin molded product. If necessary, a back surface adhesive layer (not shown) may be provided.

  As an example of the laminated structure of the decorative sheet of the present invention, a laminated structure in which a surface layer 2 / a concavo-convex protective layer 3 (adhesive layer 31 / peeling film layer 30) is sequentially laminated; Layered structure in which layer 3 (adhesive layer 31 / release film layer 30) is sequentially laminated; base layer 1 / picture layer 5 / surface layer 2 / concavo-convex protective layer 3 (adhesive layer 31 / release film layer 30) sequentially laminated Laminated structure; base layer 1 / pattern layer 5 / primer layer 4 / surface layer 2 / concavo-convex protective layer 3 (adhesive layer 31 / release film layer 30) sequentially laminated; base layer 1 / pattern Laminated structure in which layer 5 / primer layer 4 / surface layer 2 / concavo-convex protective layer 3 (release layer 32 / adhesive layer 31 / release film layer 30) are sequentially laminated; base layer 1 / pattern layer 5 / transparent resin layer 6 / primer layer 4 / surface layer 2 / unevenness protective layer 3 (release layer 32 / adhesive layer 31 / peeling Irumu layer 30) is stacked in this order and the like laminated structure or the like are sequentially stacked. FIGS. 1 and 2 show, as one embodiment of the laminated structure of the decorative sheet of the present invention, a decorative sheet in which a base layer 1 / a surface layer 2 / an uneven protective layer 3 (adhesive layer 31 / release film layer 30) are sequentially laminated. 1 shows a sectional view of a decorative sheet. FIG. 3 shows one embodiment of the laminated structure of the decorative sheet of the present invention, which is a base layer 1 / a pattern layer 5 / a transparent resin layer 6 / a primer layer 4 / a surface layer 2 / an unevenness protective layer 3 (a release layer 32 / A sectional view of a decorative sheet in which a laminated structure in which an adhesive layer 31 / a release film layer 30) are sequentially laminated is shown.

Composition of each layer of decorative sheet [base layer 1]
The base material layer 1 is a resin sheet (resin film) serving as a support in the decorative sheet of the present invention, and is provided as necessary. For example, when a surface layer 2 described below has autonomy and plays a role as a support, the decorative sheet of the present invention may not have the base layer 1.

  The resin component used for the base layer 1 is not particularly limited, and may be appropriately selected according to three-dimensional moldability, compatibility with the molding resin, and the like. Preferably, a resin film made of a thermoplastic resin is used. No. As the thermoplastic resin, specifically, acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”), acrylonitrile-styrene-acrylate resin (hereinafter referred to as “ASA resin”) ), Acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, vinyl chloride resins, polyethylene terephthalate (PET), and the like. Among them, ABS resin and acrylic resin are preferable from the viewpoint of three-dimensional moldability. Further, the base material layer 1 may be formed of a single-layer sheet of these resins, or may be formed of a multi-layer sheet of the same or different resins.

  The flexural modulus of the base material layer 1 is not particularly limited. For example, when integrating the decorative sheet of the present invention with the molding resin by the insert molding method, the bending elastic modulus at 25 ° C. of the base layer 1 in the decorative sheet of the present invention is 500 to 4,000 MPa, preferably 750 to 3,000 MPa. 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 properties and moldability are further improved. Further, when the flexural modulus at 25 ° C. is 3,000 MPa or less, sufficient tension can be applied in the case of roll-to-roll production, and sag does not easily occur. And the so-called pattern registration becomes good.

  The base material layer 1 is subjected to a physical or chemical surface treatment such as an oxidation method or a concavo-convexity method on one surface or both surfaces, as necessary, in order to improve the adhesion with a layer provided thereon. You may. 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. In addition, examples of a method for forming a surface roughness of the base material layer 1 include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of the resin component constituting the base material layer 1, and preferably include a corona discharge treatment method from the viewpoint of effects and operability.

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

  Further, the base material layer 1 may be colored using a coloring agent or may not be colored. Further, the base material layer 1 may be any one of colorless and transparent, colored and transparent, and translucent. The colorant used for the base material layer 1 is not particularly limited, but preferably includes a colorant that does not change color even at a temperature of 150 ° C. or higher, and specifically includes existing dry colors, paste colors, and masterbatch resins. And the like.

  The thickness of the base material layer 1 is appropriately set according to the use of the decorative sheet, the molding method for integrating with the molding resin, and the like, and is usually about 25 to 1000 μm, or about 50 to 700 μm. More specifically, when the decorative sheet of the present invention is subjected to the insert molding method, the thickness of the base material layer 1 is usually about 50 to 1000 μm, preferably 100 to 700 μm, and more preferably 100 to 500 μm. No. In addition, when the decorative sheet of the present invention is subjected to the injection molding simultaneous decoration method, the thickness of the base layer 1 is usually 25 to 200 μm, preferably 50 to 200 μm, and more preferably 70 to 200 μm. .

[Surface layer 2]
The surface layer 2 has an uneven shape, and is preferably formed of a cured product of a curable resin composition or a resin film.

<Uneven shape>
The concavo-convex shape formed on the surface layer 2 is not particularly limited, and may be appropriately set in accordance with the design feeling or the touch to be provided. Examples of the concavo-convex shape include a hairline pattern, a grain pattern, a geometric pattern (dots, stripes, carbon), and the like.

  The height, width, pitch between adjacent convex portions, width of concave portions, and the like of the convex portions in the concavo-convex shape formed on the surface layer 2 are appropriately determined according to the sense of design and touch to be provided. Just set it. For example, the center line average roughness (Ra) of the surface layer 2 is usually 1.0 to 20 μm, preferably 1.0 to 10 μm, more preferably 1.0 to 20 μm from the viewpoint of imparting an excellent design feeling and touch due to the uneven shape. 1.5 to 5 μm. When the center line average roughness of the surface layer 2 is 20 μm or less, when the decorative sheet is wound into a roll and stored, etc., the unevenness is too severe. This does not cause any problems.

  In addition, from the same viewpoint, the maximum height (Rmax) is usually 1.0 to 100 μm, preferably 1.0 to 80 μm, and more preferably 1.0 to 60 μm. From the same viewpoint, the ten-point average height (Rz) is usually 1.0 to 100 μm, preferably 1.0 to 80 μm, and more preferably 1.0 to 60 μm. Note that the center line average roughness (Ra), the maximum height (Rmax), and the ten-point average height (Rz) are values measured by the methods described in Examples, respectively.

  The concave and convex shape formed by the surface layer 2 may be such that the bottom of the concave portion is formed by the surface layer 2 as shown in FIG. 1 or the concave portion is formed by the bottom of the concave portion as shown in FIG. The lower layer of the surface layer 2 may be exposed, and a plurality of convex portions of the surface layer 2 may be partially provided. The former is preferred from the viewpoint of protecting the surface of the decorative resin molded product. 1 and 2 show a laminated structure in which a substrate layer 1, a surface layer 2, and an unevenness protective layer 3 are sequentially laminated for convenience.

  In the decorative sheet of the present invention, the above-mentioned uneven shape may be formed in at least a part of the region in order to give the decorative sheet a high texture due to the uneven shape. That is, in the decorative sheet of the present invention, the uneven shape that satisfies the above relationship may be formed in some regions or may be formed in all regions.

<Composition>
Examples of the resin film forming the surface layer 2 include a thermoplastic resin film. Examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and acrylic resins, and acrylic resins are preferable. When the surface layer 2 is formed of a resin film, the surface layer 2 usually has autonomy and can play a role as a support. Therefore, in this case, the decorative sheet of the present invention may not have the base material layer 1.

  In the cured product of the curable resin composition forming the surface layer 2, examples of the curable resin include a thermosetting resin and an ionizing radiation-curable resin, and an ionizing radiation-curable resin is preferable. A surface layer having an uneven shape is formed by a cured product of a resin composition containing an ionizing radiation-curable resin, and is covered by a specific uneven protective layer described later, which is generated during vacuum molding or injection molding. Deformation and disappearance of the uneven shape can be suppressed, and it is possible to impart particularly excellent design feeling and touch feeling to the decorative resin molded product.

  Examples of the thermosetting resin include a urethane resin and an epoxy resin. The thermosetting resin may be used alone or in a combination of two or more. When a thermosetting resin is used, the surface layer 2 can be formed by laminating the thermosetting resin before curing and heating and curing. The ionizing radiation-curable resin is as follows.

(Ionizing radiation curable resin)
The ionizing radiation-curable resin used for forming the surface layer 2 refers to a resin that crosslinks and cures when irradiated with ionizing radiation. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and is usually ultraviolet (UV) or electron beam (EB). , X-rays, γ-rays, and other charged particles such as α-rays, ion beams, and the like. Among ionizing radiation curable resins, electron beam curable resins are suitable for use in forming a surface layer because they can be solvent-free, do not require a photopolymerization initiator, and have stable curing properties. Is done.

  Specific examples of the ionizing radiation-curable resin include those obtained by appropriately mixing a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule.

  As the oligomer used as the ionizing radiation-curable resin, a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule is preferable, and in particular, two or more polymerizable unsaturated bonds in the molecule (2 Polyfunctional (meth) acrylate oligomers having at least one functional group are 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, silicone-modified urethane (meth) acrylate, oligomer having a cationically polymerizable functional group in the molecule (for example, novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic Group vinyl ether, etc.). Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in a polymer main chain and has a (meth) acrylate group in a terminal or a 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 is obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate. Acrylic silicone (meth) acrylate can be obtained by radically copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol or polyester polyol with a polyisocyanate with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a bisphenol-type epoxy resin or a novolak-type epoxy resin having a relatively low molecular weight and esterifying it. A carboxyl-modified epoxy (meth) acrylate obtained by partially modifying the epoxy (meth) acrylate with a dibasic carboxylic anhydride can also be used. Polyester (meth) acrylate is obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or It can be obtained by esterifying a hydroxyl group at the terminal of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. Polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to a side chain of a 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. The silicone-modified urethane (meth) acrylate is obtained, for example, by reacting a urethane prepolymer having an isocyanate group with a silicone compound having a silanol group together with hydroxy (meth) acrylate. These oligomers may be used alone or in combination of two or more.

  Further, as the monomer used as the ionizing radiation-curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in a molecule is preferable, and among them, a polyfunctional (meth) acrylate monomer is preferable. The polyfunctional (meth) acrylate monomer may be any (meth) acrylate monomer having two or more polymerizable unsaturated bonds in the molecule. As the polyfunctional (meth) acrylate monomer, specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (Meth) acrylate, ethylene oxide-modified phosphate di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri ( (Meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol Hexa (meth) acrylate and the like. These monomers may be used alone or in a combination of two or more.

  Among these ionizing radiation-curable resins, oligomers having a polymerizable unsaturated bond or an epoxy group in the molecule are preferable from the viewpoint of imparting a more excellent design feeling and touch feeling to the decorative resin molded product. More preferably, polycarbonate (meth) acrylate and acrylic silicone (meth) acrylate, and particularly preferably, polycarbonate (meth) acrylate.

  Further, among these ionizing radiation curable resins, from the viewpoint of imparting a particularly excellent design feeling and touch feeling, preferably, (1) polycarbonate (meth) acrylate and (2) other polyfunctional ( A combination of (meth) acrylate (polyfunctional (meth) acrylate oligomer or monomer); more preferably, a combination of (1) polycarbonate (meth) acrylate and (2) polyfunctional urethane (meth) acrylate.

  When the ionizing radiation-curable resin of (1) and the ionizing radiation-curable resin of (2) are used in combination, their ratio may be set in consideration of their molecular weight, the number of functional groups, and the like. For example, for example, the mass ratio of the ionizing radiation-curable resin of (1) to the ionizing radiation-curable resin of (2) (the ionizing radiation-curable resin of (1): the ionizing radiation-curable resin of (2)) However, the ratio is preferably about 50:50 to 99: 1, more preferably about 80:20 to 99: 1, and particularly preferably about 85:15 to 99: 1.

  Hereinafter, polycarbonate (meth) acrylate and polyfunctional urethane (meth) acrylate that are preferably used as the ionizing radiation-curable resin for forming the surface layer 2 will be described in detail.

Polycarbonate (meth) acrylate Polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and (meth) acrylate in the terminal or side chain, and has, for example, a polycarbonate skeleton. Urethane (meth) acrylate or the like may be used. In addition, from the viewpoint of improving crosslinking and curing, the (meth) acrylate preferably has 2 to 6 functional groups per molecule. The polycarbonate (meth) acrylate is preferably a polyfunctional polycarbonate (meth) acrylate having two or more (meth) acrylates at a terminal or a side chain. As the polycarbonate (meth) acrylate, one type may be used alone, or two or more types may be used in combination.

  The polycarbonate (meth) acrylate is obtained, for example, by converting some or all of the hydroxyl groups of a polycarbonate polyol to (meth) acrylate (acrylate or methacrylate). This esterification reaction can be performed by a usual esterification reaction. For example, 1) a method of condensing a polycarbonate polyol and an acrylic acid halide or a methacrylic acid halide in the presence of a base, 2) a method of condensing a polycarbonate polyol with an acrylic acid anhydride or a methacrylic acid anhydride in the presence of a catalyst, Or 3) a method of condensing a polycarbonate polyol with 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 two or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups at the terminal or side chain. As a typical production method of the polycarbonate polyol, a method of performing a polycondensation reaction with a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) serving as a carbonyl component can be given.

Diol compound used as a raw material of the polycarbonate polyol (A) 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, it is a linear or branched alkylene group, cyclohexylene group, or 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 of the 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 obtained by adding 1 to 5 equivalents of ethylene oxide, propylene oxide, or another alkylene oxide to the hydroxyl group of the polyhydric alcohol. Good. These polyhydric alcohols may be used alone or in combination of two or more.

  The compound (C) serving as a carbonyl component used as a raw material of the polycarbonate polyol is any compound selected from diester carbonate, phosgene, and equivalents thereof. Specific examples of the compound include carbonate diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate; phosgene; halogenated formic acids such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate. Esters and the like. These compounds may be used alone or in combination of two or more.

  The polycarbonate polyol is synthesized by subjecting the diol compound (A), the trihydric or higher polyhydric alcohol (B), and the compound (C) to be a carbonyl component to a polycondensation reaction under general conditions. The charged molar ratio of the diol compound (A) and the polyhydric alcohol (B) may be set, for example, in the range of 50:50 to 99: 1. 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 groups of the diol compound and the polyhydric alcohol. What is necessary is just to set in the range of an equivalent.

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

  The method for producing a polycarbonate polyol described above is described in, for example, JP-A-64-1726. Further, as described in JP-A-3-181517, this polycarbonate polyol can also be produced by a transesterification reaction between a polycarbonate diol and a trihydric or higher polyhydric alcohol.

  The molecular weight of the polycarbonate (meth) acrylate is not particularly limited, and examples thereof include a weight average molecular weight of 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 is, for example, 100,000 or less, preferably 50,000 or less, from the viewpoint of controlling the viscosity so as not to be too high. From the viewpoint of further improving the moldability, the weight average molecular weight of the polycarbonate (meth) acrylate is preferably more than 2,000 and 50,000 or less, more preferably 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.

<Polyfunctional urethane (meth) acrylate>
The polyfunctional urethane (meth) acrylate is not particularly limited as long as it has a urethane bond in the polymer main chain and has (meth) acrylate in the terminal or side chain. Such a urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by a reaction between a polyether polyol or a polyester polyol and a polyisocyanate with (meth) acrylic acid. Further, urethane (meth) acrylate preferably has 2 to 12 functional groups per molecule from the viewpoint of improving crosslinking and curing. The ionizing radiation-curable resin composition used for forming the surface layer 2 may further contain urethane (meth) acrylate in addition to the above-mentioned polycarbonate (meth) acrylate. The urethane (meth) acrylate may be used alone or in a combination of two or more.

  Although the molecular weight of the urethane (meth) acrylate is not particularly limited, for example, the weight average molecular weight is 2,000 or more, preferably 5,000 or more. The upper limit of the weight average molecular weight of the urethane (meth) acrylate is not particularly limited, but is, for example, 30,000 or less, and preferably 10,000 or less, from the viewpoint of controlling the viscosity so as not to be too high.

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

<Silicone ionizing radiation curable resin>
By including a silicone-based ionizing radiation-curable resin as the ionizing radiation-curable resin forming the surface layer 2, the decorative resin molded product can be easily peeled off the unevenness protective layer 3 while providing excellent design feeling and touch. A feeling can be given.

  The silicone-based ionizing radiation-curable resin is not particularly limited, but preferably includes acrylic silicone (meth) acrylate, silicone (meth) acrylate, and silicone-modified urethane (meth) acrylate, and particularly preferably acrylic silicone (meth) acrylate Is mentioned. In the present invention, “acrylic silicone (meth) acrylate” refers to “a part of the structure of the acrylic resin in one molecule is substituted with a siloxane bond (Si—O), and the acrylic resin is a functional group. Having two or more (meth) acryloyloxy groups at the side chain and / or at the terminal of the main chain ”. The term "silicone (meth) acrylate" means "modified silicone oil having a (meth) acryloyl group introduced into a side chain or both terminals of a silicone oil having polysiloxane as a main chain". Hereinafter, acrylic silicone (meth) acrylate, silicone (meth) acrylate, and silicone-modified urethane (meth) acrylate, which are preferable as the silicone-based ionizing radiation-curable resin, will be described in detail.

(Acrylic silicone (meth) acrylate)
The acrylic silicone (meth) acrylate is not particularly limited, and a part of the structure of the acrylic resin is substituted with a siloxane bond (Si—O) in one molecule, and the side chain of the acrylic resin and / or Or what is necessary is just what has two or more (meth) acryloyloxy groups (acryloyloxy group or methacryloyloxy group) at the main chain terminal. As an example of the acrylic silicone (meth) acrylate, for example, a structure of an acrylic resin having a siloxane bond in a side chain as disclosed in JP-A-2007-070544 is preferably exemplified.

  The acrylic silicone (meth) acrylate used in the present invention can be synthesized, for example, by radically copolymerizing a silicone macromonomer with a (meth) acrylate monomer in the presence of a radical polymerization initiator. Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and glycidyl (meth) acrylate. These (meth) acrylate monomers may be used alone or in combination of two or more.

  The silicone macromonomer is synthesized by, for example, using n-butyllithium or lithium silanolate as a polymerization initiator, anionically polymerizing hexaalkylcyclotrisiloxane, and then capping with a radical-polymerizable unsaturated group-containing silane. As the silicone macromonomer, the following formula (1);

The compound represented by is preferably used. Here, in the formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, and is preferably a methyl group or an n-butyl group. 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 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. The value of n is not particularly limited, and for example, the number average molecular weight of the silicone macromonomer is preferably from 1,000 to 30,000, more preferably from 1,000 to 20,000.

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

In the formulas (2), (3) and (4), R ¹ and R ³ have the same meanings as in the formula (1), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents the above (meth) acrylate R ⁶ represents an alkyl group or glycidyl group in the monomer or an alkyl group which may have a functional group such as the alkyl group or glycidyl group in the (meth) acrylate monomer, and R ⁶ represents an organic group having a (meth) acryloyloxy group. Represents a group. The above-mentioned acrylic silicone (meth) acrylate is used alone or in combination of two or more.

  The molecular weight of the acrylic silicone (meth) acrylate is measured by GPC analysis, and the weight-average molecular weight in terms of standard polystyrene is preferably 1,000 or more, more preferably 2,000 or more. . The upper limit of the weight average molecular weight of the acrylic silicone (meth) acrylate is not particularly limited, but is preferably 150,000 or less, more preferably 100,000 or less, from the viewpoint of controlling the viscosity not to be too high. It is particularly preferably from 2,000 to 100,000 from the viewpoint of achieving a three-dimensional formability, chemical resistance and scratch resistance.

  The average molecular weight between crosslink points of the acrylic silicone (meth) acrylate is preferably from 100 to 2,500. When the average molecular weight between crosslinking points is 100 or more, it is preferable from the viewpoint of three-dimensional moldability, and when it is 2500 or less, it is preferable from the viewpoint of chemical resistance and scratch resistance. From the same viewpoint, the average molecular weight between crosslinking points of the acrylic silicone (meth) acrylate is more preferably 100 to 1,500, and still more preferably 100 to 1,000.

(Silicone (meth) acrylate)
The silicone (meth) acrylate is not particularly limited as long as it is a modified silicone oil in which a (meth) acryloyl group is introduced into a side chain or both terminals of a silicone oil having polysiloxane as a main chain, and is a monofunctional or bifunctional silicone. (Meth) acrylate and polyfunctional (trifunctional or more) silicone (meth) acrylate can be used.

  As the monofunctional or bifunctional silicone (meth) acrylate, conventionally known ones can be used, and if the organic group is a (meth) acrylic group and it is a modified silicone oil having one or two organic groups, it is particularly limited. Not done. The structure of the modified silicone oil is roughly classified into a side chain type, a double-ended type, a single-ended type, and a double-ended side chain type depending on the bonding position of the organic group to be substituted. There is no particular limitation. Such a silicone (meth) acrylate preferably has a weight average molecular weight of 1,000 to 6,000, more preferably 3,000 to 6,000, and a functional group equivalent (weight average molecular weight / number of functional groups) of preferably 500 to 3,000, more preferably 1500 to 5,000. Those having a condition of 3000 are used.

  Further, as the polyfunctional (trifunctional or more) silicone (meth) acrylate used for the silicone (meth) acrylate, conventionally known ones can be used, and the organic group is a (meth) acryl group, and a plurality of such organic groups are preferably used. Is not particularly limited as long as it is a modified silicone oil having four or more, and more preferably four to six. The structure of the modified silicone oil is roughly classified into a side chain type, a double-ended type, a single-ended type, and a double-ended side chain type depending on the bonding position of the organic group to be substituted. There is no particular limitation. Such a silicone (meth) acrylate preferably has a weight average molecular weight of 3,000 to 100,000, more preferably 10,000 to 30,000, and a functional group equivalent (weight average molecular weight / number of functional groups) of preferably 750 to 25,000, and more preferably 3,000 to 5,000. Those having a condition of 6000 are used.

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

(Silicone-modified urethane (meth) acrylate)
The silicone-modified urethane (meth) acrylate is not particularly limited, and examples thereof include compounds in which a part of the side chain of urethane (meth) acrylate is modified with silicone. The silicone-modified urethane (meth) acrylate is obtained, for example, by reacting a urethane prepolymer having an isocyanate group with a silicone compound having a silanol group together with hydroxy (meth) acrylate.

  Regarding the number of functional groups and the molecular weight of the silicone-modified urethane (meth) acrylate, for example, the number of functional groups per molecule is 1 to 10, preferably 2 to 8, more preferably 3 to 6, and the weight average molecular weight is 1000 to 1000. 50,000, preferably 3,000 to 30,000, more preferably 5,000 to 10,000.

  The proportion of the silicone-based ionizing radiation-curable resin in the ionizing radiation-curable resin forming the surface layer 2 is preferably about 1 to 10% by mass, more preferably about 1 to 5% by mass, and further preferably 3 to 5% by mass. About 5% by mass.

<Other additives>
The resin composition used for forming the surface layer 2 may contain various additives depending on desired physical properties of the surface 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, and a leveling agent. , A thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a coloring agent, and the like. These additives can be appropriately selected and used from those commonly used. In addition, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used as the ultraviolet absorber or light stabilizer.

<Thickness of surface layer 2>
The thickness of the surface layer 2 after curing is not particularly limited, but is, for example, 0.01 to 20 μm, preferably 0.01 to 15 μm, and more preferably 0.01 to 12 μm. By satisfying the thickness in such a range, the uneven shape can be more effectively expressed, and excellent design feeling and touch feeling can be provided. In addition, from the same viewpoint, when the surface layer 2 is formed of a resin film, the thickness of the surface layer 2 is preferably 50 to 200 μm. In addition, the thickness of the surface layer 2 means the thickness of the convex portion of the surface layer 2.

<Formation of surface layer 2>
When a resin film is used as the surface layer 2, the resin layer is laminated on a layer located below the surface layer 2, and embossing is performed on the resin film to form the surface layer 2 having an uneven shape. Can be formed.

  When the surface layer 2 is formed using a curable resin composition, a cured product of the curable resin composition may be formed on a predetermined layer so as to have an uneven shape. Is not particularly limited. Examples of the method of providing the surface layer 2 with a concavo-convex shape include a method of embossing, and a method of applying and curing a resin composition for forming the surface layer 2 only on a portion where a convex portion is to be formed. However, a method of performing embossing is preferable.

  When the surface layer 2 is formed using the curable resin composition, the following first to third methods are specifically mentioned as a method for forming the surface layer 2 having an uneven shape.

First method: a sheet having a layer other than the surface layer 2 is prepared by sequentially laminating the substrate layer 1 and other layers provided as necessary, and embossing is performed on the side of the sheet on which the surface layer 2 is to be laminated. After applying, a method of applying a curable resin composition used for forming the surface layer 2 and curing the curable resin composition.

Second method: a sheet having a layer other than the surface layer 2 is prepared by sequentially laminating the base material layer 1 and other layers provided as necessary, and the surface layer 2 is provided on the side of the sheet on which the surface layer 2 is to be laminated. A method of applying a curable resin composition used for forming the composition, curing the curable resin composition, and then embossing the surface layer 2 side.

Third method: a sheet having a layer other than the surface layer 2 is prepared by sequentially laminating the base material layer 1 and other layers provided as necessary, and the convex portion of the sheet on which the surface layer 2 is to be laminated is formed. A method in which a curable resin composition used for forming the surface layer 2 is applied only to a portion to be formed, and the curable resin composition is cured.

  The method of applying the curable resin composition used for forming the surface layer 2 on a predetermined layer is not particularly limited, and examples thereof include a gravure coat, a bar coat, a roll coat, a reverse roll coat, and a comma coat. And preferably a gravure coat.

  When an ionizing radiation-curable resin is used as the curable resin, the ionizing radiation-curable resin composition (uncured resin layer) applied on a predetermined layer in this manner is applied to an ionizing radiation such as an electron beam or an ultraviolet ray. To cure the resin composition to form the surface layer 2. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, and the acceleration voltage is usually about 70 to 300 kV.

  In the irradiation of electron beams, the higher the acceleration voltage, the higher the transmission capability. Therefore, when a substrate that deteriorates due to the electron beam is used as the substrate layer, the transmission depth of the electron beam and the thickness of the resin layer are substantially reduced. By selecting the accelerating voltage so as to be substantially equal to each other, it is possible to suppress the irradiation of the base material layer with an extra electron beam and to minimize the deterioration of the base material due to the excess electron beam.

  The irradiation dose is preferably an amount at which the crosslinking 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).

  Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as Cockloft-Walton type, Van degraft type, resonance transformer type, insulating core transformer type, or linear type, dynamitron type, and high frequency type Can be used.

  When ultraviolet rays are used as ionizing radiation, light rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet light 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.

[Unevenness protective layer 3]
The unevenness protective layer 3 is a layer provided on the surface layer 2 so as to be in contact with the surface layer 2, is laminated so as to be peelable from the interface with the surface layer 2, and is integrally formed with a molding resin. This is a layer that is peeled off after the In the present invention, the concavo-convex protection layer 3 includes, in order from the surface layer 2 side, an adhesive layer 31 filling the concave portions of the concavo-convex shape of the surface layer 2 and a release film layer 30.

  In the present invention, the adhesive layer 31 of the unevenness protective layer 3 is formed of an adhesive, and can be formed by applying the adhesive on the surface layer 2 having the uneven shape. Therefore, the formation of the adhesive layer does not require heating by extrusion molding or thermal lamination as in the cushion layer disclosed in Patent Document 1 described above. Therefore, in the present invention, it is possible to form the unevenness protective layer 3 for protecting the unevenness of the surface layer 2 while suitably maintaining the fine unevenness of the surface layer 2.

(Adhesive layer 31)
The adhesive used for the adhesive layer 31 of the unevenness protective layer 3 can be applied so as to fill the unevenness of the surface layer 2 and can be peeled off from the surface of the surface layer 2 together with the release film 30. If so, there is no particular limitation, but a curable resin is preferably used. As the curable resin, for example, a urethane-based adhesive, an acrylic-based adhesive, an epoxy-based adhesive, a rubber-based adhesive, and the like can be given. Among them, the urethane-based adhesive can maintain a sufficient adhesive force even during injection molding. This is preferable in that it can be separated from the surface of the surface layer 2. Such urethane-based adhesives include two-component curable urethane resin-based adhesives, and two-component curable urethane resin-based adhesives include various hydroxyl groups such as polyether polyols, polyester polyols, and acrylic polyols. An adhesive using a two-part curable urethane resin containing a compound and various polyisocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate.

  The thickness of the adhesive layer 31 is not particularly limited, but is preferably about 5 to 70 μm, and more preferably about 15 to 60 μm. Note that the thickness of the adhesive layer 31 is the thickness of a portion of the lower layer (the surface layer 2 or the release layer 32) located above the convex portion.

  The adhesive layer 31 can be formed by applying the above-mentioned adhesive on a layer (the surface layer 2 or the release layer 32) located below the adhesive layer 31. Specifically, the adhesive is applied to the surface of the surface layer 2 (when the release layer 32 is provided, the adhesive is applied to the surface of the release layer 32 by a method such as gravure coating, bar coating, roll coating, reverse roll coating, or comma coating). On the surface).

(Release film 30)
The release film 30 forms the unevenness protective layer 3 together with the adhesive layer 31 and is a layer provided to suppress deformation and disappearance of the unevenness of the surface layer 2 during vacuum forming or injection molding of the decorative sheet.

  The material of the release film 30 is not particularly limited, and can be formed of, for example, a thermoplastic resin film. The thermoplastic resin constituting the thermoplastic resin film is not particularly limited, and may be an acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”); an acrylonitrile-styrene-acrylate resin; an acrylic resin; Polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resins; polyethylene terephthalate (PET) resins and the like. One kind of the thermoplastic resin may be contained alone, or two or more kinds may be contained.

  The thickness of the release film 30 is not particularly limited, but is preferably about 5 to 100 μm, and more preferably about 20 to 50 μm.

(Release layer 32)
The concave-convex protective layer 3 may include a release layer 32 for the purpose of enhancing the releasability between the concave-convex protective layer 3 and the surface layer 2. When having the release layer 32, the unevenness protective layer 3 includes the release layer 32, the adhesive layer 31, and the release film layer 30 in order from the surface layer 2 side. In addition, the release layer 32 and the adhesive layer 31 fill the concaves and convexes of the surface layer 2.

  The material for forming the release layer 32 is not particularly limited as long as it can be applied so as to fill the unevenness of the surface layer 2 and can be peeled off from the surface of the surface layer 2 as the unevenness protective layer 3. Instead, it can be formed of, for example, a resin.

  When the surface layer 2 is formed of a cured product of the ionizing radiation-curable resin composition, the release layer 32 is also preferably formed of a cured product of the ionizing radiation-curable resin composition. This makes it possible to more effectively suppress the deformation and disappearance of the uneven shape of the surface layer 2 during vacuum molding or injection molding, and to impart an excellent design feeling and a feeling of touch to the decorative resin molded product.

<Ionizing radiation curable resin in the release layer 32>
About the kind of ionizing radiation curable resin used for formation of the release layer 32, preferable thing, etc., it is the same as that used for formation of the said surface layer 2. In particular, among the ionizing radiation resins, the combination of the ionizing radiation-curable resin (1) and the ionizing radiation-curable resin (2) exemplified in the section of the surface layer 2 is not limited to the surface layer during vacuum molding or injection molding. In addition to the function of suppressing the deformation and disappearance of the uneven shape of No. 2, it can also be provided with ease of peeling when peeled after being integrally molded with the molding resin, and thus is suitably used in the release layer 32. As the ionizing radiation-curable resin in the release layer 32, trifunctional pentaerythritol acrylate is preferable. Further, the ionizing radiation curable resin used for forming the release layer 32 and the ionizing radiation curable resin used for forming the surface layer 2 may be of the same type or different types. .

<Other additives>
The ionizing radiation-curable resin composition used for forming the release layer 32 contains, as necessary, other resin components in addition to the ionizing radiation-curable resin for improving moldability and the like. You may. Examples of the resin component other than the ionizing radiation-curable resin include acrylic resin; polyvinyl acetal such as polyvinyl butyral (butyral resin); polyester resin such as polyethylene terephthalate and polybutylene terephthalate; vinyl chloride resin; urethane resin; Styrene-based resins such as polystyrene and α-methylstyrene; polyamides; polycarbonates; acetal resins such as polyoxymethylene; fluororesins such as ethylene-tetrafluoroethylene copolymer; polyimides; Acetal resins; thermoplastic resins such as liquid crystalline polyester resins. These resin components may be used alone or in a combination of two or more.

  The release layer 32 includes, in addition to the ionizing radiation-curable resin composition, a silicone-based resin, a fluorine-based resin, an acrylic-based resin (for example, an acryl-melamine-based resin is included), a polyester-based resin, a polyolefin-based resin, and polystyrene. -Based resin, polyurethane-based resin, cellulose-based resin, vinyl chloride-vinyl acetate-based copolymer resin, thermoplastic resin such as nitrified cotton, a copolymer of a monomer forming the thermoplastic resin, or these resins ) A resin modified with acrylic acid or urethane can be used alone or by using a resin composition in which a plurality of resins are mixed. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified ones thereof are preferable, and more specifically, acryl-melamine Resin alone, acrylic-melamine resin-containing composition, resin composition obtained by mixing a polyester resin and a copolymer of ethylene and acrylic acid and urethane-modified, a copolymer of an acrylic resin and styrene and acrylic And the like. Among these, it is particularly preferable that the release layer 32 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 added to the resin composition forming the release layer 32 in consideration of desired physical properties to be provided in the unevenness protective layer 3. 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, Thixotropic agents, coupling agents, plasticizers, defoamers, fillers, solvents, coloring agents, and the like can be mentioned. These additives can be appropriately selected and used from those commonly used. In addition, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used as the ultraviolet absorber or light stabilizer.

  The thickness of the release layer 32 is not particularly limited, but is preferably about 1 to 25 μm, more preferably about 5 to 15 μm. Note that the thickness of the release layer 32 is the thickness of a portion of the surface layer 2 located above the convex portion.

  The release layer 32 can be formed by applying the above-described resin composition on the surface layer 2. Specifically, the resin composition may be applied to the surface of the surface layer 3 by a method such as gravure coating, bar coating, roll coating, reverse roll coating, or comma coating.

<Total thickness of unevenness protective layer 3>
The total thickness of the concavo-convex protection layer 3 is not particularly limited, but is, for example, 5 to 150 μm. In addition, from the viewpoint of facilitating peeling of the concavo-convex protective layer after being integrated with the molding resin, the total thickness of the concavo-convex protective layer 3 is preferably 10 to 100 μm, and more preferably 15 to 100 μm. Here, the total thickness of the concavo-convex protective layer 3 means the thickness of the protective layer after curing when a cured resin is used. The total thickness of the concavo-convex protection layer 3 is the thickness of a portion of the surface layer 2 located on the convex portion.

[Primer layer 4]
The primer layer 4 is provided between the base material layer 1 and the surface layer 2 and between the base layer 1 and the surface layer 2 when the pattern layer 5 is provided for the purpose of minimizing the occurrence of fine cracks and whitening in the stretched portion of the surface layer 2. It is a layer provided as necessary between the surface layer 2 and / or between the base layer 1 and the picture layer 5.

  It is preferable that the primer layer 4 is provided directly below the surface layer 2 from the viewpoint of increasing the adhesion between the surface layer 2 and the layer located thereunder.

  Examples of the primer composition 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, and chlorinated polypropylene. And 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, a polyurethane having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent) can be used. The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, and polyether polyol. Examples of the isocyanate include a polyvalent isocyanate having two or more isocyanate groups in a molecule, an aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. And aliphatic (or alicyclic) isocyanates. It is also possible to mix urethane resin and butyral resin.

  From the viewpoint of adhesion to the surface layer 2 after cross-linking, difficulty of interaction after laminating the surface layer 2, physical properties, and moldability, acrylic polyol or polyester polyol as polyol and hexamethylene diisocyanate as cross-linking agent, It is preferable to use a combination of 4,4-diphenylmethane diisocyanate, and it is particularly preferable to use a combination of acrylic polyol and hexamethylene diisocyanate.

  Examples of the (meth) acrylic resin include a homopolymer of (meth) acrylate, a copolymer of two or more different (meth) acrylate monomers, or a copolymer of (meth) acrylate with another monomer. Polymers include, for example, poly (meth) acrylate, poly (ethyl) acrylate, poly (meth) acrylate, butyl (meth) acrylate, and methyl (meth) acrylate. Butyl (meth) acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, styrene-methyl (meth) acrylate copolymer A (meth) acrylic resin composed of a homopolymer or a copolymer containing a (meth) acrylate such as (meth) acrylate is preferably used.

  As the (meth) acryl-urethane copolymer resin, for example, an acryl-urethane (polyester urethane) block copolymer resin is preferable. As the curing agent, the various isocyanates described above are used. The acryl-urethane (polyester urethane) block copolymer resin adjusts the acryl / urethane ratio (mass ratio) in a range of preferably 9/1 to 1/9, more preferably 8/2 to 2/8, as required. Is preferred.

  The thickness of the primer layer 4 is not particularly limited, but is, for example, about 0.5 to 20 μm, and preferably 1 to 5 μm.

  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 by a silk screen, a wire bar coat, It is formed by a usual coating method such as a flow coat, a comma coat, a flowing coat, a brush coating, a spray coat, or a transfer coating method. Here, the transfer coating method is a method in which a coating film of a primer layer or an adhesive layer is formed on a thin sheet (film base material), and thereafter, the surface of a target layer in the decorative sheet is coated.

[Picture layer 5]
The picture layer 5 is provided on the opposite side of the unevenness protective layer 3 of the surface layer 2 (when the base layer 1 is provided, between the base layer 1 and the surface layer 2, When the primer layer 4 is provided, it is a layer provided as necessary between the base material layer 1 and the primer layer 4 or between the concealing layer and the surface layer 2 when the concealing layer is provided.

  The picture layer 5 can be, for example, a layer in which a desired picture is formed using an ink composition. As the ink composition used for forming the picture layer 5, a mixture obtained by appropriately mixing a binder, a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like is used. .

  The binder used in the ink composition is not particularly limited, and examples thereof include a polyurethane resin, a vinyl chloride / vinyl acetate copolymer resin, a vinyl chloride / vinyl acetate / acryl copolymer resin, a chlorinated polypropylene resin, and an acrylic resin. , Polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin and the like. These binders may be used alone or in a combination of two or more.

  The colorant used in the ink composition is not particularly limited, and examples thereof include carbon black (black ink), iron black, titanium white, antimony white, graphite, titanium yellow, red stalk, cadmium red, ultramarine blue, and cobalt blue. Organic pigments or dyes such as quinacridone red, isoindolinone yellow and phthalocyanine blue; metal pigments composed of scale-like foil pieces such as aluminum and brass; scale-like foils such as titanium dioxide-coated mica and basic lead carbonate A pearl luster (pearl) pigment composed of pieces may be used.

  The pattern formed by the pattern layer 5 is not particularly limited, either. For example, a stone pattern, a cloth pattern, or a cloth-like pattern imitating the surface of a rock such as a wood pattern, a marble pattern (for example, a travertine marble pattern) is simulated. A cloth pattern, a tiled pattern, a brickwork pattern, and the like may be mentioned, and a pattern such as a parquet or a patchwork which combines these, or a single-color solid color (so-called solid surface) may be used. These patterns are formed by multicolor printing using normal yellow, red, blue, and black process colors, but also by multicolor printing using special colors prepared by preparing individual color plates constituting the pattern. Can be formed.

  The thickness of the picture layer 5 is not particularly limited, but is, for example, 1 to 30 μm, preferably 1 to 20 μm.

  The picture layer 5 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 an evaporation method such as a vacuum evaporation method using the above-described metal, a sputtering method, and an ion plating method. The metal thin film layer may be provided on the entire surface or partially. In addition, a primer layer using a known resin may be provided on the front surface or the back surface of the metal thin film layer in order to improve the adhesiveness with an adjacent layer.

[Hiding layer]
The concealing layer is provided between the base layer 1 and the surface layer 2 or between the base layer 1 and the primer layer 2 when the primer layer 4 is provided, for the purpose of suppressing a change or variation in color of the base layer 1. Or, in the case where the picture layer 5 is provided, it is a layer provided as needed between the base material layer 1 and the picture layer 5.

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

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

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

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

[Transparent resin layer 6]
The transparent resin layer 6 is provided between the base layer 1 and the surface layer 2 when the base layer 1 is provided, and the base layer 1 when the primer layer 4 is provided, for the purpose of improving chemical resistance and scratch resistance. When the primer layer 4 and the pattern layer 5 are provided in this order between the primer layer 4 and the pattern layer 5 and the surface layer 2 when the pattern layer 5 is provided, or between the primer layer 4 and the pattern layer 5 on the base material layer 1. It is a layer provided as necessary, for example, in the middle. The transparent resin layer 6 is a layer suitably provided in the decorative sheet integrated with the molding resin by the insert molding method.

  The resin component forming the transparent resin layer 6 is appropriately selected according to transparency, three-dimensional moldability, shape stability, chemical resistance, and the like, but a thermoplastic resin is usually used. Examples of the thermoplastic resin include, but are not particularly limited to, 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 and the like, preferably, acrylic resin, polyolefin resin, polycarbonate resin, polyester resin; more preferably, acrylic resin, polyester resin; more preferably, polyester Resins.

  The transparent resin layer 6 is subjected to a physical or chemical surface treatment such as an oxidation method or an unevenness method on one surface or both surfaces, as needed, in order to improve the adhesiveness with another layer in contact with the transparent resin layer 6. You may. These physical or chemical surface treatments are the same as the surface treatment applied to the base material layer.

  The thickness of the transparent resin layer 6 is not particularly limited, but is, for example, 10 to 200 μm, and preferably 15 to 150 μm.

  The transparent resin layer 6 may be laminated via an adhesive, or may be laminated directly without using an adhesive. When laminating via an adhesive, for example, polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin resin, polyamide resin, polyolefin resin, poly Examples include vinyl acetate resin, cellulose resin, (meth) acrylic resin, polyimide resin, amino resin, rubber, and silicone resin. In the case of laminating without using an adhesive, it can be performed by a method such as an extrusion method, a sand lamination method, and a thermal lamination method.

[Backside adhesive layer]
The back surface adhesive layer (not shown) is provided on the surface of the surface layer 2 on the side opposite to the unevenness protective layer 3 for the purpose of enhancing the adhesion to the molding resin during molding of the decorative resin molded product. It is a layer provided according to.

  For the back surface adhesive layer, a thermoplastic resin or a curable resin is used 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 acrylic resin, acrylic-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride / vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, and polyamide. Resin, rubber-based resin, and the like. One of these thermoplastic resins may be used alone, or two or more thereof may be used in combination.

  In addition, examples of the thermosetting resin used for forming the back surface adhesive layer include a urethane resin and an epoxy resin. One of these thermosetting resins may be used alone, or two or more thereof may be used in combination.

Method for Manufacturing Decorative Sheet The decorative sheet of the present invention can be manufactured, for example, through the following first to third steps.

First Step of Providing Surface Layer 2 with Roughness Shape An adhesive is applied on surface layer 2 so as to fill the concave portions of the roughness shape of surface layer 2, and second step of laminating adhesive layer 31. A third step of laminating the release film layer 30 on the substrate.

  In the first to third steps, the components used for forming each layer, the specific conditions of the method for forming each layer, the method for forming the uneven shape of the surface layer 2, and the like are as described in the column of the composition of each layer. It is.

Furthermore, when the unevenness protective layer 3 is formed of a laminate of the release layer 32, the adhesive layer 31, and the release film layer 30, the second step and the third step can be performed by, for example, the following steps.
A step of applying a resin composition constituting the release layer 32 on the surface layer 2 and forming the release layer 32 so as to fill the concaves and convexes of the surface layer 2;
Forming an adhesive layer 31 on the release layer 32 by applying an adhesive to fill the concaves and convexes of the surface layer 2;
A step of laminating the release film layer 30 on the adhesive layer 31;

When the surface layer 2 is formed of a resin film, the first step can be performed, for example, by the following steps.
A step of preparing a surface layer 2 made of a resin film;
A step of performing embossing from above the surface layer 2 to form an uneven shape on the surface of the surface layer 2.

In this case, when another layer such as the picture layer 5 and the primer layer 4 is formed between the base material layer 1 and the surface layer 2, the following steps can be performed.
Step of laminating another layer such as pattern layer 5 and primer layer 4 on base layer 1 Step of laminating surface layer 2 made of a resin film on another layer such as pattern layer 5 and primer layer 4 A step of performing embossing from above the surface layer 2 to form an uneven shape on the surface of the surface layer 2.

2. Uneven protective layer-decorated resin molded article uneven protective layer-decorated resin molded article of the present invention is formed is molded by integrally molding a resin in the decorative sheet of the present invention. That is, the decorative resin molded article with the concavo-convex protective layer of the present invention comprises at least a molding resin layer 7, a surface layer 2 having a concavo-convex shape, and a peelable concavo-convex protective layer 3, which are laminated in this order. No. 3 is characterized in that it comprises, in order from the surface layer 2 side, an adhesive layer 31 filling the concave portions of the unevenness of the surface layer 2, and a release film layer 30. FIG. 4 shows a cross-sectional structure of one embodiment of a decorative resin molded product having a concavo-convex protective layer of the present invention.

  The decorative resin molded article with the concavo-convex protective layer of the present invention is, for example, using the decorative sheet of the present invention, various types of injection molding such as insert molding, simultaneous injection molding decoration, blow molding, and gas injection molding. It is produced by a method. By providing the decorative sheet of the present invention to a decorative resin molded article with a concavo-convex protective layer by subjecting it to various injection molding methods, it is possible to exert the above-described effect of suppressing the damage of the concavo-convex shape during injection molding. Therefore, a preferable example of the molded resin layer 7 constituting the decorative resin molded article with the concavo-convex protective layer of the present invention is an injection resin layer formed by injection molding. Among these injection molding methods, preferably, an insert molding method and a simultaneous injection molding decoration method are used.

  In the insert molding method, first, in a vacuum forming step, the decorative sheet of the present invention is vacuum-formed (off-line preforming) in advance to a molded product surface shape using a vacuum forming die, and then an unnecessary portion is trimmed as necessary. Obtain a molded sheet. This molded sheet is inserted into the injection mold, the injection mold is clamped, the resin in the fluid state is injected into the mold, and solidified, and the surface of the decorative sheet is formed on the outer surface of the resin molded product simultaneously with the injection molding. By integrating the layer 2 side (the side opposite to the concavo-convex protective layer 3), a decorative resin molded article with the concavo-convex protective layer is manufactured.

  More specifically, the decorative resin molded product with an uneven protective 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,
A step of trimming an excess portion of the vacuum-formed decorative sheet to obtain a molded sheet, and inserting the molded sheet obtained in the above step into an injection molding die, closing the injection molding die, and molding the resin in a fluid state into a mold. A process of integrating the resin and the molded sheet by injecting it into the interior.

  In the vacuum forming step in the insert forming method, the decorative sheet may be heated and formed. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of the resin forming the decorative sheet, the thickness of the decorative sheet, and the like. For example, when the ABS resin film is used as the base material layer. In this case, the temperature can be usually about 100 to 250 ° C, preferably about 130 to 200 ° C. In addition, in the integration step, the temperature of the resin in a fluidized state is not particularly limited, but may be generally about 180 to 320 ° C, preferably about 220 to 280 ° C.

  Further, in the simultaneous injection molding decoration method, the decorative sheet of the present invention is arranged in a female mold that is also used as a vacuum forming mold provided with a suction hole for injection molding, and preforming (in-line preforming) is performed with this female mold. After the injection molding, the injection molding die is closed, the resin in a fluid state is injected and filled into the mold, and solidified. At the same time as the injection molding, the surface layer 2 of the decorative sheet of the present invention is formed on the outer surface of the resin molded product. By integrating the side (the side opposite to the concavo-convex protective layer 3), a decorative resin molded article with the concavo-convex protective layer is manufactured.

  More specifically, the decorative resin molded article with the concavo-convex protection layer of the present invention is manufactured by the simultaneous injection molding and decoration method including the following steps.

The decorative sheet of the present invention is installed so that the surface layer 2 side of the decorative sheet (the side opposite to the unevenness protective layer 3) faces the molding surface of the movable mold having a molding surface of a predetermined shape. After that, while heating and softening the decorative sheet, vacuum suction from the movable mold side, the softened decorative sheet is brought into close contact along the molding surface of the movable mold, the decorative sheet Preforming process,
After clamping the movable mold and the fixed mold having the decorative sheet adhered along the molding surface, the resin molding material in a flowing state is injected and filled into the cavity formed by both molds. An injection molding step in which the formed resin molded body and the decorative sheet are laminated and integrated by solidification, and a resin molded body in which the movable mold is separated from the fixed mold and all layers of the decorative sheet are laminated. Step of taking out.

  In the preliminary molding step of the injection molding simultaneous decorating method, the heating temperature of the decorating sheet is not particularly limited, and may be appropriately selected according to the type of resin constituting the decorating sheet, the thickness of the decorating sheet, etc. In the case where 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 addition, in the injection molding step, the temperature of the resin in a fluidized state is not particularly limited, but can be generally about 180 to 320 ° C, preferably about 220 to 280 ° C.

  Further, the decorative resin molded product of the present invention is obtained by a decorating method of attaching the decorative sheet of the present invention onto a previously prepared three-dimensional resin molded product (molded resin layer) such as a vacuum compression method. Can also be produced.

  In the vacuum compression bonding method, first, the decorative sheet and the resin molded body of the present invention are placed in a vacuum pressing machine including a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side, and the decorative sheet is placed in the first vacuum chamber. Installed in the vacuum crimping machine so that the vacuum chamber side and the resin molded body are on the second vacuum chamber side, and the surface layer 2 side of the decorative sheet (the side opposite to the unevenness protective layer 3) faces the resin molded body side. Then, the two vacuum chambers are evacuated. The resin molded body is installed on a vertically movable platform provided on the second vacuum chamber side. Next, while the first vacuum chamber is pressurized, the molded body is pressed against the decorative sheet using the elevating table, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Stick on the surface of. Finally, the two vacuum chambers are opened to the atmospheric pressure, and an extra portion of the decorative sheet is trimmed if necessary, whereby the decorative resin molded product of the present invention can be obtained.

  In the vacuum compression bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and enhance the formability before the step of pressing the formed body against the decorative sheet. The vacuum compression bonding method including this step may be particularly called a vacuum heat compression bonding method. The heating temperature in this step may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, provided that a polyester resin film or an acrylic resin film is used as the base material layer. , Usually about 60 to 200 ° C.

  In the decorative resin molded article with the concavo-convex protective layer of the present invention, the molding resin layer may be formed by selecting a molding 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. One of these thermoplastic resins may be used alone, or two or more thereof may be used in combination.

  Examples of the thermosetting resin used as the molding resin include a urethane resin and an epoxy resin. One of these thermosetting resins may be used alone, or two or more thereof may be used in combination.

  The decorative resin molded article can be obtained by peeling and removing the uneven protective layer from the decorative resin molded article with the uneven protective layer of the present invention. Further, in the decorative resin molded article with a concave-convex protective layer, the concave-convex protective layer plays a role as a protective sheet for the decorative resin molded article. May be peeled off. By using in this manner, it is possible to prevent the decorative resin molded product from being damaged due to rubbing or the like during transportation.

3. Decorated Resin Molded Product By peeling and removing the concavo-convex protective layer 3 from the decorated resin molded product with the concavo-convex protective layer, a decorated resin molded product having a surface with a concavo-convex shape can be obtained. When the support is peeled and removed from the decorative resin molded article having the uneven protective layer, the surface layer 2 appears on the surface of the decorative resin molded article, and the uneven shape gives an excellent design feeling and touch feeling. FIG. 5 shows a cross-sectional structure of one embodiment of a decorative resin molded product from which the unevenness protective layer 3 has been removed.

  Since the decorative resin molded product of the present invention has an excellent design feeling and feel due to the uneven shape, for example, interior materials or exterior materials of vehicles such as automobiles; It can be used as fittings such as window frames and door frames; interior materials for buildings such as walls, floors and ceilings; housings for home electric 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 embodiments.

[Manufacture of decorative sheets]
Example 1
An ABS resin film (thickness: 200 μm) was used as the base material layer. A wood-grained pattern layer (5 μm thick) was formed on the base layer by gravure printing using an ink composition containing an acrylic resin. On a pattern layer, a resin composition for a primer layer containing a binder resin composed of a two-part curable resin containing 100 parts of a main agent (acryl polyol / urethane, mass ratio 9/1) and 7 parts of a curing agent (hexamethylene diisocyanate) is used. Coating and drying were performed to form a primer layer having a thickness of 2 μm, and a laminate in which a substrate layer / a pattern layer / a primer layer was sequentially laminated was obtained.

  An embossing process was performed on the primer layer side of the laminate obtained above to form a dot pattern uneven shape on the primer layer. The embossing plate depth (height from the bottom of the concave portion to the upper surface of the convex portion) of the embossing plate used for embossing is 60 μm. Next, the ionizing radiation-curable resin composition (EB1) shown in Table 1 was applied on the primer layer having the uneven shape so that the thickness after curing became 8 μm. The resin composition was irradiated with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to be cured, thereby forming a surface layer having an uneven shape.

  Next, on the surface layer, an adhesive made of a polyester resin composition was applied so that the thickness after curing became 30 μm, and an adhesive layer was formed by filling the concaves and convexes of the surface layer. . Next, a release film layer (thickness: 30 μm) formed of polyethylene is laminated on the adhesive layer, and a base layer / a pattern layer / a primer layer / a surface layer having an uneven shape / an uneven protective layer (adhesive layer / A release sheet having a laminated structure in which the release film layers were sequentially laminated was obtained.

Example 2
An acrylic resin film (thickness: 75 μm) was used as a surface layer. On the surface layer, a wood-grain pattern layer (5 μm thick) was formed by gravure printing using an ink composition containing an acrylic resin. An ABS resin film (200 μm in thickness) as a base material layer was laminated on the picture layer. Next, embossing was performed on the surface layer side of the obtained laminate to form a dot-shaped unevenness on the surface layer. The embossing plate used for embossing is the same as in Example 1. As described above, a laminate in which the base material layer / the pattern layer / the surface layer having the uneven shape was sequentially laminated was obtained. Next, in the same manner as in Example 1, an adhesive layer and a release film were laminated on the surface layer, and a base layer / a pattern layer / a surface layer having an uneven shape / an uneven protective layer (adhesive layer / release film layer). ) Were sequentially obtained to obtain a decorative sheet having a laminated structure.

Example 3
In the same manner as in Example 1, after obtaining a laminate in which the base material layer / pattern layer / primer layer was sequentially laminated, the irregular shape was obtained using the ionizing radiation-curable resin composition (EB2) shown in Table 1. Was formed. On the other hand, an ionizing radiation-curable resin composition (EB3) described later was applied on the surface layer so that the thickness after curing became 10 μm. The resin composition was irradiated with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to be cured to form a release layer on the surface layer.

  Next, on the release layer, an adhesive made of a polyester resin composition is applied so that the thickness after curing becomes 30 μm, and an adhesive layer is formed so as to fill the concaves and convexes of the surface layer. did. Next, the above-mentioned release film layer is laminated from the adhesive layer side on the adhesive layer, and the base layer / picture layer / primer layer / surface layer having irregularities / unevenness protective layer (release layer / adhesive layer) Layer / release film layer) in this order to obtain a decorative sheet having a laminated structure.

Comparative Example 1
Substrate layer / Picture layer / Surface layer with uneven shape / Uneven protective layer (polyethylene layer) in the same manner as in Example 2 except that a polyethylene layer was formed by extrusion on the surface layer having the uneven shape. ) Were sequentially obtained to obtain a decorative sheet having a laminated structure. In addition, as conditions of the extrusion molding, the temperature under the die of the extruder was 230 to 250 ° C., and the thickness of the polyethylene layer was 50 μm.

Comparative Example 2
A polyethylene film (thickness: 50 μm) was laminated on a surface layer having an uneven shape, and the surface layer and the release film layer were bonded by a thermal lamination method in the same manner as in Example 1, except that A decorative sheet having a laminated structure in which a pattern layer / a primer layer / a surface layer having a concavo-convex shape / a concavo-convex protective layer (polyethylene film layer) was sequentially laminated was obtained. The conditions for the thermal lamination method were a heating temperature of 200 to 230 ° C. and a pressure of 5 kgf / cm ² .

[Manufacture of decorative resin molded products]
Each decorative sheet was heated to 160 ° C. with an infrared heater to be softened. Next, vacuum forming was performed using a vacuum forming mold (maximum stretch ratio: 100%), and preforming was performed so as to conform to the internal shape of the mold, followed by clamping. Thereafter, a mixed resin of polycarbonate and ABS was injected into the cavity of the mold, and the decorative sheet and the molding resin were integrally molded to obtain a decorative resin molded article with a concavo-convex protective layer. Next, the decorative resin layer was peeled by hand from the obtained decorative resin molded article having the concave-convex protective layer to obtain a decorative resin molded article.

<Evaluation of uneven shape>
In order to evaluate the uneven shape of the surface of the decorative resin molded product, the center line average roughness (Ra) and the maximum were measured using a surface roughness and contour shape measuring device (Hardy Surf E-35A manufactured by Tokyo Seimitsu Co., Ltd.). The height (Rmax) and the ten-point average height (Rz) were measured. Table 1 shows the results.

<Evaluation of uneven shape of decorative sheet>
In the process of manufacturing the decorative sheets of Examples and Comparative Examples, the unevenness of the surface layer before and after the formation of the unevenness protective layer was evaluated visually and by touch for unevenness. In addition, peeling of the unevenness protective layer from the decorative sheet was performed by peeling the unevenness protective layer from the decorative sheet by hand. The evaluation criteria are as follows. Table 1 shows the results.
〇: There was almost no change in unevenness.
Δ: The unevenness was slightly changed.
X: The unevenness was significantly changed and the unevenness was not felt.

<Evaluation of uneven shape of decorative resin molded product>
Regarding the change in the uneven shape before and after manufacturing the decorative resin molded product from each decorative sheet, the feeling of unevenness was evaluated visually and by touch. The evaluation criteria are as follows. Table 1 shows the results.
〇: Even after the decorative resin molded article was formed, there was almost no change in the unevenness, and the unevenness was strongly felt.
Δ: The unevenness was slightly changed after the decorative resin molded product was formed.
×: After forming a decorative resin molded product, the unevenness was significantly changed and the unevenness was not felt.

  In Table 1, "-" indicates that no measurement was performed.

EB1
Bifunctional polycarbonate acrylate (weight average molecular weight; 10,000): 95 parts by mass Tetrafunctional urethane acrylate oligomer (weight average molecular weight; 6,000): 5 parts by mass
EB2
Bifunctional polycarbonate acrylate (weight average molecular weight; 8,000): 95 parts by mass Bifunctional silicone acrylate oligomer (weight average molecular weight; 6,000): 5 parts by mass
EB3
Trifunctional pentaerythritol acrylate (weight average molecular weight; 300): 30 parts by mass Acrylic polymer (weight average molecular weight 120,000): 70 parts by mass
Polyester resin composition for adhesive layer Polyester polyol: isocyanate = 100: 10
Polyethylene extruded in Comparative Example 1 Extruded grade low density PE
Polyethylene film heat-laminated in Comparative Example 2 Low-density PE film

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Surface layer 3 Concavo-convex protection layer 4 Primer layer 5 Picture layer 6 Transparent resin layer 7 Molding resin layer 30 Release film layer 31 Adhesive layer 32 Release layer

Claims (15)

At least, a surface layer having an uneven shape, and a peelable unevenness protective layer are laminated,
The unevenness protective layer includes, in order from the surface layer side, an adhesive layer filling a concave portion of the unevenness of the surface layer, and a release film layer,
The surface layer is formed by a cured product of a curable resin composition, or a resin film,
A decorative sheet, wherein the adhesive layer is formed of a cured product of a two-component curable urethane resin-based adhesive. The unevenness protective layer includes, in order from the surface layer side, a release layer, the adhesive layer, and the release film layer,
2. The decorative sheet according to claim 1, wherein the release layer and the adhesive layer fill in concaves and convexes of the surface layer. 3.   The decorative sheet according to claim 1, wherein the release layer is formed of a cured product of the ionizing radiation-curable resin composition. The decorative sheet according to any one of claims 1 to 3 , wherein a primer layer is laminated immediately below the surface layer. The decorative sheet according to any one of claims 1 to 4 , wherein a picture layer is laminated on a side of the surface layer opposite to the unevenness protective layer. The decorative sheet according to any one of claims 1 to 5, which has a base material layer. On the side opposite to the unevenness protective layer side of the surface layer, has a substrate layer,
  The decorative sheet according to any one of claims 1 to 6, wherein a concave portion of the concave-convex shape of the surface layer reaches the base layer. The decorative sheet according to claim 7, further comprising a picture layer between the surface layer and the base layer. A first step of preparing a surface layer having an uneven shape,
A second step of applying an adhesive on the surface layer so as to fill the concaves and convexes of the surface layer, and laminating the adhesive layer,
A third step of laminating a release film layer on the adhesive layer;
With
The surface layer is formed by a cured product of a curable resin composition, or a resin film,
A method for manufacturing a decorative sheet, wherein the adhesive layer is formed of a cured product of a two-component curable urethane resin-based adhesive. The method for manufacturing a decorative sheet according to claim 9 , wherein the first step includes the following steps.
A step of laminating a pattern layer and a primer layer in this order on the base material layer,
Performing an embossing process on the primer layer, and forming an uneven shape on the surface of the primer layer,
A step of applying a curable resin composition over the primer layer, curing the composition, and laminating a surface layer having an uneven shape. The method for manufacturing a decorative sheet according to claim 9 , wherein the first step includes the following steps.
A step of preparing a surface layer made of a resin film;
A step of performing embossing from above the surface layer to form irregularities on the surface of the surface layer. The method for manufacturing a decorative sheet according to claim 9 , wherein the first step includes the following steps.
A step of laminating a pattern layer and a primer layer in this order on the base material layer,
A step of laminating a resin film on the primer layer and laminating a surface layer,
A step of performing embossing from above the surface layer to form irregularities on the surface of the surface layer. At least, a molded resin layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order,
The unevenness protective layer includes, in order from the surface layer side, an adhesive layer filling a concave portion of the unevenness of the surface layer, and a release film layer,
The surface layer is formed by a cured product of a curable resin composition, or a resin film,
A decorative resin molded article with a concavo-convex protection layer, wherein the adhesive layer is formed of a cured product of a two-component curable urethane resin-based adhesive. A method for producing a decorative resin molded product, comprising a step of peeling the uneven protective layer from the decorative resin molded product with the uneven protective layer according to claim 13 . A method for producing a decorative resin molded article with a concavo-convex protection layer, comprising a step of injecting a resin onto the surface layer side of the decorative sheet according to any one of claims 1 to 8 to form a molded resin layer.