JP7135268B2 - decorative sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a decorative sheet having an uneven shape and having both excellent moldability and chemical resistance.

BACKGROUND ART Decorated resin molded products obtained by laminating a decorative sheet on the surface of a resin molded product are used for vehicle interior parts, building interior materials, home appliance housings, and the like. As a method for molding such a decorative resin molded product, a decorative sheet is formed into a three-dimensional shape in advance using a vacuum forming mold, the molded sheet is inserted into an injection mold, and a resin in a fluid state is injected into the mold. An insert molding method that integrates resin and a molded sheet by injection (see, for example, Patent Document 1), a decorative sheet inserted into a mold during injection molding, and a molten resin that is injected into a cavity. An injection-molding simultaneous decoration method (see, for example, Patent Documents 2 and 3) is known, in which the resin molding is integrated and the surface of the resin molded body is decorated.

The decorative sheet used in these methods is generally provided with a surface protective layer for the purpose of improving the scratch resistance of the surface of the decorative resin molded article. However, in the molding method of the above-mentioned decorative resin molded product, for example, in the insert molding method, the decorative sheet is formed in advance into a three-dimensional (three-dimensional) shape with a vacuum mold, and in the injection molding simultaneous decoration method, the decoration When the sheet is stretched along the inner surface of the cavity during preforming or injection of molten resin, the decorative sheet is stretched by the action of vacuum pressure, or by pulling due to the pressure of the molten resin, shear stress, etc. Since the molded product is stretched by more than the minimum required amount to conform to the shape of the mold, there is a problem that cracks occur in the surface protective layer of the curved surface portion of the molded product.

As a method for solving such problems, for example, Patent Document 4 discloses a decorative sheet having at least a surface protective layer on a base material, wherein the surface protective layer is composed of at least polycarbonate (meth)acrylate and polyfunctional (meth)acrylate. and an acrylate, and the mass ratio of the polycarbonate (meth)acrylate and the polyfunctional (meth)acrylate is polycarbonate (meth)acrylate:polyfunctional (meth)acrylate = 98:2 to 70:30. discloses a technique of forming a cured product of a flexible resin composition.

Japanese Patent Application Laid-Open No. 2004-322501 Japanese Patent Publication No. 50-19132 Japanese Patent Publication No. 61-17255 JP 2011-73373 A

The decorative sheet disclosed in Patent Document 4 has excellent moldability and can impart excellent scratch resistance to the decorative resin molded product.

However, in recent years, in addition to moldability, decorative sheets used for the production of decorative resin molded products have the function of imparting stain resistance to various products used in daily life to the decorative resin molded products. are required to have In particular, in recent years, skin care products such as sunscreen cosmetics and chemicals containing alcohol have tended to be frequently used. The frequency of chemicals adhering to decorative resin molded products is increasing, and there is a strong demand for decorative sheets to have even better chemical resistance to chemicals that are highly corrosive to resin surfaces. .

On the other hand, with the diversification of consumer needs, there is a demand for decorative resin molded products with various designs. In order to meet such diversifying consumer needs, there is a demand for the development of decorative resin moldings that have a sense of design and a sense of touch based on the uneven shape of the surface.

2. Description of the Related Art A decorative sheet whose surface is pre-formed with an uneven surface is used to manufacture a decorative resin molded product having an uneven surface. However, in the case of producing a decorative resin molded product using a decorative sheet having an uneven shape, when the decorative sheet is subjected to injection molding or preforming (vacuum molding) prior to injection molding, heat and pressure cause the uneven shape to become a starting point. Such cracks are likely to occur. Therefore, there is a problem that a decorative sheet having an uneven shape is inferior in moldability to a decorative sheet having a flat surface as disclosed in Patent Document 4, for example.

Under such circumstances, the present invention has excellent moldability despite having an uneven shape, and furthermore, imparts excellent chemical resistance, abrasion resistance, etc. to decorative resin molded products. The main purpose is to provide a decorative sheet that can be Another object of the present invention is to provide a decorative resin-molded article using the decorative sheet and a method for producing the same.

The inventors of the present invention have made intensive studies to solve the above problems. As a result, it is composed of a laminate comprising at least a substrate layer and a surface layer having an uneven shape, and the surface layer contains an ionizing radiation curable resin and a thermoplastic resin at a ratio of 10:90 to 25:75. The decorative sheet, which is a cured product of the resin composition contained in the mass ratio, has excellent moldability despite having an uneven shape, and has excellent chemical resistance to decorative resin molded products. , wear resistance, etc. can be imparted. The present invention has been completed through further studies based on such findings.

That is, the present invention provides inventions in the following aspects.
Section 1. It is composed of a laminate comprising at least a base material layer and a surface layer having an uneven shape,
The decorative sheet, wherein the surface layer is a cured product of a resin composition containing an ionizing radiation-curable resin and a thermoplastic resin at a mass ratio of 10:90 to 25:75.
Section 2. Item 2. The decorative sheet according to Item 1, wherein the center line average roughness Ra of the surface of the surface layer opposite to the substrate layer is 3 μm or more and 21 μm or less.
Item 3. Item 3. The decorative sheet according to Item 1 or 2, wherein a peelable thermoplastic resin film layer is provided on the surface of the surface layer opposite to the substrate layer.
Section 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the thermoplastic resin has a weight average molecular weight in the range of 90,000 or more and 150,000 or less.
Item 5. Item 5. The decorative sheet according to any one of items 1 to 4, wherein the number of functional groups of the monomer contained in the ionizing radiation curable resin is in the range of 2 to 6.
Item 6. Item 6. The decorative sheet according to any one of items 1 to 5, wherein the molecular weight of the monomer contained in the ionizing radiation curable resin is in the range of 200 or more and 2000 or less.
Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, which is used in an insert molding method or an injection molding simultaneous decoration method.
Item 8. Item 8. The decorative sheet according to any one of Items 1 to 7, wherein a primer layer is laminated directly below the surface layer.
Item 9. Item 9. The decorative sheet according to any one of Items 1 to 8, wherein a pattern layer is laminated between the base material layer and the surface layer.
Item 10. At least, a molding resin layer, a substrate layer, and a surface layer having an uneven shape are laminated in this order,
The decorative resin molded product, wherein the surface layer is a cured product of a resin composition containing an ionizing radiation-curable resin and a thermoplastic resin at a mass ratio of 10:90 to 25:75.
Item 11. Item 10. A method for producing a decorated resin molded product, comprising a step of laminating a molded resin layer on the base layer side of the decorative sheet according to any one of Items 1 to 9 by injecting a resin.

According to the present invention, the decorative sheet has excellent moldability despite having an uneven shape, and can impart excellent chemical resistance, abrasion resistance, etc. to the decorative resin molded product. can be provided. Further, according to the present invention, it is possible to provide a decorative resin molded article 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 this invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of this invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of this invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded article with a thermoplastic resin film layer of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molding of this invention.

1. Decorative Sheet The decorative sheet of the present invention is formed by laminating at least a base material layer and a surface layer having an uneven shape, and the surface layer contains an ionizing radiation curable resin and a thermoplastic resin at a ratio of 10:90. It is characterized by being a cured product of a resin composition containing at a mass ratio of 25:75. By having such a specific configuration, the decorative sheet of the present invention has excellent moldability in spite of having an uneven shape, and is also excellent for decorative resin molded products. It is possible to impart chemical resistance, wear resistance, etc.

The decorative sheet of the present invention will be described in detail below. In this specification, numerical ranges indicated by "-" mean "above" and "below", except where "above" and "below" are specified. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, in this specification, "(meth)acrylate" means "acrylate or methacrylate", and other similar terms have the same meaning. Moreover, the decorative sheet of the present invention may not have a pattern layer or the like, and may be transparent, for example.

Laminated Structure of Decorative Sheet The decorative sheet of the present invention has a laminated structure in which at least a substrate layer 1 and a surface layer 2 having an uneven shape are laminated.

The decorative sheet of the present invention is applied, if necessary, on the surface of the surface layer 2 opposite to the base layer 1 side for the purpose of protecting the uneven shape of the surface layer 2 during injection molding or the like. , a peelable thermoplastic resin film layer 3 may be provided. The surface layer 2 and the thermoplastic resin film layer 3 may be directly laminated, or another layer may be laminated between these layers. Other layers include, for example, a release layer (not shown). It is preferable that the thermoplastic resin film layer 3 and further the release layer fill the uneven concave portions of the surface layer 2 .

In the present invention, when a release layer is provided, the peel strength of the thermoplastic resin film layer from the decorative sheet or the decorative resin molded product described later is measured at the interface between the surface layer 2 and the release layer. means peel strength.

In the decorative sheet of the present invention, a primer layer 4 may be provided between the base layer 1 and the surface layer 2, if necessary, for the purpose of enhancing the adhesion between the layers.

A pattern layer 5 may be provided between the base material layer 1 and the surface layer 2 as needed for the purpose of imparting decorativeness. When the primer layer 4 is provided, the pattern layer 5 may be provided between the base material layer 1 and the primer layer 4 .

In addition, a masking layer (not shown) may be provided between the base layer 1 and the surface layer 2 as necessary for the purpose of suppressing color change and unevenness of the base layer 1 . In the case of providing the primer layer 4, the concealing layer may be provided between the base layer 1 and the primer layer 4. In the case of providing the pattern layer 5, the concealing layer is the base layer. It may be provided between 1 and the pattern layer 5 .

Furthermore, between the base material layer 1 and the surface layer 2, a transparent resin layer (not shown) may be provided as necessary for the purpose of improving abrasion resistance (scratch resistance). When the primer layer 4 is provided, the transparent resin layer may be provided between the pattern layer 5 and the primer layer 4 .

Furthermore, in the decorative sheet of the present invention, the back surface of the base material layer 1 (the surface opposite to the surface layer 2) is added for the purpose of improving the adhesion to the molding resin when molding the decorative resin molded product. may be provided with a back adhesive layer (not shown) as needed.

Examples of the laminated structure of the decorative sheet of the present invention include a laminated structure in which base layer 1/surface layer 2 is laminated; and a laminated structure in which base layer 1/surface layer 2/thermoplastic resin film layer 3 are laminated in this order. Laminated structure in which substrate layer 1 / surface layer 2 / release layer / thermoplastic resin film layer 3 are laminated in order; substrate layer 1 / pattern layer 5 / surface layer 2 / thermoplastic resin film layer 3 are laminated in order laminated structure; substrate layer 1 / pattern layer 5 / primer layer 4 / surface layer 2 / thermoplastic resin film layer 3 laminated in order; substrate layer 1 / pattern layer 5 / primer layer 4 / surface Laminated structure in which layer 2 / release layer / thermoplastic resin film layer 3 are laminated in order; substrate layer 1 / pattern layer 5 / transparent resin layer / primer layer 4 / surface layer 2 / thermoplastic resin film layer 3 in order Laminated laminated structure etc. are mentioned.

1 and 2 show cross-sectional views of a decorative sheet in which base layer 1/surface layer 2 are laminated as one embodiment of the laminated structure of the decorative sheet of the present invention. FIG. 3 shows a cross-sectional view of a decorative sheet in which base layer 1/surface layer 2/thermoplastic resin film layer 3 are laminated in this order, as one embodiment of the laminated structure of the decorative sheet of the present invention. FIG. 4 shows a decorative sheet in which base layer 1/pattern layer 5/primer layer 4/surface layer 2/thermoplastic resin film layer 3 are laminated in this order as one embodiment of the laminated structure of the decorative sheet of the present invention. A cross-sectional view is shown.

Composition of each layer of the decorative sheet [base layer 1]
The base material layer 1 is a resin sheet (resin film) that serves as a support in the decorative sheet of the present invention. The resin component used in the base material layer 1 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the molding resin, etc., but preferably a resin film made of a thermoplastic resin. mentioned. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin") and acrylonitrile-styrene-acrylic acid ester resin (hereinafter referred to as "ASA resin"). polyolefin resins such as acrylic resins, polypropylene and polyethylene, polycarbonate resins, vinyl chloride resins, and polyethylene terephthalate (PET). Among these, ABS resins and acrylic resins are preferable from the viewpoint of three-dimensional moldability. Further, the substrate 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 bending elastic modulus of the base material layer 1 is not particularly limited. For example, when the decorative sheet of the present invention is integrated with a molding resin by an insert molding method, the bending elastic modulus at 25° C. of the substrate layer 1 in the decorative sheet of the present invention is 500 to 4,000 MPa, preferably 750 to 3,000 MPa can be mentioned. Here, the flexural modulus at 25°C is a value measured according to JIS K7171. If the flexural modulus at 25° C. is 500 MPa or more, the decorative sheet will have sufficient rigidity, and even if it is subjected to the insert molding method, the surface properties and moldability will be much better. In addition, 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 slack is less likely to occur, so the pattern is printed over and over again without shifting. The so-called pattern registration becomes good.

In order to improve the adhesion with the layer provided thereon, the substrate layer 1 is subjected to a physical or chemical surface treatment such as an oxidation method or roughening method on one side or both sides, if necessary. may Examples of the oxidation method for the surface treatment of the substrate layer 1 include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment, and the like. Further, examples of the roughening method performed as the surface treatment of the base material layer 1 include a sandblasting method, a solvent treatment method, and the like. These surface treatments are appropriately selected according to the type of the resin component that constitutes the substrate layer 1, but from the viewpoint of effects, operability, and the like, a corona discharge treatment method is preferred.

Further, the substrate layer 1 may be subjected to a treatment such as forming a known adhesive layer.

Furthermore, the base material layer 1 may be colored using a coloring agent, or may be uncolored. Moreover, the base material layer 1 may be in any form of colorless and transparent, colored and transparent, and translucent. The coloring agent used for the substrate layer 1 is not particularly limited, but preferably includes a coloring agent that does not change color even under temperature conditions of 150° C. or higher. Specifically, existing dry colors, paste colors, and masterbatch resins. composition and the like.

The thickness of the base material layer 1 is appropriately set according to the application of the decorative sheet, the molding method for integration with the molding resin, and the like, and is usually about 25 to 1000 μm and about 50 to 700 μm. More specifically, when the decorative sheet of the present invention is subjected to insert molding, the thickness of the substrate layer 1 is usually about 50 to 1000 μm, preferably about 100 to 700 μm, more preferably 100 to 500 μm. degree. Further, when the decorative sheet of the present invention is subjected to the simultaneous injection molding decoration method, the thickness of the base material layer 1 is usually about 25 to 200 μm, preferably about 50 to 200 μm, more preferably about 70 to 200 μm. is mentioned.

[Surface layer 2]
The surface layer 2 has an uneven surface on the side opposite to the base material layer 1 . The surface layer 2 is made of a cured resin composition containing an ionizing radiation curable resin and a thermoplastic resin at a mass ratio of 10:90 to 25:75. As described above, the surface layer 2 having an uneven shape is composed of a cured product of a resin composition containing an ionizing radiation-curable resin and a thermoplastic resin in the above-described specific ratio, so that the decorative sheet of the present invention can Although the surface layer 2 has an uneven shape, it has excellent moldability, and can impart excellent chemical resistance and abrasion resistance to the decorative resin molded product.

<Uneven shape>
The uneven shape of the surface layer 2 is not particularly limited, and may be appropriately set according to the design feeling to be imparted. Examples of the uneven shape include hairline patterns, wood grain patterns, geometric patterns (dots, stripes, carbon, etc.).

In addition, the height of the protrusions, the width of the protrusions, the pitch between adjacent protrusions, the width of the recesses, etc. in the uneven shape of the surface layer 2 are determined according to the design feeling to be imparted to the decorative resin molded product. can be set as appropriate.

For example, the center line average roughness (Ra) of the surface of the surface layer 2 opposite to the base layer 1 side is usually 3 to 21 μm, preferably 3, from the viewpoint of imparting an excellent design feeling due to the uneven shape. up to 20 μm, more preferably 3 to 15 μm. If the center line average roughness is 21 μm or less, when the decorative sheet is rolled into a roll and stored, etc., the excessive unevenness may cause damage, breakage, collapse of the roll, etc. during transportation. is preferred.

From the same point of view, the maximum height (Rz) of the surface of the surface layer 2 opposite to the substrate layer 1 side is usually 1.0 to 100 μm, preferably 1.0 to 80 μm, more preferably 1.0 to 60 μm can be mentioned. From the same point of view, the ten-point average height (Rzjis) of the surface of the surface layer 2 opposite to the base layer 1 side is usually 1.0 to 100 μm, preferably 1.0 to 80 μm, more preferably 1.0 to 60 μm can be mentioned. Note that the center line average roughness (Ra), the maximum height (Rz), and the ten-point average height (Rzjis) are each in accordance with the provisions of JIS B 0601: 2001, and the surface layer 2 of the decorative sheet It is a value measured with the thermoplastic resin film layer 3 peeled from the surface (the part where the uneven shape is formed).

Further, the uneven shape formed by the surface layer 2 may be such that the bottom of the recess is formed by the surface layer 2 as in the embodiment shown in FIG. The lower layer of the surface layer 2 may be exposed, and the surface layer 2 may be partially provided to form projections. The former is preferable from the viewpoint of protecting the surface of the decorative resin molded product. FIGS. 1 and 2 show an uneven shape formed by, for example, a method of applying embossing which will be described later. 1 and 2 show a laminated structure in which only the substrate layer 1 and the surface layer 2 are laminated for convenience.

In the decorative sheet of the present invention, the 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 concave-convex shape that satisfies the above relationship may be formed in a part of the area or may be formed in the entire area.

Further, the uneven shape may be formed only on the surface layer 2, or a layer (for example, the primer layer 4, the pattern layer 5, the base layer 1 etc.). From the viewpoint of effectively suppressing disappearance, deformation, etc. of the uneven shape during injection molding of the decorative sheet, it is preferable that the recesses of the uneven shape reach the base material layer 1 .

<Composition>
The surface layer 2 is formed of a cured product of a resin composition containing an ionizing radiation-curable resin, a thermoplastic resin, and the above specific ratio. The mass ratio of the ionizing radiation curable resin to the thermoplastic resin in the surface layer 2 may be ionizing radiation curable resin:thermoplastic resin=10:90 to 25:75, but more preferably 15. : about 85 to 25:75, more preferably about 20:80 to 25:75.

The thermoplastic resin is not particularly limited, but preferably acrylic resin, acrylic-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, rubber system resin and the like. Among these, the standpoint is to effectively improve the moldability of the decorative sheet while imparting excellent chemical resistance and wear resistance to the decorative resin molded product, as well as an excellent design feeling based on the uneven shape. Among them, acrylic resins are particularly preferred.

Acrylic resins include homopolymers of (meth)acrylic acid esters, copolymers of two or more different (meth)acrylic acid ester monomers, and copolymers of (meth)acrylic acid esters and other monomers. Specific examples include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polypropyl (meth)acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate-(meth) ( A (meth)acrylic resin composed of a homopolymer or a copolymer containing a meth)acrylic acid ester is preferably used.

The weight-average molecular weight of the thermoplastic resin is not particularly limited, but it effectively enhances the moldability of the decorative sheet, and has excellent chemical resistance, abrasion resistance, and uneven shape for the decorative resin molded product. From the viewpoint of imparting an excellent design feeling etc. based on, it is preferably about 90,000 to 150,000, more preferably about 100,000 to 140,000, still more preferably about 110,000 to 130,000.

The weight average molecular weight of the thermoplastic resin in this specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

(Ionizing radiation curable resin)
The ionizing radiation-curable resin used for forming the surface layer 2 refers to a resin that is crosslinked and cured by irradiation with ionizing radiation. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam that has an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used. , X-rays, γ-rays, and other electromagnetic waves, α-rays, ion beams, and other charged particle beams. Among ionizing radiation curable resins, electron beam curable resins can be solvent-free, do not require a photopolymerization initiator, and provide stable curing properties, so they are suitable for use in forming the surface layer. be done.

Specific examples of ionizing radiation-curable resins include those obtained by appropriately mixing prepolymers, oligomers, and/or monomers having polymerizable unsaturated bonds or epoxy groups in the 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 suitable. Polyfunctional (meth)acrylate oligomers with higher functionality are preferred. Examples of polyfunctional (meth)acrylate oligomers 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, oligomers having cationic polymerizable functional groups in the molecule (e.g., novolac 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 the polymer main chain and a (meth)acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid. Polycarbonate (meth)acrylate may be, for example, urethane (meth)acrylate having a polycarbonate skeleton. A urethane (meth)acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and a hydroxy (meth)acrylate. Acrylic silicone (meth)acrylates can be obtained by radically copolymerizing silicone macromonomers with (meth)acrylate monomers. A urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting 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 relatively low-molecular-weight bisphenol-type epoxy resin or novolac-type epoxy resin for esterification. A carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic acid anhydride can also be used. Polyester (meth)acrylate is obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyhydric carboxylic acid and polyhydric alcohol with (meth)acrylic acid, or to polyhydric carboxylic acid. It can be obtained by esterifying the terminal hydroxyl group of the oligomer obtained by adding alkylene oxide with (meth)acrylic acid. Polyether (meth)acrylate can be obtained by esterifying the hydroxyl groups of polyether polyol with (meth)acrylic acid. Polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of polybutadiene oligomer. A silicone (meth)acrylate can be obtained by adding (meth)acrylic acid to the terminal or side chain of a silicone having a polysiloxane bond in its main chain. A silicone-modified urethane (meth)acrylate can be obtained, for example, by reacting a urethane prepolymer having an isocyanate group with a silicone compound having a silanol group together with a hydroxy (meth)acrylate. These oligomers may be used singly or in combination of two or more.

As the monomer used as the ionizing radiation-curable resin, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and among these, a polyfunctional (meth)acrylate monomer is preferable. A (meth)acrylate monomer having two or more polymerizable unsaturated bonds in the molecule may be used as the polyfunctional (meth)acrylate monomer. Specific examples of polyfunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, (Meth)acrylates, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentylglycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate (Meth)acrylates, 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 Acrylates, ethylene oxide-modified bisphenol A di(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth) Acrylates, 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 singly or in combination of two or more.

Among these ionizing radiation-curable resins, it effectively enhances the moldability of decorative sheets, and has excellent chemical resistance and wear resistance for decorative resin molded products. From the viewpoint of imparting sensation and the like, the number of functional groups of the monomer contained in the ionizing radiation-curable resin is preferably in the range of 2 to 6, more preferably in the range of 2 to 4. Further, the molecular weight of the monomer contained in the ionizing radiation curable resin is preferably about 200-2000, more preferably about 200-1500, still more preferably about 200-1000.

Furthermore, among these monomers, dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, (Meth)acrylates and the like are particularly preferred.

<Other additives>
Various additives can be added to the resin composition used to form the surface layer 2 according to the desired physical properties of the surface layer 2 . Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, etc. , a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a coloring agent, a wax, and the like. These additives can be appropriately selected and used from commonly used ones. As the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used. By adding wax, scratch resistance and wear resistance can be improved. Waxes preferably include olefin waxes such as polyethylene wax (PE wax). When wax is blended, the blending amount in the curable resin composition is preferably about 0.1 to 5% by mass, more preferably about 0.5 to 3% by mass.

Moreover, the surface layer 2 may contain a matting agent. The matting agent is not particularly limited, and examples thereof include inorganic particles and synthetic resin particles.

Preferred examples of inorganic particles include silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, kaolin, and hydrophobically treated products thereof. These inorganic particles may be used singly or in combination of two or more. Preferable synthetic resin particles include acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, polyolefin wax (polypropylene wax, polyethylene wax, mixtures thereof, etc.), and the like. These synthetic resin particles may be used singly or in combination of two or more.

The surface layer 2 may contain either inorganic particles or synthetic resin particles, or may contain a combination thereof. The average particle size of the inorganic particles and the synthetic resin particles is preferably 0.1 to 5 μm, more preferably 1 to 5 μm, even more preferably 2 to 5 μm, from the viewpoint of improving the design. The particle size of the inorganic particles and synthetic resin particles was measured using a Shimadzu laser diffraction particle size distribution analyzer SALD-2100-WJA1, and the powder to be measured was sprayed from a nozzle using compressed air. It refers to the one by the injection type dry measurement method that disperses in and measures.

<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 200 μm, preferably 0.01 to 100 μm, more preferably 0.01 to 80 μm. By satisfying the thickness in such a range, while effectively improving the moldability of the decorative sheet, it has excellent chemical resistance, abrasion resistance, and superiority based on the uneven shape for the decorative resin molded product. It is possible to give a sense of design and the like. In addition, as shown in FIGS. 1 to 4, for example, when the uneven shape is formed by embossing, the uneven shape is effectively expressed, and a particularly excellent design feeling is provided. Therefore, the thickness of the surface layer 2 after curing is preferably 0.01 to 20 μm, more preferably 0.01 to 15 μm, and still more preferably 0.01 to 12 μm. In addition, the thickness of the surface layer 2 means the thickness of the convex portions of the surface layer 2 .

<Formation of surface layer 2>
The surface layer 2 may be formed on a predetermined layer so that the cured product of the curable resin composition has an uneven shape, and the specific method is not particularly limited. Examples of the method for imparting unevenness to the surface layer 2 include a method of applying embossing, a method of applying a resin composition for forming the surface layer 2 only to the portions where the convex portions are to be formed, and curing the resin composition. . For example, a method of embossing is preferable from the viewpoint of imparting a fine uneven shape (for example, the first or second method described later).

Specific examples of the method for forming the surface layer 2 having an uneven shape include the following first method and second method.

Method 1: 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 the side of the sheet on which the surface layer 2 is laminated is embossed. After application, the resin composition used for forming the surface layer 2 is applied and the resin composition is cured.

Second 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 the surface layer 2 is placed on the side of the sheet on which the surface layer 2 is laminated. A method of applying a resin composition used for forming the above, curing the resin composition, and then embossing the surface layer 2 side.

The method of applying the resin composition used for forming the surface layer 2 onto a predetermined layer is not particularly limited. , roll coating, reverse roll coating, comma coating, etc., preferably gravure coating.

The surface layer 2 is formed by irradiating the resin composition (uncured resin layer) coated on the predetermined layer in this manner with ionizing radiation such as electron beams and ultraviolet rays to cure the resin composition. .

Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the thickness of the resin and the layer used, but the acceleration voltage is usually about 70 to 300 kV.

In electron beam irradiation, the higher the acceleration voltage, the higher the penetration ability. By selecting the accelerating voltage so as to be substantially equal, it is possible to suppress irradiation of the base material layer with excessive electron beams, and to minimize deterioration of the base material due to excessive electron beams.

The irradiation dose is preferably an amount that saturates the crosslink density of the resin layer, 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 Cockroft-Walton type, Vandegraft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. can be used.

When ultraviolet rays are used as the ionizing radiation, rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. Examples of ultraviolet light sources include, but are not limited to, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps.

When the thermoplastic resin film 3 described later is provided on the surface layer 2, the surface of the surface layer 2 ( The surface on which the irregularities are formed) may be subjected to a chemical surface treatment such as an oxidation method. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment, and the like. These surface treatments are appropriately selected according to the type of the resin component that constitutes the surface layer 2, but from the viewpoint of effects, operability, and the like, corona discharge treatment is preferred.

[Thermoplastic resin film layer 3]
In the present invention, the thermoplastic resin film layer 3 is a layer provided as necessary in order to suppress deformation or disappearance of the uneven shape of the surface layer 2 during vacuum molding or injection molding of the decorative sheet. The thermoplastic resin film layer 3 is provided on the surface of the surface layer 2 opposite to the substrate layer 1 side. The thermoplastic resin film layer 3 is laminated in a detachable state from the decorative sheet (surface layer 2), and is a layer that is peeled off from the decorative resin molded product after being integrally molded with the molding resin.

The thermoplastic resin film layer 3 and the surface layer 2 may be directly laminated, or another layer may be laminated between these layers. When the thermoplastic resin film layer 3 and the surface layer 2 are directly laminated, the thermoplastic resin film layer 3 serves as an uneven protective layer that protects the uneven shape of the surface layer 2 .

When the surface layer 2 and the thermoplastic resin film layer 3 are directly laminated, it is preferable that the thermoplastic resin film layer 3 fills at least a part of the concave portions of the surface layer 2 . Since the thermoplastic resin film layer 3 fills the uneven recesses of the surface layer 2 , the function of protecting the uneven surface layer 2 by the thermoplastic resin film layer 3 can be further enhanced.

The thermoplastic resin film layer 3 can be filled in the uneven concave portions of the surface layer 2 by, for example, extrusion molding or thermal lamination so as to fill the uneven concave portions in the surface layer 2 . A method of laminating the

In the decorative sheet of the present invention, the surface layer 2 is formed of a cured resin composition containing an ionizing radiation resin. For this reason, compared with a decorative sheet having a thermoplastic resin film having an uneven shape on its surface, deformation of the uneven shape due to heating is suppressed when the thermoplastic resin film layer 3 is laminated by thermal lamination or extrusion molding. ing. Furthermore, in the decorative sheet of the present invention, when the thermoplastic resin film layer 3 is provided, since the irregular shape of the surface layer 2 is protected by the thermoplastic resin film layer 3, injection molding and preforming prior thereto are possible. It is particularly excellent in formability during (vacuum forming). In addition, in order to sufficiently suppress the deformation of the uneven shape and to improve the workability at the time of peeling, even when the thickness of the thermoplastic resin film layer 3 is increased, the moldability is hardly impaired. Therefore, the decorative sheet of the present invention can be suitably used as a decorative sheet that requires high three-dimensional formability.

From the viewpoint of adjusting the adhesive strength so that the thermoplastic resin film layer 3 and the surface layer 2 are in close contact with each other in the state of a decorative sheet and can be easily peeled off after integral molding with the molding resin, the thermoplastic resin film layer 3 is used. are preferably laminated by extrusion molding.

The thermoplastic resin constituting the thermoplastic resin film layer 3 is not particularly limited, and acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"); acrylonitrile-styrene-acrylic acid ester resin; acrylic Resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride resin; polyester resin such as polyethylene terephthalate (PET) resin and polybutylene terephthalate (PBT) resin. One type of thermoplastic resin may be contained alone, or two or more types may be contained.

From the viewpoint of effectively improving the moldability of the decorative sheet and imparting an excellent design feeling based on the uneven shape to the decorative resin molded product, among these, the thermoplastic resin film layer 3 is made of polyolefin resin. Alternatively, it is preferably made of a polyester resin. Amorphous polyethylene terephthalate (PET) is preferably used as the polyester resin. A resin commonly known as A-PET or PET-G can be used as the amorphous PET.

Although the thickness of the thermoplastic resin film layer 3 is not particularly limited, it is preferably about 5 to 300 μm, more preferably about 5 to 100 μm. In addition, as shown in FIG. 4, for example, when the uneven shape is formed by embossing, heat treatment is required from the viewpoint of effectively expressing the uneven shape and providing an excellent design feeling. The thickness of the plastic resin film layer 3 is preferably about 5-100 μm, more preferably about 20-50 μm. Moreover, the thermoplastic resin film layer 3 may consist of multiple layers.

(release layer)
The release layer is a layer that is provided as necessary for the purpose of improving the releasability between the thermoplastic resin film layer 3 and the surface layer 2 . The release layer is also provided in contact with the surface layer 2 . In the present invention, when the release layer is laminated, the release layer fills the uneven concave portions of the surface layer 2 .

As the material for forming the release layer, any material that can be applied so as to fill the irregularities of the surface layer 2 and that can be peeled off from the surface of the surface layer 2 together with the thermoplastic resin film layer 3 is particularly preferable. Although not limited, the release layer is preferably formed of a cured product of an ionizing radiation-curable resin composition. As a result, it is possible to more effectively suppress the deformation and disappearance of the uneven shape of the surface layer 2 during vacuum molding and injection molding, and to impart an excellent design feeling to the decorative resin molded product.

<Ionizing radiation curable resin in release layer>
The types and preferred ionizing radiation-curable resins used for forming the release layer are the same as those used for forming the surface layer 2 . Trifunctional pentaerythritol acrylate is preferred as the ionizing radiation-curable resin in the release layer. The ionizing radiation-curable resin used for forming the release layer and the ionizing radiation-curable resin used for forming the surface layer 2 may be of the same type or may be of different types.

<Other additive ingredients>
In addition to the ionizing radiation-curable resin, the ionizing radiation-curable resin composition used for forming the release layer may contain other resin components as necessary to improve moldability. good too. Resin components other than such ionizing radiation-curable resins include, for example, acrylic resins; polyvinyl acetals (butyral resins) such as polyvinyl butyral; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; vinyl chloride resins; urethane resins; , polyolefins such as polypropylene; styrene resins such as polystyrene and α-methylstyrene; polyamide; polycarbonate; acetal resins such as polyoxymethylene; fluororesins such as ethylene-tetrafluoroethylene copolymer; Acetal resins; thermoplastic resins such as liquid crystalline polyester resins. These resin components may be used singly or in combination of two or more.

The release layer is made of ionizing radiation-curable resin composition, silicone resin, fluorine resin, acrylic resin (for example, acrylic-melamine resin), polyester resin, polyolefin resin, polystyrene resin. Resins, polyurethane resins, cellulose resins, vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as nitrocellulose, copolymers of monomers forming the thermoplastic resins, or these resins (meth) A resin composition modified with acrylic acid or urethane can be used alone or in combination. 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, acrylic-melamine. resin alone, acrylic-melamine resin-containing composition, resin composition obtained by mixing polyester resin with urethane-modified copolymer of ethylene and acrylic acid, copolymer of acrylic resin with styrene and acrylic and a resin composition mixed with an emulsion of Among these, it is particularly preferable to form the release layer with an acrylic-melamine resin alone or a composition containing 50% by mass or more of an acrylic-melamine resin.

Various additives can be blended into the resin composition forming the release layer in consideration of the desired physical properties of the release layer. Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents, colorants and the like. These additives can be appropriately selected and used from commonly used ones. As the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used.

Although the thickness of the release layer is not particularly limited, it is preferably about 1 to 40 μm, more preferably about 5 to 15 μm. The thickness of the release layer is the thickness of the portion of the surface layer 2 located above the projections.

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

[Primer layer 4]
The primer layer 4 is provided between the base material layer 1 and the surface layer 2 for the purpose of making it difficult for fine cracks and whitening to occur in the stretched portion of the surface layer 2. and the surface layer 2 and/or between the base material layer 1 and the pattern layer 5, etc., if necessary.

From the viewpoint of enhancing the adhesion between the surface layer 2 and the layers located therebelow, it is preferable that the primer layer 4 is provided immediately below the surface layer 2 .

The primer composition constituting the primer layer 4 includes urethane resin, (meth)acrylic resin, (meth)acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, and chlorinated polypropylene. , chlorinated polyethylene or the like as a binder resin is preferably used, and these resins can be used singly or in combination of two or more. Among these, urethane resins, (meth)acrylic resins, and (meth)acrylic-urethane copolymer resins are preferred.

As the urethane resin, a polyurethane containing polyol (polyhydric alcohol) as a main component and isocyanate as a cross-linking agent (curing agent) can be used. As the polyol, those having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used. Examples of the isocyanate include polyisocyanates having two or more isocyanate groups in the molecule, aromatic isocyanates such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as are used. It is also possible to mix urethane resin and butyral resin.

In terms of adhesion with the surface layer 2 after cross-linking, difficulty of causing interaction after lamination of the surface layer 2, physical properties, and moldability, acrylic polyol or polyester polyol as a polyol, hexamethylene diisocyanate as a cross-linking agent, A combination of 4,4-diphenylmethane diisocyanate is preferred, and a combination of acrylic polyol and hexamethylene diisocyanate is particularly preferred.

The (meth)acrylic resin may be a homopolymer of a (meth)acrylic acid ester, a copolymer of two or more different (meth)acrylic acid ester monomers, or a copolymer of a (meth)acrylic acid ester and another monomer. Polymers include, specifically, polymethyl (meth)acrylate, polyethyl (meth)acrylate, poly(meth)propyl acrylate, polybutyl (meth)acrylate, 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 comprising a homopolymer or a copolymer containing a (meth)acrylic acid ester such as is preferably used.

As the (meth)acrylic-urethane copolymer resin, for example, an acrylic-urethane (polyester urethane) block copolymer resin is preferable. As the curing agent, the various isocyanates described above are used. If desired, the acrylic/urethane ratio (mass ratio) of the acrylic-urethane (polyester urethane) block copolymer resin is preferably adjusted within the range of 9/1 to 1/9, more preferably 8/2 to 2/8. is preferred.

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

The primer layer 4 is formed using a primer composition by gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, foiler coating, dip coating, silk screen solid coating, wire bar coating, It is formed by a normal coating method such as flow coating, comma coating, flow coating, brush coating, spray coating, or a transfer coating method. Here, the transfer coating method is a method in which a coating film such as a primer layer or an adhesive layer is formed on a thin sheet (film substrate), and then the target layer surface in the decorative sheet is coated.

[Pattern layer 5]
The pattern layer 5 is provided between the base layer 1 and the surface layer 2 for the purpose of imparting decorativeness to the decorative sheet. is a layer provided between the masking layer and the surface layer 2, etc., as required.

The pattern layer 5 can be a layer in which a desired pattern is formed using an ink composition, for example. As the ink composition used for forming the pattern layer 5, a mixture of 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, but examples include polyurethane resins, vinyl chloride/vinyl acetate copolymer resins, vinyl chloride/vinyl acetate/acrylic copolymer resins, chlorinated polypropylene resins, and acrylic resins. , polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins, and the like. These binders may be used singly or in combination of two or more.

Colorants used in the ink composition are not particularly limited, but examples include carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue. organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metal pigments consisting 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 consisting of flakes and the like can be mentioned.

The pattern formed by the pattern layer 5 is not particularly limited. Examples include a fabric pattern, a tiled pattern, and a brickwork pattern, and may be a pattern such as a parquet or patchwork that combines these, or may be a single-color solid pattern (so-called all-over solid pattern). These patterns are formed by multi-color printing using the usual process colors of yellow, red, blue, and black, but they can also be formed by special-color multi-color printing by preparing individual color plates that make up the pattern. can be formed.

Although the thickness of the pattern layer is not particularly limited, it is, for example, 1 to 30 μm, preferably 1 to 20 μm.

Also, the pattern layer 5 may be a metal thin film layer. Examples of metals 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. A method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above metals. The metal thin film layer may be provided on the entire surface or may be provided partially. Further, in order to improve adhesion with adjacent layers, a primer layer using a known resin may be provided on the front and rear surfaces of the metal thin film 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 4 if the primer layer 4 is provided, for the purpose of suppressing color change and variation of the base layer 1. , or if the pattern layer 5 is provided, it is a layer provided between the base material layer 1 and the pattern layer 5 as necessary.

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

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

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

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

[Transparent resin layer]
For the purpose of improving chemical resistance and abrasion resistance, the transparent resin layer is provided between the base layer 1 and the surface layer 2, between the base layer 1 and the primer layer 4 when the primer layer 4 is provided, and the pattern layer 5 If provided, between the pattern layer 5 and the surface layer 2, or if the primer layer 4 and the pattern layer 5 are provided in this order on the base layer 1, between the primer layer 4 and the pattern layer 5, etc., if necessary. layer to be provided. The transparent resin layer is a layer preferably provided in the decorative sheet integrated with the molding resin by insert molding.

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

In order to improve the adhesion with other layers in contact with the transparent resin layer, one side or both sides of the transparent resin layer may be subjected to physical or chemical surface treatment such as an oxidation method or a roughening method, if necessary. good too. These physical or chemical surface treatments are similar to the surface treatments applied to the substrate layer.

Although the thickness of the transparent resin layer is not particularly limited, it is, for example, 10 to 200 μm, preferably 15 to 150 μm.

The transparent resin layer may be laminated via an adhesive, or may be directly laminated without an adhesive. When laminating via an adhesive, examples of adhesives used include polyester resins, polyether resins, polyurethane resins, epoxy resins, phenol resins, polyamide resins, polyolefin resins, poly Vinyl acetate resins, cellulose resins, (meth)acrylic resins, polyimide resins, amino resins, rubbers, silicone resins, and the like can be mentioned. Moreover, when laminating|stacking without an adhesive agent, methods, such as an extrusion method, a sand lamination method, and a thermal lamination method, can be performed.

[Back adhesive layer]
The back surface adhesive layer (not shown) is formed on the back surface of the base material layer 1 (the surface opposite to the surface layer 2) for the purpose of enhancing adhesion to the molding resin when molding the decorative resin molded product. , are optional layers.

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

Thermoplastic resins used for forming the back adhesive layer include, for example, acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride/vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, and polyamides. Resins, rubber-based resins, and the like can be mentioned. These thermoplastic resins may be used singly or in combination of two or more.

Thermosetting resins used for forming the back adhesive layer include, for example, urethane resins,
An epoxy resin etc. are mentioned. These thermosetting resins may be used singly or in combination of two or more.

Method for producing decorative sheet The decorative sheet of the present invention can be produced, for example, through the following first step.
A surface layer formed of a cured product of a resin composition having an uneven shape and containing an ionizing radiation curable resin and a thermoplastic resin at a mass ratio of 10:90 to 25:75 is laminated on the base layer. a first step of forming a laminated body;

Furthermore, when forming a peelable thermoplastic resin film layer on the decorative sheet of the present invention, the following second step is provided after the first step.
A second step of forming a peelable thermoplastic resin film layer on the surface layer of the laminate obtained in the first step.

In the first step and the second step, the components used for forming each layer, the specific conditions for forming each layer, the method for forming the uneven shape of the surface layer 2, etc. are as described in the section on the composition of each layer. is.

2. Decorative resin molded product (decorative resin molded product with thermoplastic resin film layer)
The decorative resin molded product of the present invention is formed by integrating the decorative sheet of the present invention with a molding resin. That is, the decorative resin molded product of the present invention comprises at least a molded resin layer 6, a substrate layer 1, and a surface layer 2 having an uneven shape, which are laminated in order, and the surface layer 2 is made of an ionizing radiation curable resin. It is characterized by being a cured product of a resin composition containing a thermoplastic resin at a mass ratio of 10:90 to 25:75.

Further, the decorative resin molded product with a thermoplastic resin film layer of the present invention is obtained by integrating the decorative sheet of the present invention and the molding resin when the decorative sheet of the present invention includes the thermoplastic resin film layer. It is molded by That is, the decorative resin molded article with a thermoplastic resin film layer of the present invention comprises at least a molded resin layer 6, a base layer 1, a surface layer 2 having an uneven shape, and a thermoplastic resin film layer 3, which are laminated in this order. The surface layer 2 is characterized by being a cured product of a resin composition containing an ionizing radiation curable resin and a thermoplastic resin in a mass ratio of 10:90 to 25:75.

The decorative resin molded product of the present invention is suitably provided with the uneven shape that the surface layer 2 of the decorative sheet has. The uneven shape of the surface layer 2 of the decorative sheet usually changes due to heat and pressure during injection molding. In the decorative resin molded product, the center line average roughness (Ra) of the surface of the surface layer 2 opposite to the base layer 1 side is usually 1 from the viewpoint of imparting an excellent design feeling due to the uneven shape. ~15 μm, preferably 2 to 13 μm, more preferably 3 to 11 μm.

From the same point of view, the maximum height (Rz) of the surface of the surface layer 2 opposite to the substrate layer 1 side is usually 5 to 50 μm, preferably 10 to 40 μm, more preferably 15 to 30 μm. mentioned. From the same point of view, the ten-point average height (Rzjis) of the surface of the surface layer 2 opposite to the substrate layer 1 side is usually 5 to 40 μm, preferably 10 to 35 μm, more preferably 15 to 30 μm. mentioned. In addition, the center line average roughness (Ra), the maximum height (Rz), and the ten-point average height (Rzjis) are each in accordance with the provisions of JIS B 0601: 2001, and the surface layer of the decorative resin molded product 2 is a value measured for the surface of No. 2.

FIG. 5 shows the cross-sectional structure of one embodiment of the decorative resin molded product with a thermoplastic resin film layer of the present invention. Moreover, FIG. 6 shows the cross-sectional structure of one mode of the decorative resin molded product of the present invention.

The decorative resin-molded product of the present invention can be produced by a method comprising the step of forming a molded resin layer by injecting a resin onto the substrate layer side of the decorative sheet of the present invention. Specifically, using the decorative sheet of the present invention, various injection molding methods such as an insert molding method, an injection molding simultaneous decoration method, a blow molding method, and a gas injection molding method are produced.

When the decorative sheet of the present invention is provided with a thermoplastic resin film layer, the decorative sheet of the present invention is subjected to various injection molding methods to produce a decorative resin molded product with a thermoplastic resin film layer. It is possible to suitably exhibit the effect of suppressing the uneven shape from being damaged during molding. A preferred example of the molded resin layer 6 constituting the decorative resin molded product of the present invention is an injection resin layer formed by injection molding. Among these injection molding methods, the insert molding method and the simultaneous injection molding decoration method are preferred. That is, the decorative sheet of the present invention is suitably used for an insert molding method or an injection molding simultaneous decoration method.

In the insert molding method, first, in the vacuum forming process, the decorative sheet of the present invention is vacuum-formed (off-line preforming) in advance into the surface shape of the molded product using a vacuum forming mold, and then, if necessary, the excess portion is trimmed. Obtain a molded sheet. This molding sheet is inserted into an injection mold, the injection mold is clamped, and the resin in a fluid state is injected into the mold and solidified. A decorative resin molded product is manufactured by integrating the material layer 1 side.

More specifically, the decorated resin molded article (or the decorated resin molded article with a thermoplastic resin film layer) of the present invention is manufactured by an insert molding method including the following steps.

a vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance using a vacuum forming mold;
A step of trimming the 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 mold, closing the injection mold, and pouring the resin in a fluid state into the mold. The process of injecting the resin and molding sheet into one.

In the vacuum forming step in the insert molding 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 resin constituting the decorative sheet and the thickness of the decorative sheet. For example, it 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 fluid state is not particularly limited, but it is usually about 180 to 320.degree. C., preferably about 220 to 280.degree.

In the simultaneous injection molding and decorating method, the decorative sheet of the present invention is arranged in a female mold that is also used as a vacuum molding mold provided with suction holes for injection molding, and preforming (in-line preforming) is performed in this female mold. After that, the injection mold is clamped, and the resin in a fluid state is injected and filled into the mold, solidified, and simultaneously with the injection molding, the base layer of the decorative sheet of the present invention is applied to the outer surface of the resin molded product. A decorative resin molded product is manufactured by integrating one side.

More specifically, the decorated resin molded article (or the decorated resin molded article with the thermoplastic resin film layer) of the present invention is manufactured by the simultaneous injection molding and decorating method including the following steps.

After the decorative sheet of the present invention is placed so that the base material of the decorative sheet faces the molding surface of a movable mold having a molding surface of a predetermined shape, the decorative sheet is heated and softened. At the same time, a step of preforming a decorative sheet by vacuum suction from the movable mold side and bringing the softened decorative sheet into close contact along the molding surface of the movable mold;
After the movable mold and fixed mold having the decorative sheet adhered along the molding surface are clamped, the resin molding material in a fluid state is injected and filled into the cavity formed by both molds. An injection molding process in which the formed resin molded body and the decorative sheet are laminated and integrated by solidification, and a resin molded body in which all layers of the decorative sheet are laminated by separating the movable mold from the fixed mold. The process of removing the

In the preforming step of the simultaneous injection molding and decorating method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. When a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can be usually about 70 to 130°C. Also, in the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but it is usually about 180 to 320.degree. C., preferably about 220 to 280.degree.

In addition, the decorative resin molded product (or the decorative resin molded product with a thermoplastic resin film layer) of the present invention is prepared by a vacuum pressure bonding method or the like on a three-dimensional resin molded product (molded resin layer) prepared in advance. It can also be produced by a decorating method of sticking the decorating sheet of the present invention.

In the vacuum crimping method, first, the decorative sheet and the resin molding of the present invention are placed in a vacuum crimping machine consisting of a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side. It is placed in the vacuum pressure bonding machine so that the vacuum chamber side, the resin molded body is on the second vacuum chamber side, and the base layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are placed in a vacuum state. do. The resin molded body is placed on a vertically movable platform provided on the side of the second vacuum chamber. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using a lifting table, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. affixed to the surface of Finally, the two vacuum chambers are opened to the atmospheric pressure, and the excess portion of the decorative sheet is trimmed as required to obtain the decorated resin molded product of the present invention.

In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve formability before the step of pressing the molding against the decorative sheet. A vacuum compression bonding method including the process is sometimes called a vacuum thermocompression bonding method. The heating temperature in this step may be appropriately selected depending on the type of resin constituting the decorative sheet and the thickness of the decorative sheet. , usually about 60 to 200°C.

In the decorative resin-molded product 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 thermoplastic resins used as molding resins include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins. These thermoplastic resins may be used singly or in combination of two or more.

Thermosetting resins used as molding resins include, for example, urethane resins and epoxy resins. These thermosetting resins may be used singly or in combination of two or more.

When the decorative sheet of the present invention is provided with a thermoplastic resin film layer, the thermoplastic resin film layer is peeled off from the decorative resin molded product with the thermoplastic resin film layer of the present invention, thereby removing the decorative resin. A molded article can be obtained. In addition, in the decorative resin molded product with a thermoplastic resin film layer, the thermoplastic resin film layer plays a role as a protective sheet for the decorative resin molded product, so it is stored as it is without being peeled off after production, and can be used. Sometimes the thermoplastic resin film layer may be peeled off. By using it in such a manner, it is possible to prevent the decorative resin molded product from being damaged due to rubbing or the like during transportation.

As described above, when the decorative sheet of the present invention has a thermoplastic resin film layer, the thermoplastic resin film layer 3 is peeled off from the decorative resin molded article with the thermoplastic resin film layer, A decorative resin molded product having an uneven surface is obtained. When the thermoplastic resin film layer 3 is peeled off from the decorative resin molded product with the thermoplastic resin film layer, the surface layer 2 appears on the surface of the decorative resin molded product, and the uneven shape of the surface layer 2 reveals an excellent design feeling. be FIG. 6 shows a cross-sectional structure of one mode of a decorated resin molded article obtained by removing the thermoplastic resin film layer 3 from the decorated resin molded article with the thermoplastic resin film layer of FIG.

Since the decorative resin molded article of the present invention has excellent chemical resistance, wear resistance, etc., it can be used, for example, as an interior or exterior material for vehicles such as automobiles; 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;

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

[Manufacturing of decorative sheets]
Examples 1 to 8, Comparative Examples 1 to 3, and Reference Example (Specifications used for simultaneous injection molding decoration method)
As a decorating method, a decorating sheet having specifications for use in the simultaneous injection molding and decorating method was produced by the following procedure. A resin film (ABS resin film or acrylic resin film) having a thickness of 125 μm shown in Table 1 or Table 3 was used as the base layer. Next, an ink composition containing an acrylic resin was used to form a wood grain pattern layer (thickness: 5 μm) on the substrate layer by gravure printing. Next, on the pattern layer, a primer layer containing a binder resin made of a two-liquid curing resin containing 100 parts by mass of the main agent (acrylic polyol/urethane, mass ratio 9/1) and 7 parts by mass of a curing agent (hexamethylene diisocyanate). A primer layer having a thickness of 2 μm was formed by coating and drying the resin composition, and a laminate was obtained in which the substrate layer/pattern layer/primer layer were laminated in this order.

Next, the primer layer side of the obtained laminate was embossed using an embossing plate of the type shown in Table 1 or Table 3 to form an uneven shape on the primer layer. Details of the embossed plate will be described later. Next, in order to form a surface layer on the primer layer on which the uneven shape is formed, a resin composition containing a thermoplastic resin and an ionizing radiation resin (EB resin) described in Table 1 or 3 is cured. The coating was applied so that the subsequent thickness (thickness of the uneven convex portions of the surface layer) was 10 μm. This resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface layer having an uneven shape. The uneven shape of the surface layer corresponds to the uneven shape of the primer layer. Next, by forming a polyethylene layer on the surface layer by extrusion molding, a substrate layer/pattern layer/primer layer/surface layer having an uneven shape/thermoplastic resin film layer (polyethylene (PE) layer) is formed. A decorative sheet having a laminated structure laminated in this order was obtained. In addition, the uneven|corrugated-shaped recessed part of a surface layer is filled with the polyethylene layer. The extruder was extruded at a temperature below the die of about 300 to 310° C., and the thickness of the polyethylene layer (thickness on the uneven convex portion of the surface layer) of 50 μm.

In addition, embossing was not performed in the reference example.

Examples 9-13 (specifications used for insert molding)
As a decorating method, a decorating sheet having specifications for use in an insert molding method was produced by the following procedure. A resin film (ABS resin film) having a thickness of 475 μm shown in Table 2 was used as the base layer. Next, an ink composition containing an acrylic resin was used to form a wood grain pattern layer (thickness: 5 μm) on the substrate layer by gravure printing. Next, on the pattern layer, a primer layer containing a binder resin made of a two-liquid curing resin containing 100 parts by mass of the main agent (acrylic polyol/urethane, mass ratio 9/1) and 7 parts by mass of a curing agent (hexamethylene diisocyanate). A primer layer having a thickness of 2 μm was formed by coating and drying the resin composition, and a laminate was obtained in which the substrate layer/pattern layer/primer layer were laminated in this order.

Next, the primer layer side of the obtained laminate was embossed to form an uneven shape on the primer layer. Details of the embossed plate will be described later. Next, in order to form a surface layer, a resin composition obtained by blending a thermoplastic resin and an ionizing radiation resin (EB resin) described in Table 2 was applied on the primer layer having the uneven shape after curing. The coating was applied so that the thickness (thickness of the uneven convex portions of the surface layer) was 10 μm. This resin composition was cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface layer having an uneven shape. The uneven shape of the surface layer corresponds to the uneven shape of the primer layer. Further, the surface layer of Example 13 was blended with 5% by mass of urethane beads having a particle size of 3 μm as a matting agent. Next, by forming a polyethylene layer on the surface layer by extrusion molding, a substrate layer/pattern layer/primer layer/surface layer having an uneven shape/thermoplastic resin film layer (polyethylene (PE) layer) is formed. A decorative sheet having a laminated structure laminated in this order was obtained. In addition, the uneven|corrugated-shaped recessed part of a surface layer is filled with the polyethylene layer. The extruder was extruded at a temperature below the die of about 320 to 330.degree.

As shown in Table 2, in Example 12, no thermoplastic resin film layer was provided.

Embossed plate A: stripe pattern, embossed plate depth 40 μm
Embossed plate B: stripe pattern, embossed plate depth 60 μm
Embossed plate C: geometric pattern, embossed plate depth 60 μm
Embossed plate D: Geometric pattern, embossed plate depth 40 μm
Embossed plate E: stripe pattern, embossed plate depth 40 μm
Embossed plate F: hairline pattern, embossed plate depth 100 μm

The trifunctional monomer (Mw=298) listed in Tables 1-3 is "pentaerythritol triacrylate" and the difunctional monomer (Mw=500) is "ethylene oxide modified bisphenol A diacrylate".

<Measurement of surface roughness of decorative sheet>
In accordance with the provisions of JIS B 0601: 2001, the thermoplastic resin film layer was peeled off from each decorative sheet obtained above, and various surface roughnesses on the surface layer side (center line average roughness (Ra), maximum Height (Rz) and ten-point average height (Rzjis)) were measured. As a measuring device, a surface roughness measuring instrument manufactured by Tokyo Seimitsu Co., Ltd. (trade name “Handy Surf E-35A”) was used. The measurement results are shown in Tables 1 to 3.

<Measurement of surface roughness of decorative resin molded product>
The thermoplastic resin film layer was peeled off from each decorative resin molded product obtained in the moldability evaluation described later, and the surface layer side surface was measured in the same manner as in <Measurement of surface roughness of decorative sheet> above. Roughness was measured. The measurement results are shown in Tables 1-3.

<Moldability evaluation>
(Specifications used for simultaneous injection molding decoration method)
Put each decorative sheet obtained in Examples 1 to 8, Comparative Examples 1 to 3, and Reference Example into a mold, heat with an infrared heater at 350 ° C. for 7 seconds, and vacuum form into the shape in the mold. It was preformed along the length and clamped (maximum draw ratio: 100%). After that, the injection resin was injected into the cavity of the mold to integrally mold the decorative sheet and the injection resin. The appearance after injection molding was evaluated according to the following criteria. The results are shown in Tables 1-3.

◯: No cracking or whitening was observed in the surface layer. In addition, fine coating film cracks and whitening were observed in a part of the three-dimensional shape part or the maximum stretched part, but there is no practical problem.
Δ: The shape of the mold could not be followed, and cracking and whitening of the coating film were slightly observed on the surface layer.
x: The shape of the mold could not be followed, and remarkable cracking and whitening of the coating film were observed on the surface layer.

(Specifications used for insert molding method)
Each decorative sheet obtained in Examples 9 to 13 was heated with an infrared heater and softened until the sheet temperature reached 160°C. Then, vacuum forming was performed using a vacuum forming mold (maximum draw ratio: 100%) to form the internal shape of the mold. After the molded decorative sheet was cooled, it was released from the mold. After that, the injection resin was injected into the cavity of the mold to integrally mold the decorative sheet and the injection resin. The appearance after injection molding was evaluated according to the following criteria. The results are shown in Tables 1-3.

◯: No cracking or whitening was observed in the surface layer. In addition, fine coating film cracks and whitening were observed in a part of the three-dimensional shape part or the maximum stretched part, but there is no practical problem.
Δ: The shape of the mold could not be followed, and cracking and whitening of the coating film were slightly observed on the surface layer.
x: The shape of the mold could not be followed, and remarkable cracking and whitening of the coating film were observed on the surface layer.

<Evaluation of design feeling and touch feeling by uneven shape>
The surface of each decorative resin molded product obtained in the moldability evaluation was visually observed and touched with a hand, and the design and texture due to the uneven shape were evaluated according to the following criteria. Tables 1 to 3 show the design evaluation results.

◯: The uneven shape was sufficiently perceived visually and by touch.
Δ: The uneven shape was slightly perceived visually and by touch.
x: No unevenness was observed visually or by touch.

<Chemical resistance of decorative sheet>
5 ml of the sunscreen cosmetic was dropped on the surface of each decorative sheet obtained above, and left in an oven at 60°C for 4 hours. Next, the decorative sheet was taken out, the surface was rinsed with a neutral detergent solution, and the state of the dripped portion was visually observed to evaluate the chemical resistance of the decorative sheet according to the following criteria. The results are shown in Tables 1-3. The sunscreen cosmetic used was commercially available and contained avobenzone (3%), homosalate (10%), octisalate (5%), octocrylene (2.8%), and oxybenzone (6%) as ingredients. It has a high erosion property on the resin surface.

Good: No change in the appearance of the surface of the decorative sheet.
◯△: Slight change in luster on the surface of the decorative sheet, but does not significantly impair the design.
Δ: There is a gloss change on the surface of the decorative sheet, but it is acceptable for practical use.
x: Whitening, swelling, and dissolution occurred on the surface of the decorative sheet.

<Chemical resistance of decorative resin molded products>
5 ml of the sunscreen cosmetic was dropped on the surface of each decorated resin molded product obtained above, and left in an oven at 60°C for 4 hours. Next, the decorated resin molded product was taken out, and after washing the surface with a neutral detergent solution, the state of the dripping portion was visually observed, and the chemical resistance of the decorated resin molded product was evaluated according to the following criteria. The results are shown in Tables 1-3. The sunscreen cosmetic used was the same as that used in <Chemical resistance of decorative sheet>.

◯: There is no change in the external appearance of the surface of the decorative resin molded product.
○△: The surface of the decorative resin molded product has a slight change in luster, but does not significantly impair the design.
Δ: There is a gloss change on the surface of the decorative resin molded article, but it is acceptable for practical use.
x: Whitening, swelling, and dissolution occurred on the surface of the decorative resin molded product.

<Abrasion resistance>
For the surface of each decorative resin molded product obtained in the above moldability evaluation, an abrasion test was performed using a Taber abrasion machine (wear wheel: CS-10, conditions: 1 kg × 200 rotations), and resistance was measured according to the following criteria. Abrasion resistance was evaluated. The results are shown in Tables 1-3.

◯: There is no exposure of the substrate (substrate layer).
Δ: More than half of the substrate is exposed.
x: There is remarkable exposure of the substrate.

1 base material layer 2 surface layer 3 thermoplastic resin film layer 4 primer layer 5 pattern layer 6 molded resin layer

Claims (12)

It is composed of a laminate comprising at least a base material layer and a surface layer having an uneven shape,
The uneven concave portion reaches a layer located below the surface layer,
The surface layer is a cured product of a resin composition containing an ionizing radiation-curable resin and a thermoplastic resin at a mass ratio of 10:90 to 25:75,
The ionizing radiation curable resin contains a polyfunctional (meth)acrylate monomer,
The thermoplastic resin includes an acrylic resin,
The maximum height Rz of the surface of the surface layer opposite to the substrate layer side is 1.0 μm or more and 60 μm or less,
The decorative sheet, wherein the ten-point average height Rzjis of the surface of the surface layer opposite to the base layer is 1.0 μm or more and 60 μm or less. 2. The decorative sheet according to claim 1, wherein the concave portion of the uneven shape reaches the base layer. 3. The decorative sheet according to claim 1, wherein the center line average roughness Ra of the surface of the surface layer opposite to the base material layer is 3 [mu]m or more and 21 [mu]m or less. The decorative sheet according to any one of claims 1 to 3, wherein a peelable thermoplastic resin film layer is provided on the surface of the surface layer opposite to the base layer. The decorative sheet according to any one of claims 1 to 4, wherein the thermoplastic resin of the surface layer has a weight average molecular weight in the range of 90,000 to 150,000. The decorative sheet according to any one of claims 1 to 5, wherein the number of functional groups of the monomer contained in the ionizing radiation curable resin is in the range of 2-6. The decorative sheet according to any one of claims 1 to 6, wherein the molecular weight of a monomer contained in said ionizing radiation curable resin is in the range of 200 or more and 2000 or less. The decorative sheet according to any one of claims 1 to 7, which is used in an insert molding method or an injection molding simultaneous decoration method. The decorative sheet according to any one of claims 1 to 8, wherein a primer layer is laminated directly below the surface layer. The decorative sheet according to any one of claims 1 to 9, wherein a pattern layer is laminated between the base material layer and the surface layer. At least, a molding resin layer, a substrate layer, and a surface layer having an uneven shape are laminated in this order,
The uneven concave portion reaches a layer located below the surface layer,
The surface layer is a cured product of a resin composition containing an ionizing radiation-curable resin and a thermoplastic resin at a mass ratio of 10:90 to 25:75,
The ionizing radiation curable resin contains a polyfunctional (meth)acrylate monomer,
The thermoplastic resin includes an acrylic resin,
The maximum height Rz of the surface of the surface layer opposite to the substrate layer side is 1.0 μm or more and 60 μm or less,
A decorative resin molded product, wherein the ten-point average height Rzjis of the surface of the surface layer opposite to the substrate layer is 1.0 μm or more and 60 μm or less. A method for producing a decorated resin molded article, comprising a step of laminating a molded resin layer by injecting a resin onto the base layer side of the decorative sheet according to any one of claims 1 to 10.

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