JP6972527B2 - Decorative sheets, decorative resin molded products, and methods for manufacturing these - Google Patents

Description

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

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

Conventionally, there has been known a technique for enhancing the texture of a decorative sheet by providing an uneven shape on the surface of the decorative sheet. As a method of providing an uneven shape on the surface of the decorative sheet, for example, a colored layer is provided on a transparent resin film, and embossing is performed on the colored layer to provide an uneven shape in which the colored layer protrudes toward the transparent resin film. The method is known.

In recent years, with the diversification of consumer needs, decorative resin molded products having various designs are required. In order to meet such diversifying consumer needs, it is required to develop decorative resin molded products that not only have a visual design feeling based on the uneven shape of the surface but also a touch feeling.

Japanese Unexamined Patent Publication No. 2004-322501 Special Publication No. 50-19132 Special Publication No. 61-17255

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

Further, the uneven shape of the decorative sheet is easily deformed or disappears due to heat and pressure during molding, and it may not be possible to impart an excellent design feeling and feel to the decorative resin molded product due to the uneven shape.

Under such circumstances, it is an object of the present invention to provide a decorative sheet capable of appropriately imparting an excellent design to a decorative resin molded product, for example, the design feeling and the feel feeling are different depending on the appearance. And. Further, it is also an object of the present invention to provide a method for manufacturing the decorative sheet, a decorative resin molded product using the decorative sheet, and a method for producing the same.

The present inventors have made diligent studies to solve the above problems. As a result, it is a decorative sheet including at least a base material layer and a surface protective layer made of a cured product of an ionizing radiation curable resin composition, and the first surface of the surface protective layer on the base material layer side is A first concavo-convex shape is provided, and a second concavo-convex shape is provided on the second surface opposite to the first surface of the surface protective layer, and the first concavo-convex shape and the second concavo-convex shape are different from each other. According to the decorative sheet, it has been found that an excellent design can be suitably imparted to a decorative resin molded product, for example, the design feeling and the touch feeling are different from each other. The present invention has been completed by further studies based on such findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. A decorative sheet including at least a base material layer and a surface protective layer made of a cured product of an ionizing radiation curable resin composition.
A first uneven shape is provided on the first surface of the surface protective layer on the base material layer side.
A second uneven shape is provided on the second surface opposite to the first surface of the surface protective layer.
A decorative sheet in which the first uneven shape and the second shape are different from each other.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the surface protective layer is a single layer or a plurality of layers.
Item 3. Item 2. The decorative sheet according to Item 1 or 2, wherein a peelable film layer is provided on the second surface of the surface protective layer.
Item 4. A decorative layer is provided between the base material layer and the surface protective layer.
Item 2. The decorative sheet according to any one of Items 1 to 3, wherein the decorative layer is provided along the first uneven shape.
Item 5. A primer layer is provided directly below the surface protective layer, and the primer layer is provided.
Item 2. The decorative sheet according to any one of Items 1 to 4, wherein the primer layer is provided along the first uneven shape.
Item 6. The process of forming the first uneven shape on the surface of the base material layer and
A step of applying an ionizing radiation curable resin composition to the surface side of the base material layer on which the first uneven shape is formed and curing the composition to form a surface protective layer.
A step of forming a second uneven shape different from the first uneven shape on the surface of the surface protective layer opposite to the base material layer,
A method of manufacturing a decorative sheet.
Item 7. A decorative resin molded product comprising at least a molding resin layer, a base material layer, and a surface protective layer made of a cured product of an ionizing radiation curable resin composition.
A first uneven shape is provided on the first surface of the surface protective layer on the base material layer side.
A second uneven shape is provided on the second surface opposite to the first surface of the surface protective layer.
A decorative resin molded product in which the first uneven shape and the second shape are different from each other.
Item 8. Item 2. A method for manufacturing a decorative resin molded product, comprising a step of laminating a molded resin layer by injecting a resin onto the base material layer side of the decorative sheet according to any one of Items 1 to 6.

According to the present invention, it is possible to provide a decorative sheet capable of appropriately imparting an excellent design to a decorative resin molded product. Further, according to the present invention, it is also possible to provide a method for manufacturing the decorative sheet, a decorative resin molded product using the decorative sheet, and a method for manufacturing 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 resin molded article of this invention.

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

Hereinafter, the decorative sheet of the present invention will be described in detail. In this specification, the numerical range indicated by "~" means "greater than or equal to" and "less than or equal to", except for the parts specified as "greater than or equal to" and "less than or equal to". For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, in the present specification, "(meth) acrylate" means "acrylate or methacrylate", and other similar substances have the same meaning.

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

In the decorative sheet of the present invention, a decorative layer 3 may be provided between the base material layer 1 and the surface protective layer 2 as necessary for the purpose of enhancing the visual design. Further, for the purpose of enhancing the adhesion between the surface protective layer 2 and the layer located below the surface protective layer 2, a primer layer 4 may be provided directly under the surface protective layer 2 if necessary. As will be described later, the decorative layer 3 and the primer layer 4 are provided along the first uneven shape 11 provided on the first surface 2a on the base material layer 1 side of the surface protective layer 2, respectively.

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

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

Further, a concealing layer (not shown) is provided between the base material layer 1 and the surface protective layer 2 as necessary for the purpose of suppressing color change and variation of the base material layer 1. May be good. When the primer layer 4 is provided, the concealing layer may be provided between the base material layer 1 and the primer layer 4, and when the decorative layer 3 is provided, the concealing layer is the base material layer. It may be provided between 1 and the decorative layer 3.

Further, in the decorative sheet of the present invention, for the purpose of improving the adhesion with the molding resin when molding the decorative resin molded product, the back surface of the base material layer 1 (the surface opposite to the surface protective layer 2). ) May be provided with a back surface adhesive layer (not shown), if necessary.

As an example of the laminated structure of the decorative sheet of the present invention, the laminated structure in which the base material layer 1 / the surface protective layer 2 is laminated; the laminated structure in which the base material layer 1 / the decorative layer 3 / the surface protective layer 2 are laminated in order; Laminated structure in which base material layer 1 / primer layer 4 / surface protective layer 2 are laminated in order; laminated structure in which base material layer 1 / decorative layer 3 / primer layer 4 / surface protective layer 2 are laminated in order; base material layer 1 / Laminated structure in which surface protective layer 2 / film layer 5 are laminated in order; Base material layer 1 / Surface protective layer 2 / Release layer / Laminated structure in which film layer 5 is laminated in order; Base material layer 1 / Decorative layer 3 / Laminated structure in which the surface protective layer 2 / film layer 5 are laminated in order; the laminated structure in which the base material layer 1 / decorative layer 3 / primer layer 4 / surface protective layer 2 / film layer 5 are laminated in order; / Decorative layer 3 / Primer layer 4 / Surface protective layer 2 / Release layer / Film layer 5 are laminated in this order; Base material layer 1 / Decorative layer 3 / Primer layer 4 / First surface protective layer 21 / First 2 Examples thereof include a laminated structure in which the surface protective layer 22 / the film layer 5 are laminated in order.

FIG. 1 shows a cross-sectional view of a decorative sheet in which a base material layer 1 / decorative layer 3 / primer layer 4 / surface protection layer 2 is laminated as one aspect of the laminated structure of the decorative sheet of the present invention. In FIG. 2, as one aspect of the laminated structure of the decorative sheet of the present invention, the base material layer 1 / decorative layer 3 / primer layer 4 / first surface protective layer 21 / second surface protective layer 22 are laminated in this order. The cross-sectional view of the sheet is shown. In FIG. 3, as one aspect of the laminated structure of the decorative sheet of the present invention, the base material layer 1 / decorative layer 3 / primer layer 4 / first surface protective layer 21 / second surface protective layer 22 / film layer 5 are sequentially arranged. The cross-sectional view of the laminated decorative sheet is shown.

Composition of each layer of decorative sheet [Base material 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 for the base material layer 1 is not particularly limited and may be appropriately selected depending on the three-dimensional moldability, compatibility with the molding resin, etc., but a resin film made of a thermoplastic resin is preferable. Can be mentioned. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as “ABS resin”) and acrylonitrile-styrene-acrylic acid ester resin (hereinafter, referred to as “ASA resin”). , Acrylic resin, polypropylene, polyolefin resin such as polyethylene, polycarbonate resin, vinyl chloride resin, polyethylene terephthalate (PET) and the like. Among these, ABS resin and acrylic resin are preferable from the viewpoint of three-dimensional moldability. Further, the base material layer 1 may be formed of a single-layer sheet of these resins, or may be formed of a multi-layer sheet of the same or different resins.

The flexural modulus of the base material layer 1 is not particularly limited. For example, when the decorative sheet of the present invention is integrated with a molding resin by an insert molding method, the flexural modulus of the base material layer 1 of the decorative sheet of the present invention at 25 ° C. is preferably 500 to 4,000 MPa. 750 to 3,000 MPa can be mentioned. Here, the flexural modulus at 25 ° C. is a value measured according to JIS K7171. When the flexural modulus at 25 ° C. is 500 MPa or more, the decorative sheet has sufficient rigidity, and the surface characteristics and moldability are further improved even when subjected to the insert molding method. Further, when the flexural modulus at 25 ° C. is 3,000 MPa or less, sufficient tension can be applied in the case of roll-to-roll manufacturing, and slack is less likely to occur. The so-called pattern register becomes good.

The base material layer 1 is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides, if necessary, in order to improve the adhesion to the layer provided on the base material layer 1. You may. Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, an ozone ultraviolet treatment method and the like. In addition, examples of the unevenness method performed as the surface treatment of the base material layer 1 include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of resin component constituting the base material layer 1, and a corona discharge treatment method is preferable from the viewpoint of effectiveness and operability.

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

Further, the base material layer 1 may or may not be colored with a colorant. Further, the base material layer 1 may be in any of colorless transparent, colored transparent, and translucent. The colorant used for the base material layer 1 is not particularly limited, but preferably includes a colorant that does not discolor even under a temperature condition of 150 ° C. or higher, and specifically, an existing dry color, paste color, or masterbatch resin. Examples include compositions.

The thickness of the base material layer 1 is appropriately set depending on the intended use of the decorative sheet, the molding method for integrating with the molding resin, and the like, but 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 the insert molding method, the thickness of the base material layer 1 is usually about 50 to 1000 μm, preferably about 100 to 700 μm, and more preferably 100 to 500 μm. The degree is mentioned. When the decorative sheet of the present invention is subjected to the injection molding simultaneous decoration method, the thickness of the base material layer 1 is usually about 25 to 200 μm, preferably about 50 to 200 μm, and more preferably about 70 to 200 μm. Can be mentioned. The thickness of the base material layer 1 is the thickness at the position where the concave portion due to the first uneven shape 11 is not formed.

[Surface protection layer 2]
The surface protective layer is a layer provided to protect the surface of the decorative resin molded product and to give an excellent design to the decorative resin molded product due to the uneven shape. The first uneven shape 11 is provided on the first surface 2a of the surface protective layer 2 on the base material layer 1 side. Further, a second uneven shape 12 is provided on the second surface 2b on the side opposite to the first surface 2a of the surface protective layer 2. In the present invention, the first uneven shape 11 and the second shape 12 are characterized in that they are different from each other. More specifically, when the decorative sheet of the present invention is viewed in a plan view, it is preferable that the design represented by the first concave-convex shape 11 and the design represented by the second shape 12 are different. As a result, for example, an excellent design can be obtained, for example, the design feeling by appearance and the feeling of touch are different. It can be confirmed from the cross-sectional shape in the thickness direction of the decorative sheet that the first uneven shape 11 and the second shape 11 are different from each other.

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

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

For example, from the viewpoint of appropriately imparting a design having a different appearance and feel to the decorative resin molded product, the first concave-convex shape 11 and the second shape 12 have the same pattern, and the convex portion has the same pattern. It is preferable that any one of the height, the width of the convex portion, the pitch between the adjacent convex portions, the width of the concave portion, and the depth of the concave portion is different. From the viewpoint of more preferably imparting the design, it is more preferable that the first uneven shape 11 and the second shape 12 represent different patterns.

In the decorative sheet of the present invention, the first uneven shape 11 and the second uneven shape 12 are formed in at least a part of the decorative sheet in order to exhibit excellent design due to the uneven shape, respectively. Just do it. As will be described later, the first uneven shape 11 is, for example, ionized on the surface side of the base layer 1 on which the first uneven shape 11 is formed after the first uneven shape 11 is formed on the surface of the base material layer 1. It can be provided by applying a radiation-curable resin composition and curing it to form the surface protective layer 2. Therefore, when the base material layer 1 and the surface protection layer 2 are in contact with each other, the first uneven shape 11 is formed by the interface between the base material layer 1 and the surface protection layer 2. On the other hand, after the first uneven shape 11 is formed on the surface of the base material layer 1, the decorative layer 3 and the primer layer 4 are provided on the surface side of the base material layer 1 on which the first uneven shape 11 is formed, and then ionization. When the radiation-curable resin composition is applied and cured to form the surface protective layer 2, the decorative layer 3 or the primer is formed between the base material layer 1 and the surface protective layer 2 in the first uneven shape 11. Layer 4 is located.

Further, as shown in FIGS. 2 and 3, for example, the surface protective layer 2 may be composed of a plurality of layers. As described above, in FIG. 2, the surface protective layer 2 has two layers, a first surface protective layer 21 constituting the first surface 2a and a second surface protective layer 22 constituting the second surface 2b. Although an example of the configuration is shown, a configuration of three or more layers may be provided in which another surface protective layer is further provided between the first surface protective layer 21 and the second surface protective layer 22.

The surface protective layer 2 is composed of a cured product of an ionizing radiation curable resin composition. That is, in the decorative sheet of the present invention, since the first uneven shape 11 and the second uneven shape 12 are composed of the surface protective layer 2 made of the cured product of the ionizing radiation curable resin composition, at the time of injection molding. The change in the uneven shape due to the heat pressure of the above is effectively suppressed, and an excellent design can be imparted to the decorative resin molded product. Hereinafter, the ionizing radiation curable resin used for forming the surface protective layer 2 will be described in detail. When the surface protective layer 2 is composed of a plurality of layers, the ionizing radiation curable resin compositions constituting each layer may be the same or different.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the surface protective layer 2 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. Examples thereof include those obtained by appropriately mixing at least one of a prepolymer, an oligomer, a monomer, and the like having the above. Here, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet (UV) or electron beam (EB) is used, but in addition, X It also includes electromagnetic waves such as rays and γ rays, and charged particle beams such as α rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin is suitable for forming the surface protective layer 2 because it can be made solvent-free, does not require a photopolymerization initiator, and stable curing characteristics can be obtained. Used for.

As the above-mentioned monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more (bifunctional or higher), preferably three or more (trifunctional or higher) polymerizable unsaturated bonds in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (). Meta) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, caprolactone-modified dicyclopentenyldi (meth) Meta) acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylol propanetri (meth) acrylate, ethylene oxide-modified trimethylol propanetri (meth) acrylate , Dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propanetri (meth) acrylate, tris (acryloxyethyl) isocyanurate , Propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate and the like. These monomers may be used alone or in combination of two or more.

Further, as the above-mentioned oligomer used as an ionizing radiation curable resin, a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule is suitable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferable. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomers having a cationically polymerizable functional group in the molecule (for example, novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) and the like. .. Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and has a (meth) acrylate group in the terminal or side chain, and for example, a polycarbonate polyol (meth) is used. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol with a polyhydric isocyanate compound and a hydroxy (meth) acrylate. Acrylic silicone (meth) acrylate can be obtained by radically copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate compound with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxylan ring of a relatively low molecular weight bisphenol type epoxy resin or a novolak type epoxy resin to esterify it. Further, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can also be used. The polyester (meth) acrylate can be obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or to a polyvalent carboxylic acid. It can be obtained by esterifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. Silicone (meth) acrylates can be obtained by adding (meth) acrylic acid to the ends or side chains of silicones that have a polysiloxane bond in the main chain. These oligomers may be used alone or in combination of two or more.

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

(Other additive ingredients)
Various additives can be added to the surface protective layer 2 according to the desired physical properties to be provided in the surface protective layer 2. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesiveness improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a coloring agent. These additives can be appropriately selected and used from those commonly used. Further, 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.

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

(Formation of surface protective layer 2)
The surface protective layer 2 is formed, for example, by preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, applying the same, and cross-linking and curing the composition. The viscosity of the ionizing radiation curable resin composition may be any viscosity that can form an uncured resin layer by the coating method described later.

In the present invention, the prepared coating liquid is applied by a known method such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat, preferably gravure coat so as to have the above-mentioned thickness, and is uncured. Form a resin layer.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer to form the surface protective layer 2. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface protection layer 2, the electron beam transmission depth and surface protection are used. The acceleration voltage is selected so that the thicknesses of the layers 2 are substantially equal. As a result, it is possible to suppress the irradiation of the layer located below the surface protective layer 2 with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam.

The irradiation dose is preferably an amount at which the crosslink density of the surface protective layer 2 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

Further, the electron beam source is not particularly limited, and various electron beam accelerators such as a cockloft Walton type, a bandegraft type, a resonance transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Can be used.

When ultraviolet rays are used as ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

By adding various additives to the surface protective layer 2 thus formed, a hard coat function, an anti-fog coat function, an anti-fouling coat function, an anti-glare coat function, an anti-reflection coat function, an ultraviolet ray shielding coat function, A process for imparting a function such as an infrared shielding coat function may be performed.

[Decorative layer 3]
The decorative layer 3 is provided between the base material layer 1 and the surface protective layer 2, and when the primer layer 4 is provided, between the base material layer 1 and the primer layer 4 or concealed for the purpose of imparting decorativeness to the decorative sheet. When the layer is provided, it is a layer provided as needed between the concealing layer and the surface protection layer 2. The decorative layer 3 is provided along the first uneven shape 11 of the surface protective layer 2.

The decorative layer 3 can be, for example, a layer in which a desired pattern is formed by using an ink composition. As the ink composition used for forming the decorative layer 3, a binder in which a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent or the like is appropriately mixed is used. ..

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

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

The pattern formed by the decorative layer 3 is also not particularly limited, but for example, a stone pattern imitating the surface of rock such as a wood grain pattern or a marble pattern (for example, a travertin marble pattern), a cloth grain or a cloth-like pattern is imitated. Examples thereof include a fabric pattern, a tiled pattern, a brick pile pattern, and the like, which may be a pattern such as a parquet, a patchwork, or the like in which these are combined, or a single color solid color (so-called solid color). These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, but they can also be printed with special colors by preparing plates of the individual colors that make up the pattern. Can be formed.

The thickness of the decorative layer is not particularly limited, and examples thereof include 1 to 30 μm, preferably 1 to 20 μm. The thickness of the decorative layer is the thickness at a position where the concave portion due to the first uneven shape 11 is not formed on the base material layer 1.

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

When the decorative layer 3 is a metal thin film layer, the thickness thereof is not particularly limited, but the optical density (OD value) is preferably 0.6 to 1.8 from the viewpoint of enhancing the design of the decorative sheet. The degree, more preferably about 0.8 to 1.4. The thickness of the metal thin film layer is the thickness at a position where the concave portion due to the first uneven shape 11 is not formed in the base material layer 1.

[Primer layer 4]
The primer layer 4 is a layer provided directly under the surface protective layer 2 as necessary for the purpose of enhancing the adhesion between the surface protective layer 2 and the layer located below the surface protective layer 2. The primer layer 4 is provided along the first uneven shape 11 of the surface protection 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 alone or in admixture of two or more. Among these, urethane resin, (meth) acrylic resin, and (meth) acrylic-urethane copolymer resin are preferable.

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

Acrylic polyol or polyester polyol as a polyol and hexamethylene as a cross-linking agent from the viewpoints of adhesion with the surface protective layer 2 after cross-linking, difficulty in occurrence of interaction after laminating the surface protective layer 2, physical properties, and moldability. It is preferable to combine it with diisocyanate and 4,4-diphenylmethane diisocyanate, and it is particularly preferable to use a combination of acrylic polyol and hexamethylene diisocyanate.

The (meth) acrylic resin is a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a co-polymer of (meth) acrylic acid ester and another monomer. Polymers include, specifically, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate-. (Meta) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl acrylate copolymer (meth) acrylate copolymer A (meth) acrylic resin comprising a single or a copolymer containing the (meth) acrylic acid ester such as the above 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 above-mentioned various isocyanates are used. For the acrylic-urethane (polyester urethane) block copolymer resin, the acrylic / urethane ratio (mass ratio) is preferably adjusted in the range of 9/1 to 1/9, more preferably 8/2 to 2/8, if desired. Is preferable.

The thickness of the primer layer 4 is not particularly limited, but is, for example, about 0.5 to 20 μm, preferably 1 to 5 μm. The thickness of the primer layer is the thickness at a position where the concave portion due to the first uneven shape 11 is not formed on the base material layer 1.

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

[Removable film layer 5]
In the present invention, the film layer 5 is provided as necessary in order to suppress deformation or disappearance of the uneven shape (particularly the second uneven shape 12) of the surface protective layer 2 during vacuum forming or injection molding of the decorative sheet. It is a layer. The film layer 5 is provided on the surface of the surface protective layer 2 opposite to the base material layer 1 side. The film layer 5 is laminated in a state where it can be peeled off from the decorative sheet (surface protective layer 2), and is a layer that is integrally molded with the molding resin and then peeled off from the decorative resin molded product.

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

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

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

In the decorative sheet of the present invention, the surface protective layer 2 is formed of a cured product of an ionizing radiation curable resin composition. Therefore, when the film layer 5 is laminated by heat laminating or extrusion molding, deformation of the uneven shape due to heating is suppressed. Further, in the decorative sheet of the present invention, when the film layer 5 is provided, since the second uneven shape 12 of the surface protective layer 2 is protected by the film layer 5, injection molding and pre-molding (vacuum) prior to the injection molding are performed. It is particularly excellent in moldability during molding). Further, in order to sufficiently suppress the deformation of the uneven shape and improve the workability at the time of peeling, the moldability is not easily impaired even when the thickness of the film layer 5 is increased. Therefore, the decorative sheet of the present invention can also be suitably used as a decorative sheet that requires high three-dimensional formation.

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

The thermoplastic resin constituting the film layer 5 is not particularly limited, and is limited to acrylonitrile-butadiene-styrene resin (hereinafter, may be referred to as “ABS resin”); acrylonitrile-styrene-acrylic acid ester resin; acrylic resin; polypropylene. , Polyethylene-based resin such as polyethylene; Polycarbonate resin; Vinyl chloride-based resin; Polyethylene terephthalate (PET) resin, Polybutylene terephthalate (PBT) resin and other polyester resins. The thermoplastic resin may be contained alone or in combination of two or more.

From the viewpoint of effectively improving the moldability of the decorative sheet, and giving the decorative resin molded product excellent chemical resistance, abrasion resistance, and an excellent design feeling based on the uneven shape, these are used. Above all, it is preferable that the film layer 5 is made of a polyolefin resin or a polyester resin. As the polyester resin, it is preferable to use amorphous polyethylene terephthalate (PET). As the amorphous PET, a resin generally known as A-PET or PET-G can be used.

The thickness of the film layer 5 is not particularly limited, but is preferably about 5 to 300 μm, and more preferably about 5 to 100 μm. The film layer 5 may be composed of a plurality of layers. The thickness of the film layer 5 is the thickness at a position where the recess of the second uneven shape 12 of the surface protection layer 2 is not filled.

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

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

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

<Other additive components>
In addition to the ionizing radiation curable resin, the ionizing radiation curable resin composition used for forming the release layer contains other resin components as necessary for improving moldability and the like. May be good. Examples of the resin component other than the ionizing radiation curable resin include acrylic resin; polyvinyl acetal (butyral resin) such as polyvinyl butyral; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; vinyl chloride resin; urethane resin; polyethylene. , Polypropylene and other polyolefins; Polystyrene, α-Methylstyrene and other styrene resins; Polyamide; Polycarbonate; Polyoxymethylene and other acetal resins; Ethylene-4 fluoride ethylene copolymer and other fluororesins; Acetal resin; examples thereof include thermoplastic resins such as liquid crystal polyester resins. These resin components may be used alone or in combination of two or more.

In addition to the ionizing radiation curable resin composition, the release layer includes a silicone-based resin, a fluororesin, an acrylic-based resin (for example, an acrylic-melamine-based resin is included), a polyester-based resin, a polyolefin-based resin, and a polystyrene-based resin. Resins, polyurethane resins, cellulose resins, vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as vitrified cotton, copolymers of monomers forming the thermoplastic resins, or these resins (meth). It can be formed by using a resin composition modified with acrylic acid or urethane, alone or in combination of two or more. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified products thereof are preferable, and more specifically, acrylic-melamine. A resin composition alone, an acrylic-melamine resin-containing composition, a resin composition obtained by mixing a polyester resin with a urethane-modified copolymer of ethylene and acrylic acid, and a copolymer of an acrylic resin and styrene and acrylic. Examples thereof include a resin composition mixed with the above emulsion. Of 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 the acrylic-melamine resin.

Various additives can be added to the resin composition forming the release layer in consideration of the desired physical properties to be provided in the release layer. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesiveness improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a coloring agent. These additives can be appropriately selected and used from those commonly used. Further, 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.

The thickness of the release layer is not particularly limited, but is preferably about 1 to 40 μm, and more preferably about 5 to 15 μm. The thickness of the release layer is the thickness at a position where the concave portion due to the second uneven shape 12 is not formed on the base material layer 1.

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

[Concealment layer]
The concealing layer is a substrate layer 1 and a primer layer 4 if a primer layer 4 is provided between the substrate layer 1 and the surface protective layer 2 for the purpose of suppressing color change and variation of the substrate layer 1. It is a layer provided as necessary between the base layer 1 and the decorative layer 3 when the space or the decorative layer 3 is provided.

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

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

The concealing layer is usually set to a thickness of about 1 to 20 μm, and it is desirable that the concealing layer is formed as a so-called solid printing layer. The thickness of the concealing layer is the thickness at the position where the recess of the second uneven shape 12 of the surface protection layer 2 is not filled.

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

[Backside adhesive layer]
The back surface adhesive layer (not shown) is the back surface of the base material layer 1 (the surface opposite to the surface protection layer 2) for the purpose of improving the adhesion with the molding resin when molding the decorative resin molded product. In addition, it is a layer provided as needed.

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

Examples of the thermoplastic resin used for forming the back surface adhesive layer include acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride / vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, and polyamide. Examples include resins and rubber-based resins. These thermoplastic resins may be used alone or in combination of two or more.

Examples of the thermosetting resin used for forming the back surface adhesive layer include urethane resin and epoxy resin. These thermosetting resins may be used alone or in combination of two or more.

Method for Manufacturing Decorative Sheet The decorative sheet of the present invention can be manufactured, for example, by a method including the following steps 1 to 3.
Step 1: Forming the first uneven shape 11 on the surface of the base material layer 1. Step 2: Apply the ionizing radiation curable resin composition to the surface side of the base material layer 1 on which the first uneven shape 11 is formed. Step 3: Forming the surface protective layer 2 by curing Step 3: A step of forming a second uneven shape 12 different from the first uneven shape 11 on the surface of the surface protective layer 2 opposite to the base material layer 1.

According to the method for producing a decorative sheet of the present invention, when the surface protective layer 2 is formed of a cured product of an ionizing radiation curable resin composition, for example, when the second uneven shape 12 is formed by embossing. Since the disappearance of the first uneven shape 11 is suppressed by the heat and pressure of the above, the first uneven shape 11 can be easily visually recognized in the obtained decorative sheet.

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

In step 1, before the first uneven shape 11 is provided on the surface of the base material layer 1, the above-mentioned decorative layer 3, the primer layer 4, and the like are laminated, if necessary, and then the first surface of the base material layer 1 is laminated. The uneven shape 11 may be formed. When the decorative layer 3, the primer layer 4, and the like are laminated, the first uneven shape 11 can be formed on the surface of the base material layer 1 by embossing from the side where these layers are laminated. Moreover, the decorative layer 3 and the primer layer 4 can be formed along the first uneven shape 11.

Further, in step 1, the first uneven shape 11 is provided on the surface of the base material layer 1 before laminating the above-mentioned decorative layer 3, the primer layer 4, and the like, and then the above-mentioned decorative layer 3, the primer layer 4, and the like are provided. May be laminated. Also in this case, the first uneven shape 11 can be formed on the surface of the base material layer 1 by laminating the decorative layer 3 and the primer layer 4 so that all the concave portions of the first uneven shape 11 are not filled. It is possible to form the decorative layer 3 and the primer layer 4 along the first uneven shape 11.

Further, in the steps 2 and 3, the method of providing the first uneven shape 11 and the second uneven shape 12 is not particularly limited, but preferably embossing is mentioned. Embossing is a known method, in which the surface of the embossed object is heated and softened, and then pressed with an embossed plate to shape the uneven shape formed on the embossed plate on the surface of the embossed object. It is a method of cooling and fixing. For embossing, a known single-wafer type or rotary type embossing machine can be used. By using the embossed plate corresponding to the first uneven shape 11 and the second uneven shape 12, the first uneven shape 11 and the second uneven shape 12 can be formed.

Further, in the case of forming the peelable film layer 5 on the decorative sheet of the present invention, the following steps are provided after the step 3.
A step of forming a peelable film layer 5 on the second uneven shape 12 of the surface protective layer 2 of the laminated body obtained in the step 3.

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

2. 2. Decorative Resin Molded Product The decorative resin molded product of the present invention is formed by integrating a molding resin into the decorative sheet of the present invention. That is, the decorative resin molded product of the present invention is a decorative resin molded product including at least a base material layer 1 and a surface protective layer 2 made of a cured product of an ionizing radiation curable resin composition, and is surface protected. The first uneven shape 11 is provided on the first surface 2a on the base material layer 1 side of the layer 2, and the second surface 2b on the side opposite to the first surface 2a of the surface protection layer 2 is provided with a second uneven shape 11. The concavo-convex shape 12 is provided, and the first concavo-convex shape 11 and the second concavo-convex shape 12 are different from each other. FIG. 4 shows a cross-sectional structure of one aspect of the decorative resin molded product of the present invention. Note that FIG. 4 is a schematic cross-sectional view of the decorative resin molded product in which the decorative sheet having the laminated structure shown in FIG. 1 and the molded resin layer 6 are integrated.

The decorative resin molded product of the present invention can be manufactured by a method comprising a step of forming a molded resin layer by injecting a resin onto the base material layer side of the decorative sheet of the present invention. Specifically, it is produced by 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 using the decorative sheet of the present invention.

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

In the insert molding method, first, in the vacuum forming step, the decorative sheet of the present invention is vacuum-formed (offline pre-molding) into the surface shape of the molded product in advance by a vacuum forming mold, and then the excess portion is trimmed if necessary. Obtain a molded sheet. This molding sheet is inserted into an injection molding mold, the injection molding mold is molded, the fluid resin is injected into the mold and solidified, and at the same time as the injection molding, the base of the decorative sheet is applied to the outer surface of the resin molded product. By integrating the material layer 1 side, a decorative resin molded product is manufactured.

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

A vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance using a vacuum forming mold.
The process of trimming the excess part of the vacuum-formed decorative sheet to obtain a molded sheet, and the molding sheet obtained in the above step is inserted into an injection molding mold, the injection molding mold is closed, and the resin in a fluid state is molded. The process of injecting inside to integrate the resin and the molded sheet.

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

Further, in the injection molding simultaneous decoration method, the decoration sheet of the present invention is placed in a female mold that also serves as a vacuum molding mold provided with a suction hole for injection molding, and pre-molding (in-line pre-molding) is performed with this female mold. After that, the injection molding mold is molded, the fluid resin is injection-filled in the mold, and solidified, and at the same time as the injection molding, the base material layer of the decorative sheet of the present invention is applied to the outer surface of the resin molded product. By integrating one side, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product (or the decorative resin molded product with a film layer) of the present invention is produced by an injection molding simultaneous decoration method including the following steps.

The decorative sheet of the present invention is placed so that the base material of the decorative sheet faces the molded surface of the movable mold having a molded surface having a predetermined shape, and then the decorative sheet is heated and softened. At the same time, a step of preforming the decorative sheet by vacuum suctioning from the movable mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable mold.
After molding a movable mold having a decorative sheet in close contact with the molding surface and a fixed mold, a fluid resin molding material 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 taking out.

In the preforming process of the injection molding simultaneous decoration 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 usually be about 70 to 130 ° C. Further, in the injection molding step, the temperature of the resin in the fluid state is not particularly limited, but can be usually about 180 to 320 ° C, preferably about 220 to 280 ° C.

Further, the decorative resin molded product of the present invention is prepared by a decorative method such as a vacuum crimping method in which a decorative sheet of the present invention is attached onto a three-dimensional resin molded body (molded resin layer) prepared in advance. Can also be produced.

In the vacuum crimping method, first, the decorative sheet and the resin molded body 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. Installed in the vacuum crimping machine so that the vacuum chamber side and the resin molded body are on the second vacuum chamber side and the base material layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state. do. The resin molded body is installed on an elevating table that can be raised and lowered up and down, which is provided on the second vacuum chamber side. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using an elevating table, and the resin molded body is stretched while stretching the decorative sheet by utilizing the pressure difference between the two vacuum chambers. Stick on the surface of. Finally, the decorative resin molded product of the present invention can be obtained by opening the two vacuum chambers to atmospheric pressure and trimming the excess portion of the decorative sheet as needed.

In the vacuum crimping method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve the moldability before the step of pressing the molded body against the decorative sheet. The vacuum crimping method including this step may be particularly called a vacuum heating crimping method. The heating temperature in the step may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, but when a polyester resin film or an acrylic resin film is used as the base material layer, it may be selected. Usually, the temperature can be 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 intended use. The molding resin may be a thermoplastic resin or a thermosetting resin.

Examples of the thermoplastic resin used as the molding resin include polyolefin resins such as polyethylene and polypropylene, ABS resin, styrene resin, polycarbonate resin, acrylic resin, vinyl chloride resin and the like. These thermoplastic resins may be used alone or in combination of two or more.

Examples of the thermosetting resin used as the molding resin include urethane resin and epoxy resin. These thermosetting resins may be used alone or in combination of two or more.

When the decorative sheet of the present invention includes a film layer, the decorative resin molded product can be obtained by peeling and removing the film layer from the decorative resin molded product with the film layer of the present invention. Further, in the decorative resin molded product with a film layer, the film layer serves as a protective sheet for the decorative resin molded product. May be good. By using it in such an embodiment, it is possible to prevent the decorative resin molded product from being scratched due to rubbing during transportation or the like.

Since the decorative resin molded product of the present invention has an excellent design, for example, an interior or exterior material of a vehicle such as an automobile; a building member such as a skirting board or a skirting board; a window frame, a door frame, etc. Joinery; Interior materials for buildings such as walls, floors, and ceilings; Housings for home appliances such as television receivers and air conditioners; Can be used as containers and the like.

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

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

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

[Example 2]
In Example 1, after forming the second uneven shape of the surface protective layer (here, the first surface protective layer), the electron beam curable resin composition having the following composition has a thickness of 10 μm after curing. The same as in Example 1 except that the uncured resin layer was coated with a bar coat as described above, and the uncured resin layer was irradiated with an electron beam having an acceleration voltage of 165 kV and a radiation dose of 50 kGy (5Mrad) to provide a second surface protective layer. Then, a decorative sheet having a laminated structure as shown in FIG. 2 was obtained.

[Example 3]
A film layer that can be peeled off by forming a laminate as shown in FIG. 2 in the same manner as in Example 2, and then laminating a polyethylene film (thickness 40 μm) on the second surface protective layer by extrusion molding. To obtain a decorative sheet having a laminated structure as shown in FIG.

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

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

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

(Visual evaluation of design feeling)
⊚: The first uneven shape was clearly visible and the design was excellent by visual inspection. 〇: The first uneven shape was sufficiently visible and felt as a design by visual inspection. It was confirmed that the design was expressed by ×: The first uneven shape could not be visually recognized.

(Feeling to the touch)
⊚: The second uneven shape could be clearly felt, and the design was excellent in touch. 〇: The second uneven shape was able to sufficiently feel the touch. △: It is a little difficult to understand, but the second unevenness. I could feel the touch due to the shape ×: I could not feel the second uneven shape by hand

1 Base material layer 11 1st uneven shape 12 2nd uneven shape 2 Surface protective layer 2a 1st surface 2b 2nd surface 21 1st surface protective layer 22 2nd surface protective layer 3 Decorative layer 4 Primer layer 5 Film layer 6 Molding resin layer

Claims (8)

A decorative sheet including at least a base material layer and a surface protective layer made of a cured product of an ionizing radiation curable resin composition.
The base material layer is formed of acrylonitrile-butadiene-styrene resin, and is formed of an acrylonitrile-butadiene-styrene resin.
A first uneven shape is provided on the first surface of the surface protective layer on the base material layer side.
A second uneven shape is provided on the second surface opposite to the first surface of the surface protective layer.
The first uneven shape and the second uneven shape are different from each other.
Wherein the first uneven shape second uneven shape, the convex height, the width of the convex portion, the pitch between adjacent convex portions, concave portions having a width, and any one of the depth of the recess varies, pressurized Decorative sheet. The decorative sheet according to claim 1, wherein the surface protective layer is a single layer or a plurality of layers. The decorative sheet according to claim 1 or 2, wherein a peelable film layer is provided on the second surface of the surface protective layer. A decorative layer is provided between the base material layer and the surface protective layer.
The decorative sheet according to any one of claims 1 to 3, wherein the decorative layer is provided along the first uneven shape. A primer layer is provided directly below the surface protective layer, and the primer layer is provided.
The decorative sheet according to any one of claims 1 to 4, wherein the primer layer is provided along the first uneven shape. The process of forming the first uneven shape on the surface of the base material layer and
A step of applying an ionizing radiation curable resin composition to the surface side of the base material layer on which the first uneven shape is formed and curing the composition to form a surface protective layer.
A step of forming a second uneven shape different from the first uneven shape on the surface of the surface protective layer opposite to the base material layer,
Equipped with
Wherein the first uneven shape second uneven shape, the convex height, the width of the convex portion, the pitch between adjacent convex portions, concave portions having a width, and any one of the depth of the recess varies, pressurized How to make a decorative sheet. A decorative resin molded product comprising at least a molding resin layer, a base material layer, and a surface protective layer made of a cured product of an ionizing radiation curable resin composition.
The base material layer is formed of acrylonitrile-butadiene-styrene resin, and is formed of an acrylonitrile-butadiene-styrene resin.
A first uneven shape is provided on the first surface of the surface protective layer on the base material layer side.
A second uneven shape is provided on the second surface opposite to the first surface of the surface protective layer.
The first uneven shape and the second uneven shape are different from each other.
Wherein the first uneven shape second uneven shape, the convex height, the width of the convex portion, the pitch between adjacent convex portions, concave portions having a width, and any one of the depth of the recess varies, pressurized Decorative resin molded product. A method for manufacturing a decorative resin molded product, comprising a step of laminating a molded resin layer by injecting a resin onto the base material layer side of the decorative sheet according to any one of claims 1 to 6.

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