JP7013746B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

The present invention relates to a decorative sheet and a decorative resin molded product.

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.

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 product. However, in the above-mentioned molding method for decorative resin molded products, for example, in the insert molding method, a decorative sheet is previously molded into a three-dimensional (three-dimensional) shape by a vacuum molding die, and in the injection molding simultaneous decoration method, decoration is performed. In the process of stretching and adhering the sheet along the inner peripheral surface of the cavity during preforming or injection of molten resin, the decorative sheet is pulled by vacuum pressure airing, or by the pressure of the molten resin or shear stress. Since it is stretched more than the minimum required amount to follow the shape of the mold, there is a problem that the surface protective layer of the curved surface portion of the molded product is cracked.

As a method for solving such a problem, for example, in Patent Document 4, in a decorative sheet having at least a surface protective layer on a substrate, the surface protective layer is provided with at least polycarbonate (meth) acrylate and polyfunctional (meth). Ionizing radiation curing containing acrylate and having a mass ratio of the polycarbonate (meth) acrylate to the polyfunctional (meth) acrylate of polycarbonate (meth) acrylate: polyfunctional (meth) acrylate = 98: 2 to 70:30. Disclosed is a technique composed of a cured product of a sex resin composition.

Japanese Unexamined Patent Publication No. 2004-322501 Special Publication No. 50-19132 Special Publication No. 61-17255 Japanese Unexamined Patent Publication No. 2011-733373

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, for example, a technique for adding inorganic particles such as silica particles to the surface layer located on the outermost surface of a decorative resin molded product to impart a low-gloss design. It has been known.

Further, there is also known a technique of imposing an uneven shape on a surface layer to give a design feeling, a feeling of touch, etc. based on the uneven shape.

In a decorative sheet having an uneven shape on the surface, cracks originating from the uneven shape are likely to occur due to heat or pressure when the decorative sheet is subjected to injection molding or pre-molding (vacuum forming) prior to the injection molding. Therefore, there is known a technique for manufacturing a decorative resin molded product by protecting the uneven shape of the surface layer of the decorative sheet with a peelable protective film layer.

Therefore, the present inventors have protected the uneven shape of the surface layer with a peelable protective film layer, and then blended inorganic particles into the surface layer having the uneven shape to give a feeling of touch due to the uneven shape and low gloss. I tried to give the design of the above to the decorative resin molded product.

However, by blending the inorganic particles in the surface layer, the adhesion between the peelable protective film layer and the surface layer having an uneven shape becomes high, and the protective film layer cannot be peeled off from the decorative resin molded product. There has occurred.

Under such circumstances, in the present invention, the uneven shape of the surface layer is protected by a peelable protective film layer, and the protective film can be suitably peeled off from the decorative resin molded product, and further protected. The main object of the present invention is to provide a decorative sheet capable of appropriately imparting a low-gloss design to a decorative resin molded product and a feeling of touch based on the uneven shape of the surface layer after the film layer is peeled off. It is also an object of the present invention to provide 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 composed of at least a base material layer, a surface layer having an uneven shape, and a laminated body including a peelable protective film layer covering the uneven shape of the surface layer, and the surface layer is 100 parts by mass of resin. On the other hand, the decorative sheet composed of a resin composition containing 1 part by mass or more and 5 parts by mass or less of inorganic particles and 1 part by mass or more and 5 parts by mass or less of synthetic resin particles is a peelable protective film layer. The uneven shape of the surface layer is protected, and the protective film can be suitably peeled off from the decorative resin molded product, and further, a feeling of touch based on the uneven shape of the surface layer after the protective film layer is peeled off. , It has been found that a low-gloss design can be suitably applied to a decorative resin molded product. 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. It is composed of at least a base material layer, a surface layer having an uneven shape, and a laminated body including a peelable protective film layer that covers the uneven shape of the surface layer.
The surface layer is composed of a resin composition containing 1 part by mass or more and 5 parts by mass or less of inorganic particles and 1 part by mass or more and 5 parts by mass or less of synthetic resin particles with respect to 100 parts by mass of the resin. Decorative sheet.
Item 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 base material layer side is 5 μm or more and 20 μm or less.
Item 3. Item 2. The decorative sheet according to Item 1 or 2, wherein the surface layer is a cured product of a resin composition containing an ionizing radiation curable resin as the resin.
Item 4. Item 6. The item 1 to 3, wherein the surface layer is a cured product of a resin composition containing an ionizing radiation curable resin and a thermoplastic resin as the resin in a mass ratio of 10:90 to 75:25. Decorative sheet.
Item 5. Item 4. The decorative sheet according to Item 4, wherein the thermoplastic resin has a weight average molecular weight in the range of 90,000 or more and 150,000 or less.
Item 6. Item 2. The decorative sheet according to any one of Items 3 to 5, wherein the number of functional groups of the monomer contained in the ionizing radiation curable resin is in the range of 1 to 6.
Item 7. Item 2. The decorative sheet according to any one of Items 3 to 6, 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 8. Item 2. The decorative sheet according to any one of Items 1 to 7, wherein a primer layer is laminated immediately below the surface layer.
Item 9. Item 2. 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, the molding resin layer, the base material layer, and the surface layer having an uneven shape are laminated in this order.
The surface layer is a decorative resin molded product containing 1 part by mass or more and 5 parts by mass or less of inorganic particles and 1 part by mass or more and 5 parts by mass or less of synthetic resin particles with respect to 100 parts by mass of resin.
Item 11. 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 9.

According to the present invention, the uneven shape of the surface layer is protected by the peelable protective film layer, and the protective film layer can be suitably peeled off from the decorative resin molded product, and the protective film layer is peeled off. It is possible to provide a decorative sheet that can suitably impart a low-gloss design to a decorative resin molded product with a feeling of touch based on the uneven shape of the subsequent surface layer. Further, according to the present invention, it is also possible to provide a decorative resin molded product using the decorative sheet and a method for producing the same.

It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of 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 with a protective film 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 composed of at least a base material layer, a surface layer having an uneven shape, and a laminated body including a peelable protective film layer covering the uneven shape of the surface layer. The layer is characterized by being composed of a resin composition containing 1 part by mass or more and 5 parts by mass or less of inorganic particles and 1 part by mass or more and 5 parts by mass or less of synthetic resin particles with respect to 100 parts by mass of the resin. do. Since the decorative sheet of the present invention has such a specific configuration, the uneven shape of the surface layer is protected by a peelable protective film layer, and the protective film layer is a decorative resin molded product. It is possible to suitably peel off the protective film layer from the above, and it is possible to appropriately impart a texture based on the uneven shape of the surface layer after peeling off the protective film layer and a low-gloss design to the decorative resin molded product. ..

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". 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. Further, 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 In the decorative sheet of the present invention, at least the base material layer 1, the surface layer 2 having an uneven shape, and the peelable protective film layer 3 covering the uneven shape of the surface layer 2 are laminated. It has a laminated structure.

The decorative sheet of the present invention has a peelable protection 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 at the time of injection molding or the like. The film layer 3 is provided. The surface layer 2 and the protective film layer 3 may be directly laminated, or another layer may be laminated between these layers. Examples of the other layer include a release layer (not shown). It is preferable that the protective film layer 3 and the release layer fill the concave-convex concave portions of the surface layer 2.

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

Further, a pattern layer 5 may be provided between the base layer 1 and the surface layer 2 as necessary 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.

Further, a concealing layer (not shown) may be provided between the base material layer 1 and the surface layer 2 as necessary for the purpose of suppressing color change and variation of the base material layer 1. 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 pattern layer 5 is provided, the concealing layer is the base material layer. It may be provided between 1 and the pattern layer 5.

Further, a transparent resin layer (not shown) may be provided between the base material layer 1 and the surface layer 2 as necessary for the purpose of improving wear 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.

Further, 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) for the purpose of improving the adhesion with the molding resin when molding the decorative resin molded product. 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, a laminated structure in which the base material layer 1 / surface layer 2 / protective film layer 3 are laminated in order; the base material layer 1 / surface layer 2 / release layer / protective film layer Laminated structure in which 3 are laminated in order; Laminated structure in which base material layer 1 / pattern layer 5 / surface layer 2 / protective film layer 3 are laminated in order; base material layer 1 / pattern layer 5 / primer layer 4 / surface layer 2 / Laminated structure in which the protective film layer 3 is laminated in order; Laminated structure in which the base material layer 1 / pattern layer 5 / primer layer 4 / surface layer 2 / release layer / protective film layer 3 are laminated in order; base material layer 1 / A laminated structure in which a pattern layer 5 / a transparent resin layer / a primer layer 4 / a surface layer 2 / a protective film layer 3 are laminated in this order can be mentioned.

1 and 2 show a cross-sectional view of a decorative sheet in which a base material layer 1 / surface layer 2 / protective film layer 3 are laminated in order as one aspect of the laminated structure of the decorative sheet of the present invention. FIG. 3 is a cross-sectional view of a decorative sheet in which a base material layer / a pattern layer 5 / a primer layer 4 / a surface layer 2 / a protective film layer 3 are laminated in this order as one aspect of the laminated structure of the decorative sheet of the present invention. Is shown.

Composition of each layer of decorative sheet [Base material layer 1]
The base material layer 1 is a resin sheet 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 colorless and 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.

[Surface layer 2]
The surface layer 2 has an uneven shape on the surface opposite to the base material layer 1. The surface layer 2 is a layer provided to suitably impart a texture based on the uneven shape and a low-gloss design to the decorative resin molded product.

<Concave and convex 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 a hairline pattern, a wood grain pattern, a geometric pattern (dots, stripes, carbon, etc.) and the like.

Further, 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, etc. in the concave-convex shape provided in the surface layer 2 depend on the design feeling to be given to the decorative resin molded product. It may be set appropriately.

For example, the 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. It is about 20 μm, more preferably 3 to 15 μm. If the average roughness of the center line is 21 μm or less, the decorative sheet may be damaged or torn during transportation, or the roll may be broken due to excessive unevenness when the decorative sheet is rolled and stored. Not suitable.

From the same viewpoint, the maximum height (Rz) of the surface of the surface layer 2 opposite to the base material layer 1 side is usually 1.0 to 100 μm, preferably 1.0 to 80 μm, and more preferably 1.0 to 80 μm. The range is 1.0 to 60 μm. From the same viewpoint, 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, and more preferably 1.0 to 80 μm. The range is 1.0 to 60 μm. The average roughness (Ra), maximum height (Rz), and ten-point average height (Rzjis) of the center line comply with the provisions of JIS B 0601: 2001, respectively, of the surface layer 2 of the decorative sheet. It is a value measured in a state where the protective film layer 3 is peeled off from the surface (a portion where an uneven shape is formed).

Further, as for the uneven shape formed by the surface layer 2, the bottom portion of the recess may be formed by the surface layer 2 as in the embodiment shown in FIG. 1, or the bottom portion of the recess may be formed 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 a convex portion. The former is preferable from the viewpoint of protecting the surface of the decorative resin molded product. 1 and 2 show, for example, an uneven shape formed by a method of embossing, which will be described later. 1 to 2 show a laminated structure in which only the base material layer 1, the surface layer 2, and the protective film layer 3 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 area in order to give the decorative sheet a high texture due to the uneven shape. That is, in the decorative sheet of the present invention, the uneven shape satisfying the above relationship may be formed in a part of the region or may be formed in the entire region.

Further, the uneven shape may be formed only on the surface layer 2, or a layer in which the concave portion of the uneven shape is located below the surface layer 2 (for example, a primer layer 4, a pattern layer 5, and a base material layer 1). Etc.) may be reached. From the viewpoint of effectively suppressing the disappearance and deformation of the uneven shape during injection molding of the decorative sheet, it is preferable that the concave and convex shaped recess reaches the base material layer 1.

<Composition>
The surface layer 2 is composed of a resin composition containing a resin, inorganic particles, and synthetic resin particles, and has 1 to 5 parts by mass of inorganic particles and 1 to 5 parts of synthetic resin particles with respect to 100 parts by mass of the resin. It is characterized by including a mass part.

The protective film layer 3 is suitably peeled off from the decorative resin molded product, and further, the texture based on the uneven shape of the surface layer 2 after the protective film layer 3 is peeled off, and the low-gloss design are suitably coated with the decorative resin. From the viewpoint of imparting to the product, the content of the inorganic particles is preferably about 1.5 to 4.0 parts by mass, more preferably about 2.0 to 3.5 parts by mass with respect to 100 parts by mass of the resin. Can be mentioned. From the same viewpoint, the content of the synthetic resin particles is preferably about 1.5 to 4.0 parts by mass, more preferably about 2.0 to 3.5 parts by mass with respect to 100 parts by mass of the resin. Be done.

The inorganic particles are not particularly limited, but from the above viewpoint, silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, kaolin, hydrophobic treated products thereof and the like are preferably mentioned, and silica particles are particularly preferable.

The particle size of the inorganic particles is not particularly limited, but from the above viewpoint, it is preferably about 0.1 to 5 μm, more preferably about 1 to 5 μm, and even more preferably about 2 to 5 μm.

The synthetic resin particles are not particularly limited as long as they are particles formed of synthetic resin, and are, for example, urethane beads, acrylic beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, and polyolefin wax (polypropylene wax). , Polyethylene wax, mixtures thereof and the like, and urethane beads are particularly preferable.

The particle size of the synthetic resin particles is not particularly limited, but from the above viewpoint, it is preferably about 0.1 to 5 μm, more preferably about 1 to 5 μm, and even more preferably about 2 to 5 μm.

The particle diameters of the inorganic particles and the synthetic resin particles in the present invention are measured by using the Shimadzu laser diffraction type particle size distribution measuring device SALD-2100-WJA1 and using compressed air to obtain the powder to be measured from the nozzle. Refers to the median diameter (d50) by a jet-type dry measurement method that injects particles and disperses them in the air for measurement.

The resin contained in the surface layer 2 is not particularly limited, but preferably contains an ionizing radiation curable resin, and more preferably contains an ionizing radiation curable resin and a thermoplastic resin. That is, in the present invention, the surface layer 2 is preferably composed of a cured product of a resin composition containing an ionizing radiation curable resin as a resin, and a resin containing an ionizing radiation curable resin and a thermoplastic resin as the resin. It is more preferable that it is composed of a cured product of the composition.

When the surface layer 2 is a cured product of a resin composition containing an ionized radiation curable resin and a thermoplastic resin, the surface layer 2 contains the ionized radiation curable resin and the thermoplastic resin in a mass ratio of 10:90 to 25:75. Is preferable. As described above, the decorative sheet of the present invention can be obtained by forming the surface layer 2 having an uneven shape with a cured product of a resin composition containing an ionizing radiation curable resin and a thermoplastic resin in the above-mentioned specific ratios. The texture based on the uneven shape of the surface layer 2 and the low-gloss design can be suitably added to the decorative resin molded product, and further, the moldability is achieved even though the surface layer 2 has the uneven shape. It is also possible to impart excellent chemical resistance and abrasion resistance to the decorative resin molded product.

The ratio (mass ratio) of the ionizing radiation curable resin to the thermoplastic resin in the surface layer 2 is more preferably about 15:85 to 25:75, and further preferably about 20:80 to 25:75.

The thermoplastic resin is not particularly limited, but is preferably acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber. Examples include based resins. Among these, the texture based on the uneven shape of the surface layer 2 and the low-gloss design can be suitably imparted to the decorative resin molded product, and even though the surface layer 2 has the uneven shape. Acrylic resin is particularly preferable from the viewpoint of providing excellent moldability and imparting excellent chemical resistance and abrasion resistance to the decorative resin molded product.

Examples of the acrylic resin include homopolymers of (meth) acrylic acid esters, copolymers of two or more different (meth) acrylic acid ester monomers, or copolymers of (meth) acrylic acid esters and other monomers. Specific examples thereof include methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate- (meth). (Butyl acrylate copolymer, ethyl (meth) acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl acrylate copolymer (meth) acrylate copolymer, etc. ( A (meth) acrylic resin comprising a single or a copolymer containing a meta) acrylic acid ester is preferably used.

The weight average molecular weight of the thermoplastic resin is not particularly limited, but a texture based on the uneven shape of the surface layer 2 and a low-gloss design can be suitably imparted to the decorative resin molded product, and further, the surface layer. Although 2 has an uneven shape, it has excellent moldability, and is preferably 90,000 to 15 from the viewpoint of imparting excellent chemical resistance and wear resistance to the decorative resin molded product. About 10,000, 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 the present specification is a value measured by the gel permeation chromatography method 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 having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet (UV) or electron beam (EB) is used, but other , X-rays, γ-rays and other electromagnetic waves, α-rays, ion-beams and other charged particle beams are also included. Among the ionizing radiation curable resins, the electron beam curable resin can be made solvent-free, does not require a photopolymerization initiator, and has stable curing properties, and is therefore suitably used for forming a surface layer. Will be done.

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

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 (2) in the molecule. A polyfunctional (meth) acrylate oligomer having (more than functional) 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, silicone-modified urethane (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). Group 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. 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 a reaction between a polyether polyol or a polyester polyol and a polyisocyanate 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. The 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 the main chain. The 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 hydroxy (meth) acrylate. These oligomers may be used alone or in combination of two or more.

Further, 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 suitable, and among them, a polyfunctional (meth) acrylate monomer is preferable. The polyfunctional (meth) acrylate monomer may be any (meth) acrylate monomer having two or more polymerizable unsaturated bonds in the molecule. Specific examples of the polyfunctional (meth) acrylate monomer 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 (Meta) acrylate, ethylene oxide modified di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethyl propanetri (meth) acrylate, ethylene oxide modified trimethyl propanthry (meth) Acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, ethylene oxide-modified trimethylol propantri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, propylene oxide modified trimethylol propantri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa. Examples thereof include (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These monomers may be used alone or in combination of two or more.

Among these ionizing radiation curable resins, the protective film layer 3 is suitably peeled off from the decorative resin molded product, and further, the texture based on the uneven shape of the surface layer after the protective film layer 3 is peeled off, and low gloss. Appropriately imparts the above design to the decorative resin molded product, and further imparts excellent chemical resistance and wear resistance to the decorative resin molded product while effectively enhancing the moldability of the decorative sheet. From the viewpoint, the number of functional groups of the monomer contained in the ionizing radiation curable resin is preferably in the range of 1 to 6, and more preferably in the range of 2 to 4. The molecular weight of the monomer contained in the ionizing radiation curable resin is preferably about 200 to 2000, more preferably about 200 to 1500, and further preferably about 200 to 1000.

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

<Other additives>
Further, various additives can be added to the resin composition used for forming the surface layer 2 according to the desired physical properties to be provided in the surface layer 2. Examples of this additive include weather resistance improving agents such as ultraviolet absorbers and light stabilizers, abrasion resistance improving agents, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesive improving agents, and leveling agents. , Chixo property imparting agent, coupling agent, plasticizer, defoaming agent, filler, solvent, colorant, wax and the like. 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. By blending wax, scratch resistance and wear resistance can be improved. Examples of the wax include olefin waxes such as polyethylene wax (PE wax). When the wax is blended, the blending amount in the resin composition is preferably about 0.1 to 5% by mass, more preferably about 0.5 to 3% by mass.

<Thickness of surface layer 2>
The thickness of the surface layer 2 after curing is not particularly limited, and examples thereof include 0.01 to 200 μm, preferably 0.01 to 100 μm, and more preferably 0.01 to 80 μm. By satisfying the thickness in such a range, the protective film layer 3 is suitably peeled off from the decorative resin molded product, and further, the feel and feel based on the uneven shape of the surface layer after the protective film layer 3 is peeled off. A low-gloss design is suitably applied to the decorative resin molded product, and further, while effectively improving the moldability of the decorative sheet, excellent chemical resistance and abrasion resistance are provided for the decorative resin molded product. Can be granted. In addition, for example, as shown in FIGS. 1 to 3, when the uneven shape is formed by embossing, for example, the viewpoint of effectively expressing the uneven shape and providing a particularly excellent design feeling and the like. The thickness of the surface layer 2 after curing is preferably about 0.01 to 20 μm, more preferably about 0.01 to 15 μm, and even more preferably about 0.01 to 12 μm. The thickness of the surface layer 2 means the thickness of the convex portion 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 thereof is not particularly limited. Examples of the method of imparting the uneven shape to the surface layer 2 include a method of embossing, a method of applying the resin composition forming the surface layer 2 only to the portion where the convex portion is formed, and the like, and curing the surface layer 2. .. For example, from the viewpoint of imparting a fine uneven shape, a method of embossing is preferable (for example, the first method or the second method described later).

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

First method: A base layer 1 and other layers provided as needed are laminated in order to prepare a sheet having a material other than the surface layer 2, and embossing is performed 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 surface layer 2 to cure the resin composition.

Second method: A base layer 1 and other layers provided as needed are laminated in order to prepare a sheet having a material other than the surface layer 2, and the surface layer 2 is on the side where the surface layer 2 of the sheet is laminated. A method in which the surface layer 2 side is embossed after the resin composition used for forming the above is applied and the resin composition is cured.

The method of applying the resin composition used for forming the surface layer 2 onto a predetermined layer is not particularly limited, but for example, in the above-mentioned first method or second method, a gravure coat or a bar coat is used. , Roll coat, reverse roll coat, comma coat and the like, and preferably a gravure coat.

The resin composition (uncured resin layer) coated on the predetermined layer in this manner is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the resin composition to form the surface layer 2. ..

Here, when an electron beam is used as the ionizing radiation, the acceleration voltage 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 the irradiation of the electron beam, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a base material deteriorated by the electron beam is used as the base material layer, the transmission depth of the electron beam and the thickness of the resin layer are substantially the same. By selecting the acceleration voltage so as to be equal to each other, it is possible to suppress the irradiation of the base material layer with the extra electron beam, and it is possible to minimize the deterioration of the base material due to the excess electron beam.

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

Further, the electron beam source is not particularly limited, and for example, various electron beam accelerators such as cockloft Walton type, van de Graaff type, resonance transformer type, insulated core transformer type, linear type, dynamistron type, and high frequency type. 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.

From the viewpoint of adjusting the adhesion and peelability between the surface layer 2 and the protective film layer 3, the surface of the surface layer 2 (the surface on the side where the uneven shape is formed) is chemically treated by an oxidation method or the like, if necessary. The surface treatment may be applied. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment method and the like. These surface treatments are appropriately selected depending on the type of resin component constituting the surface layer 2, and a corona discharge treatment method is preferable from the viewpoint of effectiveness and operability.

[Protective film layer 3]
In the present invention, the protective film layer 3 is a layer provided to suppress deformation or disappearance of the uneven shape of the surface layer 2 during vacuum forming or injection molding of a decorative sheet. The protective film layer 3 is provided on the surface of the surface layer 2 opposite to the base material layer 1 side. The protective film layer 3 covers the uneven shape of the surface layer 2. The protective film layer 3 is laminated in a state where it can be peeled off from the decorative sheet (surface 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 protective film layer 3 and the surface layer 2 may be directly laminated, or another layer may be laminated between these layers. When the protective film layer 3 and the surface layer 2 are directly laminated, the protective film layer 3 becomes an uneven protective layer that protects the uneven shape of the surface layer 2.

When the surface layer 2 and the protective film layer 3 are directly laminated, it is preferable that the protective film layer 3 fills at least a part of the uneven concave portion of the surface layer 2. Since the protective film layer 3 fills the concave-convex shape of the surface layer 2, the protective function of the protective film layer 3 for the uneven shape of the surface layer 2 can be further enhanced.

As a method of filling the concave-convex shape of the surface layer 2 with the protective film layer 3, for example, a method of laminating the protective film layer 3 by filling the concave-convex shape of the surface layer 2 by extrusion molding or thermal laminating. Can be mentioned.

Since the uneven shape of the surface layer 2 is protected by the protective film layer 3, the moldability at the time of injection molding and pre-molding (vacuum forming) prior to the injection molding is particularly excellent. 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 protective film layer 3 is increased. Therefore, the decorative sheet of the present invention can also be suitably used as a decorative sheet that requires high three-dimensional moldability.

From the viewpoint of adjusting the adhesive strength so that the protective film layer 3 and the surface 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 protective film layer 3 is extruded. It is preferable that the film is laminated with the above.

The resin constituting the protective film layer 3 is not particularly limited, and is an acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as "ABS resin"); an acrylonitrile-styrene-acrylic acid ester resin; an acrylic resin; polypropylene, Examples thereof include polyolefin resins such as polyethylene; polycarbonate resins; vinyl chloride resins; thermoplastic resins such as polyethylene terephthalate (PET) resins and polyester resins such as polybutylene terephthalate (PBT) 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 imparting an excellent design feeling based on the uneven shape to the decorative resin molded product, among these, the protective film layer 3 is made of a polyolefin resin or polyester. It is preferably composed of 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 protective film layer 3 is not particularly limited, but is preferably about 5 to 300 μm, and more preferably about 5 to 100 μm. In addition, for example, as shown in FIGS. 1 to 3, when the uneven shape is formed by embossing, for example, from the viewpoint of effectively expressing the uneven shape and providing an excellent design feeling and the like. The thickness of the protective film layer 3 is preferably about 5 to 100 μm, more preferably about 20 to 50 μm. Further, the protective film layer 3 may be composed of a plurality of layers.

(Release layer)
The release layer is a layer provided as needed for the purpose of enhancing the peelability between the protective film layer 3 and the surface layer 2. The release layer is also provided so as to be in contact with the surface layer 2. In the present invention, when the release layers are laminated, the release layer fills the concave-convex concave portions of the surface layer 2.

The material for forming the release layer is not particularly limited as long as it can be applied so as to fill the uneven shape of the surface layer 2 and can be peeled off from the surface of the surface layer 2 together with the protective film layer 3. However, the release layer is preferably formed of a cured product of the ionizing radiation curable resin composition. This makes it possible to more effectively suppress the deformation and disappearance of the uneven shape of the surface layer 2 during vacuum 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 layer 2. As the ionizing radiation curable resin in the release layer, trifunctional pentaerythritol acrylate is preferable. Further, 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 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 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.

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, in addition to the ionizing radiation curable resin composition. 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, adhesive 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 of the portion located above the convex portion of the surface layer 2.

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

[Primer layer 4]
In the primer layer 4, the pattern layer 5 is provided between the base 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. It is a layer provided as necessary between the surface layer 2 and / or between the base layer 1 and the pattern layer 5.

From the viewpoint of enhancing the adhesion between the surface layer 2 and the layer located below the surface layer 2, it is preferable that the primer layer 4 is provided directly 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 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. As the polyol, those having two or more hydroxyl groups in the molecule, 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, hexamethylene diisocyanate as a crosslinking agent, from the viewpoints of adhesion with the surface layer 2 after cross-linking, difficulty in occurrence of interaction after laminating the surface layer 2, physical properties, and moldability. It is preferable to combine it with 4,4-diphenylmethane diisocyanate, and it is particularly preferable to use it in combination with an 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- (meth) methyl 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 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 (protective film base material), and then the surface of the target layer in the decorative sheet is coated.

[Picture layer 5]
The pattern layer 5 is used between the base layer 1 and the surface layer 2, when the primer layer 4 is provided, between the base layer 1 and the primer layer 4, or a concealing layer for the purpose of imparting decorativeness to the decorative sheet. Is provided as necessary, such as between the concealing layer and the surface layer 2.

The pattern layer 5 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 pattern layer 5, 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 for example, carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal pattern, cadmium red, ultramarine, 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 pattern layer 5 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), or 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 pattern layer is not particularly limited, and examples thereof include 1 to 30 μm, preferably 1 to 20 μm.

Further, the pattern layer 5 may be a metal thin film layer. Examples of the metal forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of 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. Further, in order to improve the adhesion with the adjacent layer, a primer layer using a known resin may be provided on the front surface or the back surface of the metal thin film layer.

[Concealment layer]
The concealing layer is between the base material layer 1 and the surface layer 2, and if the primer layer 4 is provided, between the base material layer 1 and the primer layer 4 for the purpose of suppressing the color change and variation of the base material layer 1. Or, if the pattern layer 5 is provided, it is a layer provided between the substrate layer 1 and the pattern layer 5 as needed.

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 above-mentioned pattern layer.

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 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.

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

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

The transparent resin layer is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one or both sides, if necessary, in order to improve the adhesion with the other layers in contact with the transparent resin layer. May be good. These physical or chemical surface treatments are similar to the surface treatments applied to the substrate layer.

The thickness of the transparent resin layer is not particularly limited, and examples thereof include 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 the adhesive used include polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin resin, polyamide resin, polyolefin resin, and poly. Examples thereof include vinyl acetate resin, cellulose resin, (meth) acrylic resin, polyimide resin, amino resin, rubber, silicon resin and the like. Further, in the case of laminating without using an adhesive, a method such as an extrusion method, a sandwich laminating method, or a thermal laminating method can be used.

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

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

Examples of the thermoplastic resin used for forming the back surface adhesive layer include 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, through the following first and second steps.
A resin composition having an uneven shape on the base material layer and containing 1 part by mass or more and 5 parts by mass or less of inorganic particles and 1 part by mass or more and 5 parts by mass or less of synthetic resin particles with respect to 100 parts by mass of the resin. First step of forming a laminated body in which the surface layers formed by the above steps are laminated. A second step of forming a peelable protective film layer on the surface layer of the laminated body obtained in the first step.

In the first step and the second step, the components used for forming each layer, the specific conditions of the forming method of each layer, the method of forming the uneven shape of the surface layer 2 and the like are as described in the column of the composition of each layer. Is.

2. 2. Decorative resin molded product (decorative resin molded product with protective film)
The decorative resin molded product of the present invention is formed by integrating a molding resin with the decorative sheet of the present invention. That is, in the decorative resin molded product of the present invention, at least the molded resin layer 6, the base material layer 1, and the surface layer 2 having an uneven shape are laminated in this order, and the surface layer 2 has 100 mass of resin. It is characterized by containing 1 to 5 parts by mass of inorganic particles and 1 to 5 parts by mass of synthetic resin particles with respect to the portion. The decorative resin molded product can be obtained by peeling the protective film layer 3 from the decorative resin molded product with a protective film described later.

The decorative resin molded product with a protective film of the present invention is formed by integrating the decorative sheet of the present invention and the molding resin. That is, in the decorative resin molded product with a protective film of the present invention, at least the molded resin layer 6, the base material layer 1, the surface layer 2 having an uneven shape, and the protective film layer 3 are laminated in this order, and the surface layer 2 is formed. However, it is characterized by containing 1 to 5 parts by mass of inorganic particles and 1 to 5 parts by mass of synthetic resin particles with respect to 100 parts by mass of the resin.

The decorative resin molded product of the present invention is preferably provided with the uneven shape provided in the surface layer 2 of the decorative sheet. The uneven shape of the surface layer 2 of the decorative sheet usually changes due to heat and pressure during injection molding. In a decorative resin molded product, the 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. It is about 15 μm, preferably 2 to 13 μm, and more preferably 3 to 11 μm.

From the same viewpoint, the maximum height (Rz) of the surface of the surface layer 2 opposite to the base layer 1 side is usually 5 to 50 μm, preferably 10 to 40 μm, and more preferably 15 to 30 μm. Can be mentioned. From the same viewpoint, the ten-point average height (Rzjis) of the surface of the surface layer 2 opposite to the base layer 1 side is usually 5 to 40 μm, preferably 10 to 35 μm, and more preferably 15 to 30 μm. Can be mentioned. The center line average roughness (Ra), maximum height (Rz), and ten-point average height (Rzjis) each comply with JIS B 0601: 2001, and are the surface layers of the decorative resin molded product. It is a value measured about the surface of 2.

FIG. 4 shows a cross-sectional structure of one aspect of the decorative resin molded product with a protective film of the present invention. Further, FIG. 5 shows a cross-sectional structure of one aspect of the decorative resin molded product of the present invention.

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.

By using the decorative sheet of the present invention for various injection molding methods to produce a decorative resin molded product with a protective film, the effect of suppressing the uneven shape from being impaired during injection molding can be suitably exhibited. Can be done. 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 protective film) 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 fluid 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 protective film) 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 (decorative resin molded product with a protective film) is obtained by adding the present invention on a three-dimensional resin molded body (molded resin layer) prepared in advance by a vacuum pressure bonding method or the like. It can also be produced by a decoration method in which a decoration sheet is attached.

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 resins, styrene resins, polycarbonate resins, acrylic resins, vinyl chloride resins 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.

A decorative resin molded product can be obtained by peeling and removing the protective film layer from the decorative resin molded product with a protective film of the present invention. Further, in the decorative resin molded product with a protective film, the protective film layer serves as a protective sheet for the decorative resin molded product, so that the protective film layer should be stored as it is without being peeled off after manufacturing. You may peel it off. 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.

As described above, by peeling and removing the protective film layer 3 from the decorative resin molded product with the protective film, a decorative resin molded product having an uneven shape on the surface can be obtained. When the protective film layer 3 is peeled off and removed from the decorative resin molded product with the protective film, the surface layer 2 appears on the surface of the decorative resin molded product, and the uneven shape thereof expresses an excellent design feeling and the like. FIG. 5 shows a cross-sectional structure of an aspect of the decorative resin molded product in which the protective film layer 3 is removed from the decorative resin molded product with the protective film of FIG.

The decorative resin molded product of the present invention has a texture based on the uneven shape of the surface layer 2 and a low-gloss design. Therefore, for example, an interior material or an exterior material of a vehicle such as an automobile; Building members such as edges; Joinery such as window frames and door frames; Interior materials for buildings such as walls, floors and ceilings; Housings for home appliances such as TV receivers and air conditioners; Can be used as containers, etc. ..

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.

[Manufacturing of decorative sheets]
Examples 1 to 8 and Comparative Examples 1 to 9
A decorative sheet was manufactured by the following procedure. An ABS resin film having a thickness of 475 μm was used as the base material layer. Next, a wood grain pattern layer (thickness 5 μm) was formed by gravure printing on the base material layer using an ink composition containing an acrylic resin. Next, a primer layer containing a binder resin composed of a two-component curable resin containing 100 parts by mass of the main agent (acrylic polyol / urethane, mass ratio 9/1) and 7 parts by mass of the curing agent (hexamethylene diisocyanate) on the pattern layer. The resin composition for use 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 pattern layer / a primer layer was laminated in this order was obtained.

Next, the primer layer side of the obtained laminate was embossed to form an uneven shape on the primer layer. Details of the embossed version are as described below. Next, in order to form the surface layer, the resin composition in which the ionizing radiation resin (EB resin) shown in Tables 1 and 2 and the particles are blended on the primer layer on which the uneven shape is formed is cured. The coating was applied so that the thickness (thickness of the convex portion of the uneven shape of the surface layer) was 10 μm. This resin composition was irradiated with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad) to cure it, and a surface layer having an uneven shape was formed. The uneven shape of the surface layer corresponds to the uneven shape of the primer layer. Next, by laminating a protective film layer formed of a polyethylene film by extrusion molding on the surface layer, a base material layer / a pattern layer / a primer layer / a surface layer having an uneven shape / a protective film layer (polyethylene (polyethylene) A decorative sheet having a laminated structure in which PE) layers) were laminated in this order was obtained. The uneven concave portion of the surface layer is filled with the protective film layer. Further, as the conditions for extrusion molding, the temperature under the die of the extruder was set to about 320 to 330 ° C., and the thickness of the polyethylene layer (thickness on the convex portion of the uneven shape of the surface layer) was set to 80 μm.

Embossed version A: Geometric pattern, embossed version depth 60 μm
Embossed version B: Geometric pattern, embossed version depth 60 μm
Embossed version C: Wood grain pattern, embossed version depth 60 μm
Embossed version D: Geometric pattern, embossed version depth 60 μm
Embossed version E: Striped pattern, embossed version depth 60 μm

<Measurement of surface roughness of decorative sheet>
In accordance with JIS B 0601: 2001, the protective film layer is peeled off from each decorative sheet obtained above, and various surface roughness (center line average roughness (Ra), maximum height) of the surface layer side surface is obtained. (Rz) and ten-point average height (Rzjis)) were measured. As the 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 and 2.

<Measurement of surface roughness of decorative resin molded products>
The protective film layer is peeled off from each decorative resin molded product obtained in the moldability evaluation described later, and the surface on the surface layer side has various surface roughness in the same manner as in the above <Measurement of surface roughness of decorative sheet>. Was measured. The measurement results are shown in Tables 1 and 2.

<Evaluation of moldability>
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. After cooling the molded decorative sheet, it was released from the mold. Then, the injection resin was injected into the cavity of the mold, the decorative sheet and the injection resin were integrally molded, and at the same time as being taken out from the mold, a decorative resin molded product was obtained. The appearance after injection molding was evaluated according to the following criteria. The results are shown in Tables 1 and 2.
A: No cracks or whitening were observed on the surface layer. In addition, fine cracks and whitening of the coating film were observed in a part of the three-dimensional shape portion or the maximum stretched portion, but there is no problem in practical use.
B: The shape of the mold could not be followed, and the surface layer was slightly cracked or whitened.
C: The shape of the mold could not be followed, and remarkable cracking and whitening of the coating film was observed on the surface layer.

<Evaluation of peelability of protective film layer>
The peelability when peeling the protective film layer from each decorative resin molded product obtained in the above moldability evaluation was evaluated according to the following criteria. The results are shown in Tables 1 and 2.
A: The protective film layer is in close contact with the surface layer and can be easily peeled off by hand.
A-: The protective film layer is in close contact with the surface layer, and although it feels a little heavy when peeled off, it can be peeled off by hand without difficulty.
B +: The protective film layer is strongly adhered to the surface layer and feels heavy at the time of peeling, which reduces the efficiency of the peeling work, but can be peeled by hand.
B: The peeling strength of the protective film layer is high, and there is a part that cannot be peeled off.
C: The peel strength of the protective film layer is too low to properly protect the surface layer.
D: The peeling strength of the protective film layer is too high to peel off the protective film layer.

<Low gloss design evaluation>
The protective film layer was peeled off from each decorative resin molded product obtained in the above moldability evaluation, and the surface was visually observed to evaluate the low-gloss design property according to the following criteria. The results are shown in Tables 1 and 2.
A +: Very low gloss and not cloudy.
A: It has low luster and is not cloudy.
B: It has a low gloss, but it becomes cloudy white, so there is a problem in actual use.
C: High gloss.

<Evaluation of design and feel due to uneven shape>
The protective film layer is peeled off from each decorative resin molded product obtained in the above moldability evaluation, the surface is visually observed, and the surface is touched by hand. did. The evaluation results of these designs are shown in Tables 1 and 2.
A: The uneven shape was clearly felt by visual inspection and touch.
B: An uneven shape was felt by visual inspection and touch.
C: The uneven shape was slightly felt by visual inspection and touch.
D: No uneven shape was felt by visual inspection and touch.

<Abrasion resistance>
The surface of each decorative resin molded product obtained in the above moldability evaluation was subjected to a wear test using a Taber wear machine (wear wheel: CS-10, condition: 1 kg x 200 rotations), and withstands the following criteria. Abrasion property was evaluated. The results are shown in Tables 1 and 2.
A: There is no exposure of the substrate (base material layer).
B: The substrate is more than half exposed.
C: There is a significant exposure of the substrate.

<Chemical resistance of decorative sheet>
The protective film layer was peeled off from each decorative sheet obtained in the above moldability evaluation, 5 ml of sunscreen cosmetic was dropped on the surface of the decorative sheet, and the mixture was left in an oven at 60 ° C. for 4 hours. Next, after taking out the decorative sheet and rinsing the surface with a neutral detergent solution, the state of the dropped portion was visually observed, and the chemical resistance of the decorative sheet was evaluated according to the following criteria. The results are shown in Tables 1 and 2. The sunscreen cosmetic used was commercially available and contained avobenzone (3%), homosalate (10%), octisalate (5%), octocrylene (2.8%) and oxybenzone (6%). The resin surface is highly erosive.
A: There is no change in the appearance of the decorative sheet surface.
B: There was a slight change in gloss on the surface of the decorative sheet, but no obvious whitening, swelling, dissolution, etc. were observed.
C: There was whitening, swelling, and dissolution on the surface of the decorative sheet.

1 Base layer 2 Surface layer 3 Protective film layer 4 Primer layer 5 Picture layer 6 Molding resin layer

Claims (11)

It is composed of at least a base material layer, a surface layer having an uneven shape, and a laminated body including a peelable protective film layer that covers the uneven shape of the surface layer.
The surface layer is composed of a resin composition containing 1 part by mass or more and 5 parts by mass or less of inorganic particles and 1 part by mass or more and 5 parts by mass or less of synthetic resin particles with respect to 100 parts by mass of the resin .
A decorative sheet in which the uneven concave portion of the surface layer reaches the base material layer . 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 side is 5 μm or more and 20 μm or less. The decorative sheet according to claim 1 or 2, wherein the surface layer is a cured product of a resin composition containing an ionizing radiation curable resin as the resin. The surface layer is a cured product of a resin composition containing an ionizing radiation curable resin and a thermoplastic resin as the resin in a mass ratio of 10:90 to 25:75 , according to any one of claims 1 to 3. The described decorative sheet. The decorative sheet according to claim 4, wherein the weight average molecular weight of the thermoplastic resin is in the range of 90,000 or more and 150,000 or less. The decorative sheet according to any one of claims 3 to 5, wherein the number of functional groups of the monomer contained in the ionizing radiation curable resin is in the range of 1 to 6. The decorative sheet according to any one of claims 3 to 6, 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. The decorative sheet according to any one of claims 1 to 7, wherein a primer layer is laminated immediately below the surface layer. The decorative sheet according to any one of claims 1 to 8, wherein a pattern layer is laminated between the base material layer and the surface layer. At least, the molding resin layer, the base material layer, and the surface layer having an uneven shape are laminated in this order.
The surface layer contains 1 part by mass or more and 5 parts by mass or less of inorganic particles and 1 part by mass or more and 5 parts by mass or less of synthetic resin particles with respect to 100 parts by mass of resin .
A decorative resin molded product in which the uneven concave portion of the surface layer reaches the base material layer . A method for producing 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 9.

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