JP6658847B2 - Decorative sheet and method for producing the same - Google Patents

Description

  The present invention relates to a decorative sheet that can suppress an increase in the size of a manufacturing apparatus and has excellent scratch resistance, a decorative resin molded product using the decorative sheet, and a method for manufacturing these.

  Conventionally, decorative sheets are laminated on the surface of various articles for the purpose of decoration. For example, a decorative resin molded product in which a decorative sheet is laminated on a molded resin layer is used as a vehicle interior / exterior component, a home appliance housing, and the like. Further, a decorative board formed by attaching a decorative sheet to a wood-based adherend is used for floor materials, doors, furniture, and the like.

  In the production of decorative resin molded products, a molding method or the like is used in which a decorative sheet provided with a design in advance is integrated with a resin by injection molding. As a typical example of such a method of manufacturing a decorative resin molded product, for example, an insert molding method is known. In the insert molding method, a decorative sheet is formed into a three-dimensional shape in advance by a vacuum forming die, the decorative sheet is inserted into an injection molding die, and the resin in a fluid state is injected into the injection molding die, so that the resin and the decorative sheet are formed. This is a method of integrating with a sheet.

  Since decorative sheets are used as surface materials for decorative resin molded products and the like, they are required to have surface characteristics such as scratch resistance. Further, with the recent consumer preference for high quality, decorative sheets are required to have designs that exhibit high texture.

  For example, as a technique for imparting a high texture to a decorative resin molded product, a pattern layer, a first protective layer, and a second protective layer partially provided on the first protective layer are provided on a base material. A technique using a decorative sheet is known (for example, see Patent Documents 1 and 2). According to the method disclosed in these documents, the gloss is changed between the first and second protective layers of the decorative sheet, and the pattern layer and the second protective layer are synchronized, so that the decorative resin molded article can be obtained. High texture can be given.

JP 2009-113387 A JP 2014-193535 A

  In the decorative sheets disclosed in Patent Literatures 1 and 2, in order to synchronize the picture layer and the second protective layer, it is necessary to control the position with high accuracy. It is necessary to perform the printing process in-line (that is, to continuously perform the process without once winding the raw decorative sheet material). As the resin forming the protective layer, a curable resin, particularly an ionizing radiation-curable resin, is preferably used from the viewpoint of imparting scratch resistance, abrasion resistance and the like. In this case, the step of applying the ionizing radiation-curable resin composition and the step of irradiating the ionizing radiation-curable resin composition with ionizing radiation and curing are generally performed in-line. Therefore, an apparatus for performing these steps tends to be large.

Further, in recent years, the decorative sheet has been required to have a higher design due to consumers' preference for high-quality products. In order to enhance the design of the decorative sheet, a method of increasing the number of colors of the picture layer can be considered. However, when increasing the number of colors of the pattern layer, it is necessary to increase the number of pattern printing units by the number of colors to be increased. For this reason, when the step of applying or curing the protective layer as described above is included, there is a problem that the size of the apparatus is further increased. In addition, the process of irradiating ionizing radiation to the ionizing radiation-curable resin forming the protective layer is performed off-line to avoid an increase in the size of the apparatus. Performing the step), the ionizing radiation-curable resin forming the second protective layer located on the outermost surface of the decorative sheet is wound up uncured. Then, in the raw decorative sheet, there were problems such as damage to the protective layer and blocking between the base layer and the protective layer.
Under such circumstances, an object of the present invention is to provide a decorative sheet that can suppress an increase in the size of a decorative sheet manufacturing apparatus and also has excellent scratch resistance.

  The present inventor has conducted intensive studies in order to solve the above problems. As a result, at least a base layer, a picture layer, a first protection layer, and a second protection layer partially provided on the first protection layer so as to be synchronized with the picture layer. And the first protective layer is formed of a cured product of the ionizing radiation-curable resin composition, and the second protective layer is formed of a cured product of the thermosetting resin composition. The present inventors have found that a decorative sheet can be manufactured by performing curing of an ionizing radiation-curable resin off-line, and the size of a decorative sheet manufacturing apparatus can be suppressed. Further, the present inventors have found that the decorative sheet has excellent scratch resistance. The present invention has been completed by further study based on these findings.

That is, the present invention provides the following aspects of the invention.
Item 1. At least a substrate layer, a pattern layer, a first protective layer, and a second protective layer partially provided on the first protective layer so as to be synchronized with the pattern layer. Have in order,
The first protective layer is formed of a cured product of the ionizing radiation-curable resin composition,
A decorative sheet, wherein the second protective layer is formed from a cured product of a thermosetting resin composition.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the cured product of the thermosetting resin composition forming the second protective layer contains a two-component curable urethane resin.
Item 3. Item 3. The decorative sheet according to item 1 or 2, wherein the ionizing radiation-curable resin composition forming the first protective layer contains polycarbonate (meth) acrylate.
Item 4. Item 4. The decorative sheet according to item 3, wherein the ionizing radiation-curable resin composition forming the first protective layer further includes a polyfunctional (meth) acrylate.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein at least one of the first protective layer and the second protective layer contains a matting agent.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein the total proportion of the area of the portion where the second protective layer is formed on the surface of the first protective layer is in the range of 5 to 95%. .
Item 7. Step 1 of laminating a picture layer on the base material layer,
A step 2 of applying an ionizing radiation-curable resin composition on the pattern layer and laminating an uncured first protective layer;
On the uncured first protective layer, a thermosetting resin composition is partially laminated so as to be synchronized with the picture layer, and then heated to form a cured product of the thermosetting resin composition. Step 3 of laminating the formed second protective layer;
Winding the decorative sheet material obtained by laminating the base layer, the picture layer, the uncured first protective layer, and the second protective layer obtained in the steps 1 to 3 Step 4,
The decorative sheet material is unwound from the wound body of the decorative sheet material, and the uncured first protective layer is irradiated with ionizing radiation to cure the uncured first protective layer. Step 5 of forming a protective layer of No. 1;
A method for manufacturing a decorative sheet, comprising:
Item 8. At least a substrate layer, a pattern layer, an uncured first protective layer, and a second partly provided on the uncured first protective layer so as to be synchronized with the pattern layer. Having a protective layer in this order,
The uncured first protective layer is formed of an uncured ionizing radiation-curable resin composition,
An original sheet of decorative sheet, wherein the second protective layer is formed of a cured product of a thermosetting resin composition.
Item 9. Step 1 of laminating a picture layer on the base material layer,
A step 2 of applying an ionizing radiation-curable resin composition on the pattern layer and laminating an uncured first protective layer;
A thermosetting resin composition is partially laminated on the uncured first protective layer so as to be synchronized with the pattern layer, and then heated to form a cured product of the thermosetting resin composition. Step 3 of laminating the formed second protective layer;
The decorative sheet material obtained by laminating the base material layer, the picture layer, the uncured first protective layer, and the second protective layer obtained in Steps 1 to 3 is wound up. Step 4,
And a method for producing a raw sheet of decorative sheet.
Item 10. Item 7. A decorative resin molded product obtained by laminating the decorative sheet according to any one of Items 1 to 6 on a molded resin layer.
Item 11. Item 7. A decorative plate comprising the decorative sheet according to any one of Items 1 to 6 attached to an adherend.

  ADVANTAGE OF THE INVENTION According to the decorative sheet of this invention, the enlargement of the manufacturing apparatus of a decorative sheet can be suppressed and the decorative sheet excellent also in the scratch resistance, the decorative resin molded article using the said decorative sheet, and these manufacturing A method can be provided.

It is a schematic sectional drawing of an example of the decorative sheet of this invention. It is a schematic sectional drawing of an example of the decorative sheet of this invention. It is a schematic sectional drawing of an example of the decorative resin molded article manufactured using the decorative sheet of this invention. It is a schematic sectional drawing of an example of the decorative resin molded article manufactured using the decorative sheet of this invention.

1. Decorative sheet The decorative sheet of the present invention is at least partially provided on the base layer, the picture layer, the first protective layer, and the first protective layer so as to be synchronized with the picture layer. A second protective layer in this order, the first protective layer is formed from a cured product of the ionizing radiation-curable resin composition, and the second protective layer is formed by curing the thermosetting resin composition. It is characterized by being formed by an object. In the decorative sheet of the present invention, by providing such a configuration, the ionizing radiation-curable resin can be cured and manufactured off-line, thereby suppressing an increase in the size of the decorative sheet manufacturing apparatus. it can. Furthermore, the decorative sheet of the present invention has excellent scratch resistance.

  Specifically, as described later, in the process of manufacturing the decorative sheet of the present invention, after applying the ionizing radiation-curable resin composition for forming the first protective layer on the pattern layer, the uncured first A thermosetting resin composition is applied from above the protective layer, and is thermoset to obtain a decorative sheet material. In this decorative sheet material, since the thermosetting second protective layer is partially formed on the uncured first protective layer, even if the decorative sheet material is once wound up, In this way, damage to the second protective layer and the uncured first protective layer and blocking of the decorative sheet material are effectively suppressed. Therefore, the decorative sheet of the present invention can be manufactured by applying the ionizing radiation-curable resin and then curing the ionizing radiation-curable resin off-line, thereby effectively suppressing an increase in the size of the decorative sheet manufacturing apparatus. can do.

  Furthermore, in the decorative sheet of the present invention, since the first protective layer is formed of a cured product of the ionizing radiation-curable resin composition, the first protective layer is also excellent in scratch resistance. Hereinafter, the decorative sheet of the present invention will be described in detail.

  In this specification, unless otherwise specified, “(meth) acrylic acid” means “acrylic acid or methacrylic acid”, and other similar notations have the same meaning.

Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure in which at least the base layer 1, the picture layer 2, the first protective layer 3, and the second protective layer 4 are laminated in this order. . For example, as shown in FIG. 1, the picture layer 2 is provided on the base material layer 1. Further, the first protective layer 3 is provided on the picture layer 2. Further, the second protective layer 4 is provided on a part 4 a of the surface of the first protective layer 3. On the surface of the first protective layer 3, an uneven shape is formed by a portion 4 a provided with the second protective layer 4 and a portion 4 b not provided with the second protective layer 4. .

  In the decorative sheet of the present invention, if necessary, for the purpose of increasing the adhesion between the first protective layer 3 and the layer adjacent thereto, such as between the first protective layer 3 and the picture layer 2. Alternatively, a primer layer 5 may be provided. Also, for the purpose of enhancing the formability of the decorative sheet, for example, between the picture layer 2 and the first protective layer 3, or between the picture layer 2 and the primer layer 5 if the primer layer 5 is provided. If necessary, a transparent film layer 6 may be provided. In addition, a shielding layer (not shown) may be provided as needed between the base layer 1 and the picture layer 2 for the purpose of suppressing a change or variation in the color of the base layer 1. Further, an adhesive layer (not shown) or the like may be provided on the surface on the base material layer 1 side.

  As a laminated structure of the decorative sheet of the present invention, a laminated structure in which a base layer / a pattern layer / a first protective layer / a second protective layer is laminated in this order; a substrate layer / a pattern layer / a primer layer / a first layer. A laminated structure in which a protective layer / second protective layer is laminated in this order; a laminated structure in which a base layer / concealing layer / picture layer / first protective layer / second protective layer are laminated in this order; / Laminated structure in which / concealing layer / picture layer / transparent film layer / first protective layer / second protective layer are laminated in this order; adhesive layer / base layer / concealing layer / picture layer / first protective layer / A laminated structure in which a second protective layer is laminated in this order; an adhesive layer / base layer / concealing layer / picture layer / transparent film layer / primer layer / first protective layer / second protective layer are laminated in this order Laminated structure. FIG. 1 is a schematic cross-sectional view of an example of a decorative sheet in which a base layer / a pattern layer / a first protective layer / a second protective layer are laminated in this order as one embodiment of the laminated structure of the decorative sheet of the present invention. Is shown. FIG. 2 shows, as an embodiment of the laminated structure of the decorative sheet of the present invention, a decorative sheet in which a base layer / a pattern layer / a transparent film layer / a primer layer / a first protective layer / a second protective layer are laminated in this order. 1 shows a schematic cross-sectional view of an example of FIG.

Composition of each layer forming the decorative sheet [base layer 1]
The base material layer 1 is a layer that functions as a support in the decorative sheet of the present invention. The substrate layer 1 is not particularly limited, and a fibrous sheet, a resin sheet, a metal sheet, a wood-based substrate sheet, or the like can be used according to the use of the decorative sheet. When three-dimensional moldability is required, for example, it is preferable to be formed of a resin sheet (resin film). The resin component used in the base material layer 1 is not particularly limited, and may be appropriately selected according to three-dimensional moldability, compatibility with the molded resin layer, and the like, and is preferably a thermoplastic resin. Specific examples of the thermoplastic resin include an acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as an “ABS resin”); an acrylonitrile-styrene-acrylate resin; an acrylic resin; a polyolefin such as polypropylene and polyethylene. Resins; polycarbonate resins; vinyl chloride resins; polyethylene terephthalate (PET) and the like. Among them, ABS resin is preferable from the viewpoint of three-dimensional moldability. As the resin component forming the base material layer 1, only one kind may be used, or two or more kinds may be mixed and used. Further, the base material layer 1 may be formed of a single-layer sheet, or may be formed of a multi-layer sheet of the same or different kinds of sheets.

  The base material layer 1 may be subjected to a physical or chemical surface treatment such as an oxidation method or a roughening method on one or both surfaces thereof, if necessary, in order to improve the adhesiveness with an adjacent layer. . Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment. In addition, examples of a method for forming a surface roughness of the base material layer 1 include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of the resin component constituting the base material layer 1, and preferably include a corona discharge treatment method from the viewpoint of effects and operability.

  In addition, the base material layer 1 may be colored with a coloring agent or the like, painted for adjusting the color, or formed with a pattern for providing design.

  The thickness of the base material layer 1 is not particularly limited and is appropriately set depending on the use of the decorative sheet and the like, but is usually about 50 to 800 μm, preferably about 100 to 600 μm, and more preferably about 200 to 500 μm. . When the thickness of the base material layer 1 is within the above range, the decorative sheet can be provided with more excellent three-dimensional moldability, designability, and the like.

[Picture layer 2]
The picture layer 2 is provided on the base material layer 1 and gives decorativeness to the decorative sheet, and is formed by printing various patterns using ink and a printing machine. The pattern formed by the picture layer 2 is not particularly limited, and is, for example, a grain pattern that imitates a rock surface such as a wood pattern, a marble pattern (for example, a travertine marble pattern), or a cloth that imitates a cloth or cloth pattern. Patterns, tiled patterns, brickwork patterns, and the like, as well as composite parquet, patchwork, and other patterns are also included. These patterns are formed by multicolor printing using normal yellow, red, blue, and black process colors, and also by multicolor printing using special colors prepared by preparing individual color plates constituting the pattern. It is formed.

  As the picture ink used for the picture layer 2, an ink obtained by appropriately mixing a binder with a coloring agent such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like is used. The binder is not particularly limited and includes, for example, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acryl copolymer resin, chlorinated polypropylene resin, acrylic resin, Examples include polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins. These resins may be used alone or in a combination of two or more.

  The colorant is not particularly limited. For example, carbon black (ink), iron black, titanium white, antimony white, graphite, titanium yellow, red iron oxide, inorganic pigments such as cadmium red, ultramarine blue, cobalt blue, and quinacridone red Organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue, metal pigments composed of scale-like foil pieces such as aluminum and brass, pearl luster composed of scale-like foil pieces such as titanium dioxide-coated mica and basic lead carbonate ) Pigments and the like.

  The thickness of the picture layer 2 is not particularly limited, but is, for example, about 1 to 30 μm, preferably about 1 to 20 μm.

[First protective layer 3]
The first protective layer 3 is a layer provided to enhance the scratch resistance, weather resistance, and the like of the decorative sheet, and to impart a high texture to the decorative sheet together with a second protective layer 4 described later. The first protective layer 3 is formed of a cured product of the ionizing radiation-curable resin composition. The ionizing radiation-curable resin used for forming the first protective layer 3 is a resin that crosslinks and cures when irradiated with ionizing radiation, and specifically, includes a polymerizable unsaturated bond or A mixture obtained by appropriately mixing at least one of a prepolymer, an oligomer, a monomer, and the like having an epoxy group is exemplified. Here, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule. Usually, ultraviolet (UV) or electron beam (EB) is used. It also includes charged particles such as electromagnetic waves such as X-rays and γ-rays, α-rays and ion beams. Among ionizing radiation-curable resins, the electron beam-curable resin can be made solvent-free, does not require a photopolymerization initiator, and has stable curing characteristics. Therefore, formation of the first protective layer 3 Is preferably used.

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

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

  When three-dimensional moldability is required for a decorative sheet, such as when used in the production of a decorative resin molded product, among the above-mentioned ionizing radiation-curable resins, from the viewpoint of obtaining excellent three-dimensional moldability, many types of resins are used. It is preferable to use a functional polycarbonate (meth) acrylate. In the decorative sheet of the present invention, the first protective layer is formed of a cured product of the ionizing radiation-curable resin composition containing polycarbonate (meth) acrylate, so that the second protective layer is formed of the thermosetting resin composition. Excellent three-dimensional moldability can be obtained even with a cured product. From the viewpoint of achieving both three-dimensional moldability and scratch resistance, it is more preferable to use a combination of a polyfunctional polycarbonate (meth) acrylate and a polyfunctional (meth) acrylate. When a polyfunctional (meth) acrylate monomer is used as the ionizing radiation-curable resin, it is preferable to use it in combination with a thermoplastic resin such as an acrylic resin from the viewpoint of obtaining excellent three-dimensional moldability. From the viewpoint of achieving both compatibility and scratch resistance, the mass ratio of the polyfunctional (meth) acrylate monomer and the thermoplastic resin in the ionizing radiation-curable resin composition is more preferably 25:75 to 75:25. . Hereinafter, the polyfunctional polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate will be described in detail.

<Polyfunctional polycarbonate (meth) acrylate>
The polyfunctional polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and has two or more (meth) acrylates in the terminal or side chain. In addition, from the viewpoint of improving crosslinking and curing, the (meth) acrylate preferably has 2 to 6 functional groups per molecule. The polyfunctional polycarbonate (meth) acrylate may be used alone or in combination of two or more.

  The polyfunctional polycarbonate (meth) acrylate is obtained, for example, by converting some or all of the hydroxyl groups of the polycarbonate polyol to (meth) acrylate (acrylate or methacrylate). This esterification reaction can be performed by a usual esterification reaction. For example, 1) a method of condensing a polycarbonate polyol and an acrylic acid halide or a methacrylic acid halide in the presence of a base, 2) a method of condensing a polycarbonate polyol with an acrylic acid anhydride or a methacrylic acid anhydride in the presence of a catalyst, Or 3) a method of condensing a polycarbonate polyol with acrylic acid or methacrylic acid in the presence of an acid catalyst.

  The polycarbonate polyol is a polymer having a carbonate bond in a polymer main chain and having two or more, preferably 2 to 50, and more preferably 3 to 50 hydroxyl groups at a terminal or a side chain. As a typical production method of the polycarbonate polyol, a method of performing a polycondensation reaction with a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) serving as a carbonyl component can be given.

Diol compound used as a raw material of the polycarbonate polyol (A) is represented by the general formula HO-R ¹ -OH. Here, R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain an ether bond. R ¹ is, for example, a linear or branched alkylene group, cyclohexylene group, or phenylene group.

  Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5 pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2 -Hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in combination of two or more.

  Examples of the trihydric or higher polyhydric alcohol (B) used as a raw material of the polycarbonate polyol include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin, and sorbitol. Is mentioned. The trihydric or higher polyhydric alcohol may be an alcohol having a hydroxyl group obtained by adding 1 to 5 equivalents of ethylene oxide, propylene oxide, or another alkylene oxide to the hydroxyl group of the polyhydric alcohol. Good. These polyhydric alcohols may be used alone or in combination of two or more.

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

  The polycarbonate polyol is synthesized by subjecting the diol compound (A), the trihydric or higher polyhydric alcohol (B), and the compound (C) to be a carbonyl component to a polycondensation reaction under general conditions. The charged molar ratio of the diol compound (A) and the polyhydric alcohol (B) may be set, for example, in the range of 50:50 to 99: 1. The charged molar ratio of the compound (C) serving as the carbonyl component to the diol compound (A) and the polyhydric alcohol (B) is, for example, 0.2 to 2 with respect to the hydroxyl groups of the diol compound and the polyhydric alcohol. What is necessary is just to set in the range of an equivalent.

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

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

  Although the molecular weight of the polyfunctional polycarbonate (meth) acrylate is not particularly limited, for example, the weight average molecular weight is 5,000 or more, preferably 10,000 or more. The upper limit of the weight average molecular weight of the polyfunctional polycarbonate (meth) acrylate is not particularly limited, but is, for example, 100,000 or less, preferably 50,000 or less from the viewpoint of controlling the viscosity so as not to be too high. The weight average molecular weight of the polyfunctional polycarbonate (meth) acrylate is preferably 10,000 to 50,000, and more preferably 10,000, from the viewpoint of further improving the expression effect of a textured and rich low glossiness and the moldability. To 20,000.

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

  The content of the polyfunctional polycarbonate (meth) acrylate in the ionizing radiation-curable resin composition used for forming the first protective layer 3 is not particularly limited as long as the effects of the present invention are exhibited, but is not particularly limited. The unevenness formed by the first protective layer 3 and the second protective layer 3 described below is maintained even by heat and pressure during molding and the like, and the deterioration of the high texture displayed on the decorative sheet is more effectively prevented. From the viewpoint of suppression, the amount is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more.

<Polyfunctional (meth) acrylate>
Although it does not specifically limit as a polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate is preferable. The polyfunctional urethane (meth) acrylate is not particularly limited as long as it has a urethane bond in the polymer main chain and has two or more (meth) acrylates in the terminal or side chain. Such a polyfunctional 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. The number of functional groups per molecule of the polyfunctional urethane (meth) acrylate is preferably 2 to 12 from the viewpoint of improving crosslinking and curing. Further, the polyfunctional (meth) acrylate may be a silicone-modified one. The polyfunctional (meth) acrylate may be used alone or in combination of two or more.

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

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

  The content of the polyfunctional (meth) acrylate in the ionizing radiation-curable resin composition used for forming the first protective layer 3 is not particularly limited, as long as the effects of the present invention can be obtained. The unevenness formed by the first protective layer 3 and the second protective layer 3 described below is maintained even by heat and pressure during molding and the like, and the deterioration of the high texture displayed on the decorative sheet is more effectively prevented. From the viewpoint of suppression, the content is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.

  When the polyfunctional polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate are used in combination in the ionizing radiation-curable resin composition used for forming the first protective layer 3, the mass ratio (polyfunctional polycarbonate ( (Meth) acrylate: The polyfunctional (meth) acrylate is preferably about 50:50 to 99: 1, more preferably about 80:20 to 99: 1, and further preferably about 85:15 to 99: 1. .

  The first protective layer 3 may include a matting agent. These additives are used to lower the gloss of the protective layer 3 and to further improve the scratch resistance.

  Matting agents include, for example, inorganic particles and resin particles. In addition, in the first protective layer 3, the inorganic particles and the resin particles mainly have a function of reducing the gloss of the first protective layer 3, and the function of decreasing the gloss is generally the same as that of the inorganic particles. They tend to be larger than resin particles. When the first protective layer 3 contains inorganic particles or resin particles, these particles are dispersed in the first protective layer 3.

  The inorganic particles are not particularly limited as long as they are particles formed of an inorganic compound, and include, for example, silica particles, calcium carbonate particles, barium sulfate particles, alumina particles, and glass balloon particles. Particles. One kind of the inorganic particles may be used alone, or two or more kinds may be used in combination. The particle diameter of the inorganic particles is, for example, about 0.5 to 20 μm, preferably about 1 to 10 μm. In the present invention, the particle diameter of the inorganic particles is measured by using a Shimadzu laser diffraction type particle size distribution analyzer SALD-2100, injecting the powder to be measured from a nozzle using compressed air, and dispersing the particles in the air. This is a value measured by a spray-type dry measurement method.

  When the first protective layer 3 contains inorganic particles, the content of the inorganic particles is not particularly limited, but is preferably about 1 to 60 parts by mass with respect to 100 parts by mass of the above-described ionizing radiation-curable resin. Preferably, about 10 to 40 parts by mass is used. One kind of the inorganic particles may be used alone, or two or more kinds may be used in combination.

  The resin particles are not particularly limited as long as they are particles formed of a resin.Examples include urethane beads, nylon beads, acrylic beads, silicone beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, and polyethylene. Beads. Among these resin particles, urethane beads are preferable from the viewpoint of further improving the scratch resistance of the decorative sheet. One type of resin particles may be used alone, or two or more types may be used in combination. The particle size of the resin particles is, for example, about 0.5 to 30 μm, and preferably about 1 to 20 μm. The particle size of the resin particles is a value measured by the same method as that for the above-mentioned inorganic particles.

  When the first protective layer 3 contains resin particles, the content of the resin particles is not particularly limited, but based on 100 parts by mass of the ionizing radiation-curable resin contained in the ionizing radiation-curable resin composition described above. Preferably about 1 to 200 parts by weight, more preferably about 10 to 150 parts by weight.

  When at least one of the inorganic particles and the resin particles is included in the first protective layer 3, some of these particles may project from the surface of the first protective layer 3, Particles may be buried inside the layer 3.

  In the first protective layer 3, other than the above-mentioned polyfunctional polycarbonate (meth) acrylate, polyfunctional (meth) acrylate, inorganic particles, and resin particles, depending on desired physical properties to be provided in the first protective layer 3. Thus, various additives can be blended. Examples of the additive include a weather resistance improver such as an ultraviolet absorber and a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, Thixotropic agents, coupling agents, plasticizers, defoamers, fillers, solvents, coloring agents, and the like can be mentioned. These additives can be appropriately selected and used from those commonly used. In addition, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used as the ultraviolet absorber or light stabilizer.

  The thickness of the cured first protective layer 3 is not particularly limited, but is, for example, about 0.1 to 20 μm, preferably about 0.5 to 10 μm, and more preferably about 1 to 5 μm. When the thickness in such a range is satisfied, sufficient physical properties as a first protective layer such as scratch resistance can be obtained. In addition, since the ionizing radiation-curable resin composition forming the first protective layer 3 can be uniformly irradiated with ionizing radiation, the resin composition can be cured uniformly, which is economically advantageous. Become. When the first protective layer 3 includes at least one of the above-described inorganic particles and resin particles, the thickness of the first protective layer 3 means that the inorganic particles or the resin particles are located on the surface of the first protective layer 3. Refers to the thickness of the part that is not done

  The first protective layer 3 is formed, for example, by preparing the above-mentioned ionizing radiation-curable resin composition containing the above-mentioned polyfunctional polycarbonate (meth) acrylate, applying the same, and crosslinking and curing the composition. In addition, the viscosity of the ionizing radiation-curable resin composition may be a viscosity capable of forming an uncured resin layer on a layer adjacent to the first protective layer 3 by a coating method described below. In the present invention, the prepared coating solution is coated on the layer adjacent to the first protective layer 3 so as to have the thickness described above by a known method such as a gravure coat, a bar coat, a roll coat, a reverse roll coat, and a comma coat. , Preferably by gravure coating to form an uncured resin layer. The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam or ultraviolet light to cure the uncured resin layer to form the first protective layer 3. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, and the acceleration voltage is usually about 70 to 300 kV.

  In the electron beam irradiation, the higher the accelerating voltage, the higher the transmission capability. Therefore, when a resin which is easily deteriorated by the electron beam irradiation is used under the first protective layer 3, the electron beam transmission depth and The acceleration voltage is selected so that the thickness of the first protective layer 3 becomes substantially equal. This makes it possible to suppress the irradiation of an extra electron beam to the layer located below the first protective layer 3, and to minimize the deterioration of each layer due to the excess electron beam. The irradiation dose is preferably an amount at which the crosslinking density of the first protective layer 3 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). . Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as Cockloft-Walton type, Van degraft type, Resonant transformer type, Insulated core transformer type, Linear type, Dynamitron type, High frequency type, etc. Can be used. When ultraviolet rays are used as ionizing radiation, light rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet light source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

[Second protective layer 4]
The second protective layer 4 is provided on a part of the first protective layer 3 in the decorative sheet of the present invention, and imparts a high texture to the decorative sheet by the uneven shape formed thereby. I have. Further, by providing a gloss difference between the second protective layer 4 and the first protective layer 3, a high texture can be imparted to the decorative sheet. For example, the second protective layer 4 is set to a high gloss state (gloss), the first protective layer 3 is set to a low gloss state (mat), and both layers, that is, a part where the second protective layer 4 is formed and a part where the second protective layer 4 is not formed are formed. By expressing a gloss difference between them, a high texture can be imparted to the decorative sheet.

  In the present invention, the second protective layer 4 is partially provided so as to be synchronized with the picture layer 2. More specifically, the shape of the concave portion formed by the portion 4a where the second protective layer 4 is provided and the portion 4b where the second protective layer 4 is not provided on the surface of the first protective layer 3, and the pattern layer 2 described later By synchronizing with the pattern to be formed, the decorative sheet can be given a high texture and a genuine design feeling. For example, when the pattern formed on the pattern layer 2 described later is a woodgrain pattern, the conduit part represented by the pattern and the concave portion of the uneven shape are synchronized to give the woodgrain pattern a realistic feeling. Can be. Further, in the present invention, since the first protective layer 3 is formed of a cured product of the above-described ionizing radiation-curable resin composition, the first protective layer 3 and the second protective layer 4 form a decorative sheet. It is effectively suppressed that the expressed high texture and genuine design feeling are deteriorated during molding of the decorative resin molded product.

  The second protective layer 4 is formed from a cured product of a thermosetting resin composition. The thermosetting resin used for forming the second protective layer 4 is not particularly limited, and examples thereof include an acrylic polyol resin, an epoxy resin, a phenol resin, a urea resin, an unsaturated polyester resin, a melamine resin, an alkyd resin, and a polyimide. Examples thereof include resins, silicone resins, hydroxyl-functional acrylic resins, carboxyl-functional acrylic resins, amide-functional copolymers, and urethane resins. Of these, hydroxyl-functional acrylic resins and urethane resins are preferable. The thermosetting resin may be used alone or in a combination of two or more.

  As the hydroxyl-functional acrylic resin, an acrylic polyol resin is preferably used. Further, the acrylic polyol resin is not particularly limited. For example, (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate ) Acrylic acid alkyl esters and (meth) acrylic acid having a hydroxyl group in the molecule such as 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Those obtained by copolymerizing with an ester are exemplified. As the urethane resin, preferably, a two-component curable urethane resin is used.

  As the urethane resin, a polyurethane containing a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent) can be used. The polyol may be a compound having two or more hydroxyl groups in the molecule, and specific examples thereof include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, and polyether polyol. Specific examples of the isocyanate include a polyvalent isocyanate having two or more isocyanate groups in a molecule; an aromatic isocyanate such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate; Aliphatic (or alicyclic) isocyanates such as hydrogenated diphenylmethane diisocyanate.

  Among the urethane resins, from the viewpoint of improving adhesion after crosslinking, etc., preferably, an acrylic polyol or a polyester polyol as the polyol, and a combination of hexamethylene diisocyanate and 4,4-diphenylmethane diisocyanate as the crosslinking agent; Is a combination of acrylic polyol and hexamethylene diisocyanate.

  The acrylic resin is not particularly limited, but may be, for example, a homopolymer of (meth) acrylate, a copolymer of two or more different (meth) acrylate monomers, or (meth) acrylate. And a copolymer with the above monomer. As the (meth) acrylic resin, more specifically, poly (meth) acrylate, poly (ethyl) acrylate, poly (meth) acrylate, butyl (meth) acrylate, (meth) acrylate Methyl- (meth) butyl acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, styrene-methyl (meth) acrylate (Meth) acrylic acid esters such as polymers are exemplified. These acrylic resins may be used alone or in a combination of two or more.

  The (meth) acryl-urethane copolymer resin is not particularly limited, and examples thereof include an acryl-urethane (polyester urethane) block copolymer-based resin. Further, as the curing agent, the above-described various isocyanates are used. The ratio of the acryl to the urethane ratio in the acryl-urethane (polyester urethane) block copolymer resin is not particularly limited. For example, the acryl / urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8 / 2 to 2/8.

  The weight-average molecular weight of the thermosetting resin is not particularly limited. For example, if it is an acrylic polyol resin, it is preferably about 30,000 to 200,000, and more preferably about 70,000 to 150,000. The weight average molecular weight of the acrylic polyol resin in the present specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

  The mode of curing these thermosetting resins is not particularly limited, and for example, the following modes can be exemplified. For example, in the case of an epoxy resin, examples thereof include a reaction with an amine, an acid catalyst, a carboxylic acid, an acid anhydride, a hydroxyl group, dicyandiamide or ketimine. In the case of a phenol resin, a reaction between a base catalyst and an excess of aldehyde may be mentioned. In the case of a urea resin, a polycondensation reaction under alkaline or acidic conditions may, for example, be mentioned. In the case of an unsaturated polyester resin, a co-condensation reaction between maleic anhydride and a diol may, for example, be mentioned. In the case of a melamine resin, a heating polycondensation reaction of methylolmelamine and the like can be mentioned. In the case of an alkyd resin, a reaction of unsaturated groups introduced into a side chain or the like by air oxidation may be mentioned. In the case of a polyimide resin, a reaction in the presence of an acid or a weak alkali catalyst, a reaction with an isocyanate compound (in the case of a two-pack type), and the like can be mentioned. In the case of a silicone resin, examples include a condensation reaction in the presence of an acid catalyst for a silanol group. In the case of a hydroxyl group-functional acrylic resin, a reaction between a hydroxyl group and its own amino resin (in the case of a one-pack type) may be mentioned. In the case of a carboxyl functional acrylic resin, a reaction with a carboxylic acid such as acrylic acid or methacrylic acid and an epoxy compound can be mentioned. In the case of an amide-functional copolymer, a reaction with a hydroxyl group or a self-condensation reaction can be mentioned. As the urethane resin, a reaction between a resin containing a hydroxyl group, such as a polyester resin, a polyether resin, and an acrylic resin, and an isocyanate compound or a modified product thereof may be mentioned.

  The second protective layer 4 may include a matting agent or a wax as an additive. These additives are used to reduce the gloss of the second protective layer 4 and to further improve the scratch resistance. The matting agent is not particularly limited, and examples thereof include inorganic particles and resin particles. As the inorganic particles and the resin particles, the same particles as the inorganic particles and the resin particles exemplified in the first protective layer 3 can be exemplified. In addition, in the second protective layer 4, the inorganic particles and the resin particles mainly exert a function of reducing the gloss of the second protective layer 4. As described above, by providing a gloss difference between the first protective layer 3 and the second protective layer 4, a high texture can be imparted to the decorative sheet. When inorganic particles and resin particles are contained in the second protective layer 4, these particles are dispersed in the second protective layer 4.

  The particle size of the inorganic particles contained in the second protective layer 4 is not particularly limited, but is preferably about 0.5 to 15 μm, and more preferably about 1 to 10 μm. The particle size of the resin particles is not particularly limited, but is preferably about 0.1 to 20 μm, more preferably about 0.5 to 15 μm.

  When the second protective layer 4 contains inorganic particles, the content of the inorganic particles contained in the second protective layer 4 is not particularly limited, and 100 parts by mass of the resin contained in the second protective layer 4 To about 1 to 50 parts by weight, and more preferably about 5 to 30 parts by weight. The content of the resin particles is not particularly limited, and is preferably about 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, based on 100 parts by mass of the resin contained in the second protective layer 4. Parts.

  As the wax, a polyolefin wax such as a polypropylene wax and a polyethylene wax can be used. One type of wax may be used alone, two or more types may be used in combination, or may be used in combination with inorganic particles or resin particles.

  When the second protective layer 4 contains a wax, the content of the wax contained in the second protective layer 4 is not particularly limited, and may be based on 100 parts by mass of the resin contained in the second protective layer 4. And preferably about 0.1 to 5 parts by mass, more preferably about 0.5 to 2 parts by mass.

  When at least one of the inorganic particles and the resin particles is included in the second protective layer 4, some of these particles may project from the surface of the second protective layer 4, or the second protective layer 4 Particles may be buried inside the layer 4.

  Although the total ratio of the area of the portion where the second protective layer 4 is formed to the surface of the first protective layer 3 is not particularly limited, the blocking ratio when the decorative sheet material is used as a roll is From the viewpoint of effective suppression, the range is preferably 5 to 95%, more preferably 10 to 95%, and further preferably 20 to 95%.

  The thickness of the second protective layer 4 is not particularly limited, but gives a texture to the decorative sheet, and retains the uneven shape formed by the second protective layer 4 even after molding, and is exposed on the decorative sheet. From the viewpoint of effectively suppressing the deterioration of the high texture, the thickness is preferably about 0.1 to 20 μm, more preferably about 0.5 to 10 μm, and still more preferably about 1 to 5 μm. When the second protective layer 4 includes at least one of the above-described inorganic particles and resin particles, the thickness of the second protective layer 4 means that the inorganic particles or the resin particles are located on the surface of the second protective layer 4. It refers to the thickness of the part that is not done.

  The second protective layer 4 can be formed by a method similar to that of the first protective layer 3 described above. Specifically, a thermosetting resin composition for forming the second protective layer 4 is prepared, and a known printing method such as gravure printing, offset printing, silk screen printing, inkjet printing, or the like is used so as to have the thickness described above. Preferably, it can be formed by applying a resin composition to a part of the first protective layer 3 by gravure printing, and curing the thermosetting resin composition by heating. As described above, in the present invention, the formation of the second protective layer 4 can be performed by applying a thermosetting resin composition on the uncured first protective layer 3 and heating and curing.

[Primer layer 5]
The primer layer 5 is a layer included as necessary for the purpose of increasing the adhesion between the first protective layer 3 and a layer located thereunder. The primer layer 5 can be formed of a resin.

  The resin forming the primer layer 5 is not particularly limited, and examples thereof include a urethane resin, an acrylic resin, a (meth) acryl-urethane copolymer resin, a polyester resin, and a butyral resin. Among these resins, preferably, a urethane resin, an acrylic resin, and a (meth) acryl-urethane copolymer resin are used. These resins may be used alone or in a combination of two or more.

  The same urethane resin as that of the second protective layer 4 can be used.

  The thickness of the primer layer 5 is not particularly limited, but is, for example, about 0.1 to 10 μm, preferably about 1 to 10 μm. When the primer layer 5 satisfies such a thickness, cracking, breakage, whitening, and the like of the first protective layer 3 can be effectively suppressed.

  The primer layer 5 is formed by using a resin for forming the primer layer 5, gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, It is formed by a normal coating method such as a wire bar coating, a flow coating, a comma coating, a flowing coating, a brush coating, a spray coating or a transfer coating method. Here, the transfer coating method is a method in which a coating film such as a primer layer or an adhesive layer is formed on a thin sheet (film base material), and then coated on the surface of a target layer in the decorative sheet.

[Transparent film layer 6]
The transparent film layer 6 not only enhances the scratch resistance and weather resistance of the decorative sheet of the present invention, but also functions as a support for enhancing the moldability, and, if necessary, forms a layer on the base layer 1 and the picture layer 2. Is provided. The transparent film layer 6 is formed of a resin film. The provision of the transparent film layer 6 enhances the moldability, and makes it difficult for the first protective layer 3 and the second protective layer 4 to crack when the decorative sheet is three-dimensionally molded. The resin film forming the transparent film layer 6 is not particularly limited as long as it can enhance the formability of the decorative sheet and does not mask the design of the pattern layer 2 when provided on the pattern layer 2. And a film of a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or a film of an acrylic resin.

  The thickness of the transparent film layer 6 is not particularly limited, but is usually about 15 to 200 μm, preferably about 30 to 150 μm.

  The method for forming the transparent film layer 6 is not particularly limited. For example, a method of laminating the above resin film on the surface of an adjacent layer such as the base material layer 1 or the picture layer 2 by heat lamination, dry lamination, or the like Is mentioned.

[Hiding layer]
The concealing layer is provided between the base layer 1 and the first protective layer 3 or between the base layer 1 and the pattern if the pattern layer 2 is provided, for the purpose of suppressing color change and variation of the base layer 1. This layer is provided as needed between the layer 2 and the like.

  The concealing layer is provided as an opaque layer in general, because the concealing layer is provided to prevent the base material layer 1 from adversely affecting the color tone and the pattern of the decorative sheet.

  The concealing layer is formed using an ink composition in which a 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 are appropriately mixed with a binder. The ink composition for forming the concealing layer is appropriately selected from those used for the picture layer 2 described above.

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

[Adhesive layer]
The adhesive layer is a layer provided as needed on the back surface of the base material layer 1 for the purpose of improving the adhesion between the decorative sheet and the adherend or the injection resin. The resin forming the adhesive layer is not particularly limited as long as the adhesiveness between the decorative sheet and the adherend or the injection resin can be improved, and for example, a thermoplastic resin or a thermosetting resin is used. Can be Examples of the thermoplastic resin include an acrylic resin, an acrylic-modified polyolefin resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer, a thermoplastic urethane resin, a thermoplastic polyester resin, a polyamide resin, and a rubber-based resin. . The thermoplastic resins may be used alone or in combination of two or more. In addition, examples of the thermosetting resin include a urethane resin and an epoxy resin. The thermosetting resin may be used alone or in a combination of two or more.

  The adhesive layer is not necessarily a necessary layer, but when it is assumed that the decorative sheet of the present invention is applied to a decorative method by sticking on a resin molded body prepared in advance, such as a vacuum pressure bonding method described later. Is preferably provided. When used in a vacuum compression bonding method, it is preferable to form an adhesive layer by using a commonly used resin that exhibits adhesiveness when pressed or heated, among the various resins described above.

  The adhesive layer can be formed by applying the above resin to the surface of the base material layer 1. The thickness of the adhesive layer is not particularly limited, but is preferably about 1 to 20 μm.

2. Method for Manufacturing Decorative Sheet The above-described decorative sheet of the present invention can be manufactured by a method including the following steps 1 to 5.
Step 1 of laminating a picture layer on a base material layer
Step 2 of applying an ionizing radiation curable resin composition on the pattern layer and laminating an uncured first protective layer
On the uncured first protective layer, a thermosetting resin composition is partially laminated so as to be synchronized with the picture layer, and then heated to form a cured product of the thermosetting resin composition. Of laminating the formed second protective layer 3
Winding the decorative sheet material obtained by laminating the base layer, the picture layer, the uncured first protective layer, and the second protective layer obtained in the steps 1 to 3 Step 4
The decorative sheet material is unwound from the wound body of the decorative sheet material, and the uncured first protective layer is irradiated with ionizing radiation to cure the uncured first protective layer. Step 5 of forming the first protective layer.

  When laminating the above-mentioned primer layer 5, transparent film layer 6, concealing layer, and the like on the decorative sheet, before step 1 or step 2, or when laminating an adhesive layer, after step 5, A step of stacking layers may be provided. The components used for forming each layer, the thickness, the specific conditions of the method for forming each layer, and the like are as described in the column of the composition of each layer.

  As described above, in the manufacturing process of the decorative sheet of the present invention, after the ionizing radiation-curable resin composition forming the first protective layer 3 is applied onto the pattern layer 2 (step 2), the uncured A thermosetting resin composition is applied from the top of the protective layer 1 and thermally cured to obtain a decorative sheet raw material (step 3). In this decorative sheet material, the heat-cured second protective layer 4 is partially formed on the uncured first protective layer 3. Even when the film is wound up, scratching of the second protective layer 4 and the uncured first protective layer 3 and blocking of the original decorative sheet material are effectively suppressed. Therefore, in the method for producing a decorative sheet according to the present invention, after applying the ionizing radiation-curable resin, the ionizing radiation-curable resin can be cured offline to produce a decorative sheet. Enlargement can be effectively suppressed.

  The decorative sheet raw material produced in the production process of the decorative sheet of the present invention includes at least the base material layer 1, the picture layer 2, the uncured first protective layer 3, and the uncured first protective layer. On the protective layer 3, a second protective layer 4 partially provided so as to be synchronized with the picture layer 2 is provided in this order, and the uncured first protective layer 3 is The second protective layer 4 is formed of an uncured resin composition, and the second protective layer 4 is formed of a cured thermosetting resin composition.

As described in the method for manufacturing a decorative sheet according to the present invention, the raw sheet of the present invention is subjected to the following steps 1 to 3 (in the case of a wound body of the raw decorative sheet, steps 1 to 4). )).
Step 1 of laminating a picture layer on a base material layer
Step 2 of applying an ionizing radiation curable resin composition on the pattern layer and laminating an uncured first protective layer
On the uncured first protective layer, a thermosetting resin composition is partially laminated so as to be synchronized with the picture layer, and then heated to form a cured product of the thermosetting resin composition. Of laminating the formed second protective layer 3
Winding the decorative sheet material obtained by laminating the base layer, the picture layer, the uncured first protective layer, and the second protective layer obtained in the steps 1 to 3 Step 4.

3. Decorative resin molded article The decorative resin molded article of the present invention is formed by integrating a molding resin with the decorative sheet of the present invention. That is, the decorative resin molded product of the present invention includes at least a molding resin layer 7, a base layer 1, a picture layer 2, a first protective layer 3, and the first protective layer 3. A second protective layer 4 partially provided so as to be synchronized with the picture layer 2 in this order, and the first protective layer 3 is formed of a cured product of the ionizing radiation-curable resin composition. The second protective layer 4 is formed of a cured product of a thermosetting resin composition. In the decorative resin molded product of the present invention, if necessary, at least one layer such as the above-described picture layer 2, concealing layer, transparent film layer 6, primer layer 5, and adhesive layer may be further provided (FIG. See 3, 4).

  The decorative resin molded product of the present invention is produced, for example, by using the decorative sheet of the present invention by various injection molding methods such as insert molding, simultaneous injection molding decoration, blow molding, and gas injection molding. . In the present invention, the decorative sheet of the present invention is subjected to various injection molding methods to produce a decorative resin molded product, thereby exhibiting the above-described effect of suppressing a loss of texture during injection molding. Can be. Among these injection molding methods, preferably, an insert molding method and a simultaneous injection molding decoration method are used.

  In the insert molding method, first, in the vacuum forming step, the decorative sheet of the present invention is vacuum-formed (off-line preforming) in advance to the surface shape of a molded product using a vacuum forming die, and then, if necessary, trimming an excess portion to form. Get a sheet. This molded sheet is inserted into the injection mold, the injection mold is clamped, the resin in the fluid state is injected into the mold and solidified, and the decorative sheet is integrated with the outer surface of the resin molded product simultaneously with the injection molding. By doing so, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance by a vacuum forming die,
A trimming step of trimming an excess part of the vacuum-formed decorative sheet to obtain a molded sheet, and inserting the molded sheet into an injection mold, closing the injection mold, and injecting a resin in a flowing state into the injection mold. Process to integrate the resin and molded sheet.

  In the vacuum forming step in the insert forming method, the decorative sheet may be heated and formed. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. For example, if an ABS resin film is used as the base material layer, , Usually about 120 to 200 ° C. In addition, in the integration step, the temperature of the resin in a fluidized state is not particularly limited, but can be generally about 180 to 320 ° C.

  In the simultaneous decorating method for injection molding, the decorative sheet of the present invention is placed in a female mold that is also used as a vacuum mold having suction holes for injection molding, and pre-molding (in-line preliminary molding) is performed with this female mold. After that, by closing the injection mold, the resin in the flow state is injected into the mold, solidified, and the decorative sheet of the present invention is integrated with the outer surface of the resin molded product simultaneously with the injection molding. Then, a decorative resin molded product is manufactured.

More specifically, the decorated resin molded article of the present invention is manufactured by the simultaneous injection molding and decorating method including the following steps.
After installing the decorative sheet of the present invention such that the surface of the base material layer of the decorative sheet faces the forming surface of the movable mold having a predetermined-shaped forming surface, the decorative sheet is heated and softened. A pre-forming step of pre-forming the decorative sheet by vacuum-sucking from the movable die side and bringing the softened decorative sheet into close contact with the forming surface of the movable die;
After clamping a movable mold and a fixed mold having a decorative sheet closely adhered along a molding surface, injecting, filling and solidifying a resin in a flow state into a cavity formed by both molds. Forming a resin molded body, and laminating and integrating the resin molded body and the decorative sheet, and separating the movable mold from the fixed mold to take out the resin molded body in which all layers of the decorative sheet are laminated. Removal process.

  In the preliminary molding step of the simultaneous injection molding and decorating method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. If a polyester resin film or an acrylic resin film is used, the temperature can usually be set to about 70 to 130 ° C. In addition, in the injection molding step, the temperature of the resin in a fluidized state is not particularly limited, but can be generally about 180 to 320 ° C.

  Further, the decorative resin molded product of the present invention can be obtained by a decorative method of attaching the decorative sheet of the present invention to a previously prepared three-dimensional resin molded product (molded resin layer 7) such as a vacuum compression method. Can also be produced. In the vacuum compression bonding method, first, the decorative sheet and the resin molded article of the present invention are placed in a vacuum pressing machine including a first vacuum chamber located on the upper side and a second vacuum chamber positioned on the lower side, and the decorative sheet is a first vacuum chamber. The two vacuum chambers are evacuated so that the resin molded body is on the second vacuum chamber side and the base material layer 1 side of the decorative sheet is facing the resin molded body side. The resin molded body is installed on a vertically movable platform provided on the second vacuum chamber side. Next, the first vacuum chamber is pressurized, and the molded body is pressed against the decorative sheet using the elevating table, and the surface of the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Stick it on Finally, the two vacuum chambers are opened to the atmospheric pressure, and an extra portion of the decorative sheet is trimmed if necessary, whereby the decorative resin molded product of the present invention can be obtained.

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

  In the decorative resin molded product of the present invention, the molded resin layer 7 may be formed by selecting a resin according to the application. The molding resin forming the molding resin layer 7 may be a thermoplastic resin or a thermosetting resin.

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

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

4. Decorative board A decorative board can be obtained by sticking the decorative sheet of the present invention on an adherend. The adherend is not limited, and the same material as that used for a known decorative board can be used. Examples of the adherend include wood materials, metals, ceramics, plastics, and glass. In particular, the decorative sheet can be suitably used for wood materials. Specific examples of wood materials include veneers made of various materials such as cedar, cypress, zelkova, pine, lauan, teak, and melapie, veneer, wood plywood, particle board, and medium density fiberboard (MDF). , A chip board, or a composite base material on which the chip boards are laminated. As the wood material, it is preferable to use wood plywood, particle board, and medium density fiberboard (MDF).

  The method of attaching the decorative sheet to the adherend is not limited, and for example, a method of attaching the decorative sheet to the adherend with an adhesive can be adopted. The adhesive may be appropriately selected from known adhesives according to the type of the adherend and the like. For example, in addition to polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer and the like, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber and the like can be mentioned. These adhesives are used alone or in combination of two or more. By sticking the decorative sheet of the present invention on an adherend, a decorative plate can be obtained. The adherend is not limited, and the same material as that used for a known decorative board can be used. Examples of the adherend include wood materials, metals, ceramics, plastics, and glass. In particular, the decorative sheet can be suitably used for wood materials. Specific examples of the wood material include veneers made of various materials such as cedar, cypress, zelkova, pine, lauan, teak, and melapie, veneer veneer, wood plywood, particle board, and medium density fiberboard (MDF) , A chip board, or a composite base material on which a chip board is laminated. As the wood material, it is preferable to use wood plywood, particle board, or medium density fiberboard (MDF).

  The method of attaching the decorative sheet to the adherend is not limited, and for example, a method of attaching the decorative sheet to the adherend with an adhesive can be adopted. The adhesive may be appropriately selected from known adhesives according to the type of the adherend and the like. For example, polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, etc., butadiene / acrylonitrile rubber, neoprene rubber, natural rubber and the like can be mentioned. These adhesives are used alone or in combination of two or more.

  Since the decorative resin molded product and decorative board of the present invention have high scratch resistance and excellent design, for example, interior materials or exterior materials of vehicles such as automobiles; fittings such as window frames and door frames. Interior materials of buildings such as walls, floors and ceilings; housings of home electric appliances such as television receivers and air conditioners; and containers and the like.

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

<Examples 1-2 and Comparative Examples 1-3>
(Production of decorative sheet)
Picture layer (5 μm thickness) by gravure printing using an ink containing vinyl chloride resin / vinyl acetate-acrylic copolymer (mass ratio 50:50) on an ABS resin film (400 μmm thickness) as a base material layer Was formed. The pattern of the picture layer was a wood grain pattern. Next, an uncured first protective layer (thickness: 3 μm) was formed on the pattern layer by gravure printing using a resin composition having the composition shown in Table 1. Next, using the resin composition having the composition shown in Table 1 on the uncured first protective layer, the grain of the picture layer was formed so that the position corresponding to the wood-grained conduit portion was a non-formed portion. A second protective layer (thickness: 3 μm) synchronized with the pattern was formed in a pattern and cured by heating (at a temperature of 80 ° C.) to obtain a decorative sheet material. Next, the raw decorative sheet (length: 500 m) was wound around a cylindrical core tube having a circular cross section of 48 cm in diameter. From the obtained wound body, the decorative sheet material is unwound, and an electron beam is irradiated from the second protective layer side of the decorative sheet material (acceleration voltage: 165 kV, irradiation dose: 50 kGy (5 Mrad)) to obtain a first sheet. A decorative sheet in which a protective layer or a second protective layer is cured, and a base layer / picture layer / first protective layer / second protective layer having a configuration as shown in Table 1 is laminated in this order. I got In addition, in the decorative sheets obtained in Examples 1 and 2 and Comparative Examples 1 to 3, the total ratio of the area of the portion where the second protective layer is formed to the surface of the first protective layer is about 50. %Met.

(Evaluation of blocking of raw sheet of decorative sheet)
The rolls of the original sheets of the decorative sheets of Examples and Comparative Examples were stored at room temperature (20 ° C.) for one week. Next, blocking when the decorative sheet material was unwound from the wound body was evaluated according to the following criteria. Table 1 shows the results.
〇: No blocking was observed, and there was no change in the state of the first protective layer and the second protective layer after unwinding.
X: Blocking was observed, and the state of the first protective layer and the second protective layer after unwinding was changed.

(Evaluation of formability of decorative sheet)
Each decorative sheet of the example and the comparative example was heated to 160 ° C. with an infrared heater, respectively, to be softened. Next, using a vacuum forming die, vacuum forming was performed under the condition that the maximum stretching ratio was 150%, and a decorative sheet was formed so as to have the internal shape of the vacuum forming die. Next, after cooling the decorative sheet, it was released from the vacuum forming mold. The moldability of each of the released decorative sheets was evaluated according to the following evaluation criteria. Table 1 shows the results.
〇: No cracking or whitening was observed on the surface of the released decorative sheet, and the internal shape of the vacuum forming mold was followed satisfactorily. ×: Cracking or whitening was observed on the surface of the stretched portion of less than 100%. And could not follow the internal shape of the vacuum forming mold

(Scratch resistance evaluation test)
The surface of each decorative sheet of Examples and Comparative Examples was scratched 10 times with nails, the state of the surface was visually observed, and evaluated according to the following criteria. Table 1 shows the results.
〇: No scratch on the surface and no increase in gloss was observed. △: Fine scratches and increase in gloss were observed on the surface, but there was no problem in practical use. X: Significant scratches on the surface, gloss Increased

The following components were used as the components shown in Table 1.
(resin)
AU: 100 parts by mass of acrylic polyol / urethane resin (mass ratio 8: 2), 2-part curable resin EB: 7 parts by mass of hexamethylene diisocyanate EB: Bifunctional polycarbonate acrylate (weight average molecular weight 10,000) / bifunctional polycarbonate acrylate (weight) Mixed resin of average molecular weight 20,000) / 4-functional silicone-modified urethane acrylate (weight average molecular weight 6,000) (mass ratio 64.7 / 32.3 / 3)
(Inorganic particles)
1.3S: silica particles having a particle diameter of 1.3 μm 2S: silica particles having a particle diameter of 2 μm (additive: resin particles)
3U: urethane beads having a particle diameter of 3 μm (additive: wax)
WAX: mixture of polypropylene wax and polyethylene wax having a particle diameter of 5 μm

As shown in Table 1, in the raw decorative sheet, the first protective layer was formed of an uncured ionizing radiation-curable resin composition, and the second protective layer was formed of a thermosetting resin composition. In Examples 1 and 2 formed of the cured product, the blocking of the decorative sheet material is suppressed, and the decorative sheet after curing of the first protective layer is also excellent in moldability and scratch resistance. You can see that.
On the other hand, in the raw sheets of the decorative sheets of Comparative Examples 1 and 2 in which the uncured ionizing radiation-curable resin composition was used for the second protective layer, blocking occurred. Furthermore, the decorative sheet of Comparative Example 2 was inferior in moldability and scratch resistance. In the decorative sheet raw material of Comparative Example 3 in which both the first protective layer and the second protective layer were formed from a cured product of the thermosetting resin composition, the blocking was effectively suppressed. Was inferior in moldability and scratch resistance.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Picture layer 3 ... First protective layer 4 ... Second protective layer 5 ... Primer layer 6 ... Transparent film layer 7 ... Molding resin layer

Claims (10)

At least a substrate layer, a pattern layer, a first protective layer, and a second protective layer partially provided on the first protective layer so as to be synchronized with the pattern layer. Have in order,
The first protective layer is formed with a cured product of an ionizing radiation curable resin composition weight-average molecular weight by the number of functional groups 2-3 comprises more than 5000 polycarbonate (meth) acrylate,
A decorative sheet, wherein the second protective layer is formed from a cured product of a thermosetting resin composition.   The decorative sheet according to claim 1, wherein the cured product of the thermosetting resin composition forming the second protective layer includes a two-component curable urethane resin.   The decorative sheet according to claim 1, wherein the ionizing radiation-curable resin composition forming the first protective layer further includes a polyfunctional (meth) acrylate.   The decorative sheet according to any one of claims 1 to 3, wherein at least one of the first protective layer and the second protective layer contains a matting agent.   The makeup according to any one of claims 1 to 4, wherein a total ratio of an area of a portion where the second protective layer is formed to a surface of the first protective layer is in a range of 5 to 95%. Sheet.   Step 1 of laminating a picture layer on the base material layer,
  An ionizing radiation-curable resin composition containing a polycarbonate (meth) acrylate having a number of functional groups of 2 to 3 and a weight average molecular weight of 5000 or more is applied on the picture layer, and an uncured first protective layer is applied. Step 2 of laminating
  On the uncured first protective layer, a thermosetting resin composition is partially laminated so as to be synchronized with the picture layer, and then heated to form a cured product of the thermosetting resin composition. Step 3 of laminating the formed second protective layer;
  Winding the decorative sheet material obtained by laminating the base layer, the picture layer, the uncured first protective layer, and the second protective layer obtained in the steps 1 to 3 Step 4,
  The decorative sheet material is unwound from the wound body of the decorative sheet material, and the uncured first protective layer is irradiated with ionizing radiation to cure the uncured first protective layer. Step 5 of forming a protective layer of No. 1;
A method for manufacturing a decorative sheet, comprising:   At least a substrate layer, a pattern layer, an uncured first protective layer, and a second partly provided on the uncured first protective layer so as to be synchronized with the pattern layer. Having a protective layer in this order,
  The uncured first protective layer is formed of an uncured ionizing radiation-curable resin composition containing a polycarbonate (meth) acrylate having a number of functional groups of 2 to 3 and a weight average molecular weight of 5000 or more,
  An original sheet of decorative sheet, wherein the second protective layer is formed of a cured product of a thermosetting resin composition.   Step 1 of laminating a picture layer on the base material layer,
  An ionizing radiation-curable resin composition containing a polycarbonate (meth) acrylate having a number of functional groups of 2 to 3 and a weight average molecular weight of 5000 or more is applied on the picture layer, and an uncured first protective layer is applied. Step 2 of laminating
  On the uncured first protective layer, a thermosetting resin composition is partially laminated so as to be synchronized with the picture layer, and then heated to form a cured product of the thermosetting resin composition. Step 3 of laminating the formed second protective layer;
  Winding the decorative sheet material obtained by laminating the base layer, the picture layer, the uncured first protective layer, and the second protective layer obtained in the steps 1 to 3 Step 4,
And a method for producing a raw sheet of decorative sheet.   A decorative resin molded product obtained by laminating the decorative sheet according to any one of claims 1 to 5 on a molded resin layer.   A decorative board comprising the decorative sheet according to any one of claims 1 to 5 adhered to an adherend.