JP2020049838A - Decorative sheet and method for producing the same, and decorative resin molding - Google Patents

Abstract

To provide a decorative sheet which suitably expresses a design by a pattern layer.SOLUTION: A decorative sheet 10 is formed of a laminate including at least a coloring layer 2, a transparent base material layer 1, a pattern layer 4, a first protective layer 31 and a second protective layer 32 in this order, in which the second protective layer 32 is partially stacked.SELECTED DRAWING: Figure 1

Description

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

  2. Description of the Related Art Conventionally, decorative resin molded products obtained by laminating a decorative sheet on the surface of a resin molded product have been used for vehicle interior / exterior parts, building material interior materials, home electric appliance housings, and the like. In the production of such a decorative resin molded product, a molding method of integrating a decorative sheet, which is provided with a design in advance, with a resin by injection molding is used. As a typical example of such a molding method, a decorative sheet is previously formed into a three-dimensional shape by a vacuum forming die, the decorative sheet is inserted into an injection molding die, and a resin in a fluid state is injected into the die. By the insert molding method that integrates the resin and the decorative sheet by means of simultaneous injection molding, the decorative sheet inserted into the mold during injection molding is integrated with the molten resin injected into the cavity Decorating method can be mentioned. In addition to the molding method by injection molding, a decorative sheet is also used in a decorating method such as a vacuum compression bonding method, which is performed while applying heat and pressure to a preformed molded body while applying heat and pressure.

  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 Document 1). According to the technique disclosed in this document, by changing the gloss between the first and second protective layers of the decorative sheet and synchronizing the picture layer and the second protective layer, the decorative resin molded article can be obtained. High texture can be given.

JP 2014-193535 A

  Conventionally, for the purpose of suppressing the color change and variation of the base material layer, a concealing layer may be provided between the base material layer and the picture layer, for example, in the decorative sheet disclosed in Patent Document 1 Also, there is described an embodiment in which a concealing layer is provided between a base material layer and a picture layer. Alternatively, in order to express a desired design, a colored layer different from the picture layer may be provided between the base material layer and the picture layer in a solid or picture pattern.

  However, the present inventors have studied, for example, such as a geometric pattern, when the pattern is clear and precise design is expressed by the pattern layer, when the pattern layer is printed on a colored layer such as a concealment layer It has been found that the ink forming the picture layer is difficult to print properly due to the influence of the fine irregularities of the colored layer formed by printing.

  Under such circumstances, an object of the present invention is to provide a decorative sheet that appropriately expresses a design using a picture layer. Still another object of the present invention is to provide a method for manufacturing the decorative sheet and a decorative resin molded product using the decorative sheet.

  The present inventors have conducted intensive studies in order to solve the above problems. As a result, it is composed of a laminate including at least a coloring layer, a transparent base material layer, a picture layer, a first protective layer, and a second protective layer in this order, and the second protective layer is partially laminated. It has been found that the decorative sheet suitably expresses the design by the picture layer. 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 colored layer, a transparent substrate layer, a pattern layer, a first protective layer, and a laminate comprising a second protective layer in this order,
A decorative sheet, wherein the second protective layer is partially laminated.
Item 2. Item 4. The decorative sheet according to Item 1, wherein the pattern formed by the picture layer is a geometric pattern.
Item 3. Item 3. The decorative sheet according to Item 1 or 2, wherein the first protective layer contains a filler.
Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the picture layer and the transparent base material layer are in contact with each other.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the picture layer is partially formed on the transparent base material layer.
Item 6. Item 1. The pattern of the picture layer and the second protective layer are synchronized, and a transparent resin layer is laminated between the picture layer and the first protective layer. The decorative sheet described in.
Item 7. Item 7. The decorative sheet according to any one of Items 1 to 6, wherein a transparent resin layer is laminated between the picture layer and the first protective layer.
Item 8. A step of laminating a colored layer on one side of the transparent base material layer,
A step of laminating at least a picture layer, a first protective layer, and a second protective layer in this order on the side opposite to the colored layer side of the transparent base material layer,
With
The method for manufacturing a decorative sheet, wherein the second protective layer is partially laminated on the first protective layer.
Item 9. At least a molded resin layer, a colored layer, a transparent substrate layer, a pattern layer, a first protective layer, and a laminate comprising a second protective layer in this order,
A decorative resin molded product, wherein the second protective layer is partially laminated.

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet which expresses the design by a pattern layer suitably can be provided. Further, according to the present invention, it is possible to provide a method for manufacturing the decorative sheet, and a decorative resin molded product using the decorative sheet.

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

1. Decorative sheet The decorative sheet of the present invention comprises a laminate having at least a coloring layer, a transparent substrate layer, a picture layer, a first protective layer, and a second protective layer in this order, and a second protective layer. Are partially laminated. Since the decorative sheet of the present invention has such a configuration, it is possible to suitably express a design using the picture layer. More specifically, in the decorative sheet of the present invention, the coloring layer is provided on the back surface of the transparent base material layer, and since the picture layer is laminated without interposing the concealing layer, for example, In the case where a design such as a pattern with a clear and precise design is expressed by the design layer, the ink of the design layer is appropriately printed on the transparent base material layer, and the design by the design layer can be suitably expressed. it can. In addition, since the decorative sheet is manufactured by sequentially laminating the pattern layer, the first protective layer, and the second protective layer on the transparent base material layer, the pattern of the pattern layer is partially Synchronization with the provided second protective layer can be performed with high accuracy, and a design using a picture layer can be suitably exhibited.

  Note that, in the present invention, the pattern of the pattern layer and the synchronization with the second protective layer include, for example, the position where the pattern layer is formed when the decorative sheet is observed in plan view, and the position of the second protective layer. A mode in which the position where the layer is formed corresponds (so-called positive), and a mode in which the position where the pattern layer is formed and the position where the second protective layer is not formed ( So-called negative). FIGS. 1 to 4 illustrate a negative mode as an example of the synchronization between the pattern of the picture layer and the second protective layer.

  Hereinafter, the decorative sheet of the present invention will be described in detail. In the present specification, the numerical range indicated by “to” means “over” and “below”, except for the numerical range indicated as “over” and “below”. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. In this specification, “(meth) acrylate” means “acrylate or methacrylate”, and other similar substances have the same meaning.

Laminated Structure of Decorative Sheet As shown in FIGS. 1 and 2, the decorative sheet 10 of the present invention includes at least a colored layer 2, a transparent base material layer 1, a picture layer 4, a first protective layer 31, and The second protective layer 32 has a laminated structure in which the second protective layer 32 is laminated in this order. The second protective layer 32 is provided partially. That is, the second protective layer 32 is provided on a part of the surface of the first protective layer 31. On the first protective layer 31, an uneven shape is formed by a portion 3a provided with the second protective layer 32 and a portion 3b not provided with the second protective layer 32.

  In the decorative sheet 10 of the present invention, as shown in FIG. 2, for the purpose of improving chemical resistance and the like, if necessary, a transparent resin may be interposed between the picture layer 4 and the first protective layer 31. A layer 5 may be provided.

  As a laminated structure of the decorative sheet of the present invention, a laminated structure in which a colored layer / transparent substrate layer / picture layer / first protective layer / second protective layer are laminated in this order; colored layer / transparent substrate layer / A laminated structure in which a picture layer / transparent resin layer / first protective layer / second protective layer are laminated in this order is exemplified. FIG. 1 shows one embodiment of the laminated structure of the decorative sheet of the present invention, which is a decorative sheet in which a colored layer / transparent substrate layer / picture layer / first protective layer / second protective layer are laminated in this order. 1 shows a schematic cross-sectional view of an example. In FIG. 2, as one embodiment of the laminated structure of the decorative sheet of the present invention, a colored layer / transparent substrate layer / picture layer / transparent resin layer / first protective layer / second protective layer are laminated in this order. 1 shows a schematic sectional view of an example of a decorative sheet.

Composition of each layer forming the decorative sheet [Transparent substrate layer 1]
The transparent base material layer 1 is a layer provided for imparting rigidity to the decorative sheet 10 and maintaining its shape. Further, the transparent base material layer 1 is provided in order to form a decorative sheet suitable for vacuum forming (three-dimensional forming) by insert molding or the like.

  The transparent base material layer 1 is transparent to the extent that the colored layer 2 is visible (when the colored layer 2 is a concealing layer, the concealing effect is exhibited) (transparent in the present invention includes translucent. ). That is, the transparent base material layer 1 is usually transparent (colorless transparent, colored transparent, translucent). For example, the transparent substrate layer 1 may include a matting agent such as silica, a coloring agent, and the like. As the coloring agent, the coloring agents exemplified in the picture layer 4 described later can be used. Further, the transparent base material layer 1 may be subjected to coating for adjusting colors, formation of a pattern for imparting designability, and the like.

  The transparent base material layer 1 can be made of a transparent resin, a paper base material, or the like from the viewpoint of making the decorative sheet 10 suitable for three-dimensional molding. It is preferable that the transparent resin is formed of a transparent thermoplastic resin. The transparent thermoplastic resin is not particularly limited, but is a transparent acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”), an acrylic resin; a polyolefin-based resin such as polypropylene and polyethylene; a polycarbonate resin; Vinyl chloride resin; polyethylene terephthalate (PET) resin; acrylonitrile-butadiene-styrene resin; acrylonitrile-styrene-acrylate resin, and the like. Among these, the transparent substrate layer 1 is preferably formed of a transparent acrylic resin because of its high surface smoothness. The resin forming the transparent base material layer 1 may be one type or two or more types.

  The transparent 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 adhesion between the transparent substrate layer 1 and the adjacent layer. Good. Examples of the oxidation method performed as the surface treatment of the transparent 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 of forming a surface roughness of the transparent 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 transparent base material layer 1. From the viewpoint of effects and operability, a corona discharge treatment method is preferably used.

  The thickness of the transparent 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 500 μm, preferably about 75 to 200 μm, and more preferably about 100 to 150 μm. No. When the thickness of the transparent 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. In addition, the distance between the colored layer 2 and the picture layer 4 becomes appropriate, and when the decorative sheet is viewed in a plan view, a unique design such that the picture layer 4 floats appears.

[Coloring layer 2]
The colored layer 2 suppresses a change in color of the transparent base material layer 1 as a concealing layer (for example, yellowing due to ionizing radiation when the first protective layer 31 and the second protective layer 32 are cured) and variations. The transparent substrate layer 1 is provided on the side opposite to the picture layer 4 side for the purpose of expressing a desired design in combination with the picture layer 4 and the like. In the decorative sheet 10 of the present invention, since the coloring layer 2 is provided on the back surface of the transparent base material layer 1 and has a laminated configuration in which the picture layer 4 is laminated without the coloring layer 2 interposed therebetween, for example, In the case where a scientific pattern or the like is expressed by a design layer, the ink of the design layer 4 is appropriately printed on the transparent base material layer 1 so that the design by the design layer 4 can be suitably exhibited. Furthermore, since the decorative sheet 10 is manufactured by sequentially laminating the pattern layer 4, the first protective layer 31, and the second protective layer 32 on the transparent base material layer 1, the decorative layer 10 The pattern and the partially provided second protective layer 32 can be synchronized with high accuracy, and the design by the picture layer 4 can be suitably exhibited.

  As described above, the colored layer 2 is a layer provided for the purpose of imparting concealing properties to the decorative sheet 10 as a concealing layer, expressing a desired design in combination with the picture layer 4, and the like.

  The coloring layer 2 is usually formed using an ink composition in which additives such as a filler, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed with a coloring agent such as a binder, a pigment and a dye, and a solvent. , Designed according to the purpose. The colored layer 2 is preferably formed of a resin composition containing a binder and a pigment.

  The binder is appropriately selected from those used for the picture layer 4 described later. For example, when imparting a function as a concealing layer, an opaque layer using a pigment such as titanium oxide having a high concealing property is provided on the entire surface of one side of the transparent base material layer 1. If the purpose is to express a design, a colored transparent or colored opaque layer using a pigment having a desired color is formed on the entire surface of one side of the transparent base material layer 1 in a single color or in a pattern. May be formed so as to express. When the colored layer 2 is formed so as to express a pattern, it is difficult in manufacturing to print so as to be synchronized with the pattern layer 4 and the second protective layer 32 provided on the opposite side of the transparent base material layer 1. Is usually not synchronized.

  The thickness of the coloring layer 2 is selected according to the function to be provided, but is usually about 1 to 20 μm.

  As described above, the colored layer 2 is a layer provided for the purpose of imparting concealing properties to the decorative sheet 10 as a concealing layer or expressing a desired design in combination with the picture layer 4. Usually, a binder, a coloring agent such as a pigment and a dye, and a solvent, an extender pigment, a stabilizer, a plasticizer, a catalyst, are formed using an ink composition in which additives such as a curing agent are appropriately blended. Designed. The binder is appropriately selected from those used for the picture layer 4 described later. For example, when imparting a function as a concealing layer, an opaque layer using a pigment such as titanium oxide having a high concealing property is provided on the entire surface of one side of the transparent base material layer 1. If the purpose is to express a design, a colored transparent or colored opaque layer using a pigment having a desired color is formed on the entire surface of one side of the transparent base material layer 1 in a single color or in a pattern. May be formed so as to express. When the colored layer 2 is formed so as to express a pattern, it is difficult in manufacturing to print so as to be synchronized with the pattern layer 4 and the second protective layer 32 provided on the opposite side of the transparent base material layer 1. Is usually not synchronized. The thickness of the coloring layer is selected according to the function to be provided, but is usually about 1 to 20 μm.

[Picture layer 4]
The picture layer 4 is provided on the opposite side of the transparent base material layer 1 from the colored layer 2 side, and is a layer that gives decorativeness to the decorative sheet. More specifically, in the decorative sheet of the present invention, no colored layer is provided between the transparent base material layer 1 and the picture layer 4. Further, it is preferable that the transparent base material layer 1 and the picture layer 4 are in contact with each other.

  The picture layer 4 is formed, for example, by printing various patterns using ink and a printing machine. The pattern formed by the picture layer 4 is not particularly limited, and is, for example, a stone pattern, a cloth pattern, or a cloth pattern imitating a rock surface such as a geometric pattern, a wood pattern, a marble pattern (for example, a travertine marble pattern). , A tiled pattern, a brickwork pattern, and the like, and a pattern of parquet, patchwork, and the like obtained by combining these. 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 described above, among these patterns, in particular, in the case of expressing a clear and precise design with a pattern layer, such as a geometric pattern, when the pattern layer is printed on another colored layer, the printing is performed. Is affected by the fine irregularities of the colored layer formed by the above, it is difficult to print the ink forming the picture layer properly, but in the decorative sheet 10 of the present invention, the picture layer 4 is not interposed through the coloring layer 2. Since it is laminated on the transparent base material layer 1, the design by the picture layer can be suitably exhibited without being affected by the fine irregularities of the other colored layers. Therefore, in the decorative sheet of the present invention, a geometric pattern or the like is particularly suitable as the pattern formed by the picture layer 4.

  In addition, the picture layer 4 may be provided partially on the transparent base material layer 1 or may be provided on the entire surface. As described later, in the case where the pattern layer 4 is partially provided, for example, when the first protective layer 31 contacts the transparent base material layer 1 from a portion where the pattern layer 4 is not provided. , Chemical resistance is likely to be reduced. Therefore, when the picture layer 4 is partially provided, it is preferable to provide the transparent resin layer 5 between the picture layer 4 and the first protective layer 31.

  As the pattern ink used for the pattern layer 4, a mixture of a binder, a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like is appropriately used. The binder is not particularly limited, and examples thereof include a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin, a mixed resin of a vinyl chloride-vinyl acetate copolymer and an acrylic copolymer, and chlorinated polypropylene. Resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, and the like. 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 4 is not particularly limited, but is, for example, about 1 to 30 μm, and preferably about 1 to 20 μm.

[First protective layer 31]
The first protective layer 31 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 32 described later. The first protective layer 31 is preferably formed of a cured product of the ionizing radiation-curable resin composition. The ionizing radiation-curable resin used for forming the first protective layer 31 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 the ionizing radiation curable resins, the electron beam curable resin can be solvent-free, does not require a photopolymerization initiator, and has stable curing characteristics. 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 hydroxyl groups 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 the decorative sheet, such as when used in the manufacture of a decorative resin molded product, among the ionizing radiation-curable resins described above, from the viewpoint of obtaining excellent three-dimensional moldability, It is preferable to use a polyfunctional 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 described below is formed of a thermosetting resin. Excellent three-dimensional moldability can be obtained even with a cured product of the composition. 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 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 31 is not particularly limited as long as the effects of the present invention are obtained, but is not limited. The unevenness formed by the first protective layer 31 and the second protective layer 32 described below is maintained even by heat and pressure during molding and the like, so that the deterioration of the high texture displayed on the decorative sheet is improved. From the viewpoint of effective 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 31 is not particularly limited, as long as the effects of the present invention can be obtained. The unevenness formed by the first protective layer 31 and the second protective layer 32 described below is maintained even by heat and pressure during molding and the like, so that the deterioration of the high texture displayed on the decorative sheet is improved. From the viewpoint of effective 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.

  In the case where 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 31, their 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 31 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 the first protective layer 31, the inorganic particles and the resin particles mainly have a function of reducing the gloss of the first protective layer 31, 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 31 contains inorganic particles or resin particles, these particles are dispersed in the first protective layer 31.

  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.

  When the first protective layer 31 contains inorganic particles, the content of the inorganic particles is not particularly limited, but is preferably 1 to 60 parts by mass with respect to 1100 parts by mass of the resin contained in the first protective layer 31. And more preferably about 10 to 40 parts by mass. 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. From the viewpoint of further improving the scratch resistance of the decorative sheet, urethane beads are preferably used. 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.

  When the first protective layer 31 contains resin particles, the content of the resin particles is not particularly limited, but is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the resin contained in the first protective layer 31. And more preferably about 10 to 150 parts by mass.

  In the present invention, the particle diameter of the particles is measured by using a Shimadzu laser diffraction type particle size distribution analyzer SALD-2100, injecting powder to be measured from a nozzle using compressed air, and dispersing the powder in the air. This is a value measured by a spray-type dry measurement method.

  In the case where at least one of the inorganic particles and the resin particles is included in the first protective layer 31, some of these particles may project from the surface of the first protective layer 31, Particles may be buried inside the layer 31.

  Various additives can be compounded in the first protective layer 31 according to desired physical properties to be provided in the first protective layer 31. 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 31 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 31 can be uniformly irradiated with ionizing radiation, the resin composition can be cured uniformly, which is economically advantageous. Become. When the first protective layer 31 includes at least one of the above-described inorganic particles and resin particles, the thickness of the first protective layer 31 means that the inorganic particles or the resin particles are located on the surface of the first protective layer 31. It refers to the thickness of the part that is not done.

  The first protective layer 31 is formed, for example, by preparing the above-mentioned ionizing radiation-curable resin composition, applying the composition, 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 31 by a coating method described below. In the present invention, the prepared coating solution is coated on a layer adjacent to the first protective layer 31 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, thereby forming the first protective layer 31. 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 transmission capability increases as the acceleration voltage increases. Therefore, when a resin which is easily deteriorated by electron beam irradiation is used under the first protective layer 31, the electron beam transmission depth and The acceleration voltage is selected so that the thickness of the first protective layer 31 is substantially equal. This makes it possible to suppress the irradiation of an extra electron beam to the layer located below the first protective layer 31, and to minimize the deterioration of each layer due to the excess electron beam. The irradiation dose is preferably an amount at which the crosslink density of the first protective layer 31 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 32]
The second protective layer 32 is provided on a part of the first protective layer 31 in the decorative sheet of the present invention, and a high texture is imparted to the decorative sheet by the uneven shape formed thereby. Is done. Further, by providing a gloss difference between the second protective layer 32 and the first protective layer 31, a high texture can be imparted to the decorative sheet. For example, the second protective layer 32 is set to a high gloss state (gloss), the first protective layer 31 is set to a low gloss state (mat), and both layers, that is, the formation portion and the non-formation portion of the second protection layer 32 are formed. By expressing a difference in gloss between them, a high texture can be imparted to the decorative sheet.

  In the present invention, the second protective layer 32 may be partially provided so as to be synchronized with the picture layer 4. More specifically, a concave shape formed by a portion 3a where the second protective layer 32 is provided and a portion 3b where the second protective layer 32 is not provided on the surface of the first protective layer 31 and a pattern layer 4 which will be described later. By synchronizing with the pattern to be formed, the decorative sheet can be given an excellent design feeling. As described above, in the decorative sheet 10 of the present invention, the decorative sheet is obtained by sequentially laminating the picture layer 4, the first protective layer 31, and the second protective layer 32 on the transparent base material layer 1. Is manufactured, the pattern of the picture layer 4 and the partially provided second protective layer 32 can be synchronized with high accuracy, and the design by the picture layer can be suitably expressed. Further, in the present invention, by forming the first protective layer 31 from a cured product of the ionizing radiation-curable resin composition, the first protective layer 31 and the second protective layer 32 form a decorative sheet. It is possible to effectively suppress deterioration of the provided excellent design feeling during molding of the decorative resin molded product.

  The resin constituting the second protective layer 32 is not particularly limited, and includes the above-described ionizing radiation resin, thermoplastic resin, thermosetting resin, and the like. Among these, the second protective layer 32 is preferably formed of a cured product of the ionizing radiation resin composition. As the ionizing radiation-curable resin, the same as those exemplified for the first protective layer 31 are exemplified.

  The second protective layer 32 may include a matting agent or a wax as an additive. These additives are used to reduce the gloss of the second protective layer 32 or to further improve the scratch resistance. The matting agent is not particularly limited, and examples thereof include inorganic particles and resin particles. Examples of the inorganic particles and the resin particles may be the same as the inorganic particles and the resin particles illustrated in the first protective layer 31, respectively. In addition, in the second protective layer 32, the inorganic particles and the resin particles mainly exert a function of reducing the gloss of the second protective layer 32. As described above, by providing a gloss difference between the first protective layer 31 and the second protective layer 32, a high texture can be imparted to the decorative sheet. When inorganic particles and resin particles are included in the second protective layer 32, these particles are dispersed in the second protective layer 32.

  The particle size of the inorganic particles contained in the second protective layer 32 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 32 contains inorganic particles, the content of the inorganic particles contained in the second protective layer 32 is not particularly limited, and 100 parts by mass of the resin contained in the second protective layer 32 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 32. Parts.

  In the case where at least one of the inorganic particles and the resin particles is included in the second protective layer 32, some of these particles may project from the surface of the second protective layer 32, Particles may be buried inside the layer 32.

  The total proportion of the area of the portion where the second protective layer 32 is formed on the surface of the first protective layer 31 is not particularly limited, but is preferably 5 to 95%, more preferably 10 to 95%, Furthermore, the range of 20 to 95% is mentioned.

  The thickness of the second protective layer 32 is not particularly limited, but is preferably about 0.1 to 20 μm, more preferably about 0.5 to 10 μm, and more preferably about 0.5 to 10 μm, from the viewpoint of giving the decorative sheet an excellent design feeling. Preferably, it is about 1 to 5 μm. In the case where the second protective layer 32 includes at least one of the above-described inorganic particles and resin particles, the thickness of the second protective layer 32 means that the inorganic particles or the resin particles are located on the surface of the second protective layer 32. It refers to the thickness of the part that is not done.

  The second protective layer 32 can be formed by a method similar to that of the first protective layer 31 described above. In the present invention, the formation of the second protective layer 32 can be performed by applying an ionizing radiation-curable resin composition on the uncured first protective layer 31 and irradiating it with ionizing radiation.

[Transparent resin layer 5]
The transparent resin layer 5 is a layer included as necessary between the picture layer 4 and the first protective layer 31 for the purpose of improving the chemical resistance of the decorative sheet and the like. The transparent resin layer 5 can be formed by applying ink. For example, when the pattern layer 4 is partially provided, for example, when the first protective layer 31 contacts the transparent base material layer 1 from a portion where the pattern layer 4 is not provided, Chemical properties are likely to decrease. Therefore, when the picture layer 4 is partially provided, it is preferable to provide the transparent resin layer 5 between the picture layer 4 and the first protective layer 31. Further, when the first protective layer 31 contains a filler such as silica, the chemical resistance between the transparent base material layer 1 and the first protective layer 31 may not be sufficient. In such a case, it is particularly preferable to provide the transparent resin layer 5 between the picture layer 4 and the first protective layer 31.

  As the ink for forming the transparent resin layer 5, known inks can be used. For example, melamine resin, polyurethane resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer and acrylic resin Examples thereof include a resin mixed with a copolymer, a chlorinated polypropylene resin, an acrylic resin, a polyester resin, a polyamide resin, a butyral resin, a polystyrene resin, a nitrocellulose resin, and a cellulose acetate resin. These resins may be used alone or in a combination of two or more.

  The thickness of the transparent resin layer 5 is not particularly limited, but is, for example, about 0.1 to 10 μm, and preferably about 1 to 10 μm. When the transparent resin layer 5 satisfies such a thickness, the chemical resistance of the decorative sheet 10 can be improved.

  The transparent resin layer 5 is formed by a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, and a silk screen using an ink for forming the transparent resin layer 5. It is formed by an ordinary coating method such as solid coating, wire bar coating, flow coating, comma coating, pouring coating, brush coating, spray coating and the like.

2. The decorative sheet 10 of the present invention described above has a step of laminating the colored layer 2 on one surface of the transparent substrate layer 1 and a step of laminating the colored layer 2 of the transparent substrate layer 1 on the side opposite to the colored layer 2 side. Laminating at least the picture layer 4, the first protective layer 31, and the second protective layer 32 in this order, and partially arranging the second protective layer 32 on the first protective layer 31. It can be manufactured by laminating on.

  When other layers such as the above-described transparent resin layer 5 are laminated on the decorative sheet, these layers may be laminated in Step 2 or the like. 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.

3. Decorative resin molded article The decorative resin molded article 20 of the present invention is formed by integrating a molding resin with the decorative sheet of the present invention. That is, as shown in the schematic views of FIGS. 3 and 4, the decorative resin molded product 20 of the present invention includes at least the molded resin layer 6, the transparent base material layer 1, the first protective layer 31, And a second protection layer 32. The second protection layer 32 is partially laminated. In the decorative resin molded product 20 of the present invention, at least one layer such as the transparent resin layer 5 described above may be further provided as necessary (see FIG. 4).

  The decorative resin molded product of the present invention is produced by using the decorative sheet of the present invention, for example, by various injection molding methods such as insert molding, simultaneous injection molding decoration, blow molding, and gas injection molding. You. In the present invention, by providing the decorative sheet of the present invention to various injection molding methods to produce a decorative resin molded product, the decorative sheet and the molded resin layer can exhibit excellent adhesion. Among these injection molding methods, preferably, an insert molding method and a simultaneous injection molding decoration method are used.

  In the insert molding method, first, in a vacuum forming step, the decorative sheet of the present invention is vacuum-formed (off-line preforming) in advance to a molded product surface shape using a vacuum forming die, and then an unnecessary portion is trimmed as necessary. Obtain a molded sheet. This molded sheet is inserted into the injection mold, the injection mold is closed, 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. Thus, 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,
Trimming process of trimming the excess portion of the vacuum formed decorative sheet to obtain a molded sheet, inserting the molded sheet into the injection mold, closing the injection mold, and injecting the resin in the flow state into the injection mold Integration 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, when an ABS resin film is used as the transparent base material layer If so, the temperature can usually be set to 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.

  Further, in the simultaneous injection molding decoration method, the decorative sheet of the present invention is arranged in a female mold that is also used as a vacuum forming mold provided with a suction hole for injection molding, and preforming (in-line preforming) is performed with this female mold. After performing, the injection molding die is clamped, the resin in a fluid state is injected and filled in the mold, and 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. Thereby, 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 concealing layer 2 side 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. Pre-forming step of pre-forming the decorative sheet by vacuum-sucking from the movable mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable die.
After clamping the movable mold and the fixed mold having the decorative sheet closely adhered along the molding surface, the resin in the flowing state is injected, filled, and solidified in the cavity formed by both molds. An integrated process of forming a resin molded article by laminating and integrating the resin molded article and the decorative sheet, and a resin molding in which the movable mold is separated from the fixed mold and all layers of the decorative sheet are laminated. Removal process to take out the body.

  In the preliminary molding step of the injection molding simultaneous decorating method, the heating temperature of the decorating sheet is not particularly limited, and may be appropriately selected according to the type of resin constituting the decorating sheet, the thickness of the decorating sheet, etc. In the case where a polyester resin film or an acrylic resin film is used as the transparent base material layer, the temperature can usually be about 70 to 130 ° C. In addition, in the injection molding step, the temperature of the resin in a fluidized state is not particularly limited, but can be generally about 180 to 320 ° C.

  In addition, the decorative resin molded product of the present invention is a decorative method of attaching the decorative sheet of the present invention to a previously prepared three-dimensional resin molded product (molded resin layer 6) such as a vacuum compression method. Can also be produced. In the vacuum compression bonding method, first, the decorative sheet and the resin molded body of the present invention are placed in a vacuum pressing machine including a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side, and the decorative sheet is placed in the first vacuum chamber. The vacuum chamber is installed in a vacuum crimping machine such that the resin molded body is on the second vacuum chamber side, and the transparent substrate layer 1 side of the decorative sheet is facing the resin molded body, and the two vacuum chambers are in a vacuum state. And The resin molded body is installed on a vertically movable platform provided on the second vacuum chamber side. Next, while the first vacuum chamber is pressurized, the molded body is pressed against the decorative sheet using the elevating platform, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Stick on the surface of. Finally, the two vacuum chambers are opened to the atmospheric pressure, and an extra portion of the decorative sheet is trimmed if necessary, whereby the decorative resin molded product of the present invention can be obtained.

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

  In the decorative resin molded product of the present invention, the molded resin layer 6 may be formed by selecting a resin according to the application. The molding resin forming the molding resin layer 6 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, vinyl chloride resins, and the like. Among them, ABS resin is preferable. 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.

  The decorative resin molded product of the present invention includes, 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; It can be used as a housing for home appliances such as machines;

  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.

(Preparation of decorative sheet)
<Example 1>
An acrylic resin film (125 μm thickness) was used as a transparent base material layer. Includes an ink for forming a concealing layer (mixed resin of vinyl chloride-vinyl acetate copolymer and acrylic resin (mass ratio 50:50), titanium oxide-based white pigment, and solvent on one surface of the transparent base material layer Using an ink, a concealing layer (thickness: 1 μm) was formed on the entire surface of the transparent substrate layer. Next, the other surface of the transparent base material layer contains a pattern layer forming ink (a mixed resin of vinyl chloride-vinyl acetate copolymer and an acrylic resin (mass ratio of 50:50), a carbon-based black pigment, and a solvent). A pattern layer (2 μm thick) was formed by gravure printing using the ink. The pattern layer was partially formed on the surface of the transparent base material layer to express the design of a geometric pattern (dot pattern having a diameter of 1 mm and a pitch of 0.5 mm). Next, using a resin composition containing 30 parts by mass of an ionizing radiation resin (polycarbonate urethane acrylate) and a silica (particle diameter of 2 μm) resin on the pattern layer, uncured first protection by gravure printing. A layer (thickness: 3 μm) was formed on the entire surface. Next, on the uncured first protective layer, using a resin composition containing 30 parts by mass of ionizing radiation resin: pentaerythritol triacrylate and 70 parts by mass of a non-crosslinkable acrylic resin, Specifically, the second protective layer is not formed in the dot pattern forming portion of the picture layer, and the second protective layer is formed only in the non-pattern forming portion, A second protective layer (thickness 3 μm) was formed in a pattern. Next, an electron beam is irradiated from the second protective layer side of the obtained laminate (acceleration voltage: 165 kV, irradiation dose: 50 kGy (5 Mrad)) to cure the first protective layer and the second protective layer, A decorative sheet in which a concealing layer / transparent substrate layer / picture layer / first protective layer / second protective layer were laminated in this order was obtained. The total ratio of the area of the portion where the second protective layer was formed to the surface of the first protective layer was about 50%.

<Example 2>
On the picture layer, a transparent resin layer (thickness: 1 μm) is laminated using an ink containing a mixed resin of vinyl chloride-vinyl acetate copolymer and an acrylic resin (mass ratio: 50:50). Except for the lamination of the first protective layer, a concealing layer / transparent base layer / picture layer / transparent resin layer / first protective layer / second protective layer were laminated in this order in the same manner as in Example 1. The obtained decorative sheet was obtained.

<Comparative Example 1>
A transparent substrate layer / concealing layer / pattern layer / first layer was formed in the same manner as in Example 1 except that a picture layer, a first protective layer, and a second protective layer were laminated on the concealing layer. A decorative sheet having a protective layer / second protective layer laminated in this order was obtained.

<Comparative Example 2>
An acrylic resin film (125 μm thickness) was used as a transparent base material layer. Includes an ink for forming a picture layer (mixed resin of vinyl chloride-vinyl acetate copolymer and acrylic resin (mass ratio 50:50), carbon black pigment, and solvent) on one surface of the transparent base material layer A pattern layer (2 μm thick) was formed by gravure printing using the ink. The pattern layer was partially formed on the surface of the transparent base material layer to express the design of a geometric pattern (dot pattern having a diameter of 1 mm and a pitch of 0.5 mm). Next, the concealing layer is formed using an ink for forming the concealing layer (a mixed resin of a vinyl chloride-vinyl acetate copolymer and an acrylic resin (mass ratio of 50:50), a titanium oxide-based white pigment, and a solvent). (Thickness: 2 μm) was formed over the entire surface of the picture layer. Next, a transparent resin layer (thickness: 1 μm) is formed on the other surface of the transparent substrate layer using an ink containing a mixed resin of vinyl chloride-vinyl acetate copolymer and an acrylic resin (mass ratio: 50:50). did. Next, using a resin composition containing 30 parts by mass with respect to the ionizing radiation resin (polycarbonate-based urethane acrylate) and silica (particle diameter 2 μm) resin on the transparent resin layer, the uncured first resin is gravure-printed. (Thickness: 3 μm) was formed on the entire surface. Next, a second protective layer is formed on the uncured first protective layer using a resin composition containing 30 parts by mass of ionizing radiation resin: pentaerythritol triacrylate and 70 parts by mass of a non-crosslinkable acrylic resin. A layer (thickness: 3 μm) was formed in a pattern. Next, an electron beam is irradiated from the second protective layer side of the obtained laminate (acceleration voltage: 165 kV, irradiation dose: 50 kGy (5 Mrad)) to cure the first protective layer and the second protective layer, A decorative sheet was obtained in which the concealing layer / design layer / transparent substrate layer / first protective layer / second protective layer were laminated in this order. The total ratio of the area of the portion where the second protective layer was formed to the surface of the first protective layer was about 50%.

<Design based on picture layer>
[Printability of picture layer]
Each decorative sheet obtained in the example and the comparative example was observed from the second protective layer side, and it was evaluated according to the following evaluation criteria whether or not the picture layer developed a design that was appropriately printed. Table 2 shows the results.
A: The dot pattern can be clearly expressed. B: Some irregularities are formed around the dot pattern, and the cell pattern is slightly visible in the dot, so the dot pattern is slightly unclear. C: Inside the dot The dot pattern is unclear because the cells and streaks are remarkably visible and the color cannot be expressed correctly

[Synchronization between picture layer and second protective layer]
Each decorative sheet obtained in Examples and Comparative Examples was observed from the second protective layer side, and a geometric pattern of the picture layer and a concavo-convex shape of the second protective layer exhibited a design synchronized with each other. (Specifically, when the decorative sheet is viewed in plan from the second protective layer side, the formed portion of the second protective layer has a relatively high gloss and the non-formed portion has a low gloss.) Whether or not was evaluated according to the following evaluation criteria. Table 2 shows the results.
A: When the decorative sheet is viewed in plan from the second protective layer side, the dot pattern forming portion feels low gloss, and the dot pattern non-forming portion feels high gloss, and the design is synchronized with the gloss. It was excellent.
C: When the decorative sheet was viewed from the second protective layer side in a plan view, a pattern with high and low gloss on the surface was formed to be shifted from the dot pattern, and the design was inferior.

<Chemical resistance>
The surface of the second protective layer of each of the decorative sheets obtained in the examples and the comparative examples was coated with gauze immersed in ethanol (99.5%) using a weight (1.5 kg load) having a gauze attached first. Rubbing was performed reciprocally, the surface state of the decorative sheet was visually observed, and the chemical resistance was evaluated according to the following evaluation criteria. Table 2 shows the results.
A: There is no change in the design before and after rubbing.
B: There is neither a pattern nor a second protective layer, the printed layer is peeled off only at the first protective layer, and the base material is visible.
C: All the printed layers on the rubbing surface were peeled off, and whitening and tearing of the base layer and the printed layer were observed.

DESCRIPTION OF SYMBOLS 1 ... Transparent base material layer 2 ... Coloring layer 31 ... First protective layer 32 ... Second protective layer 4 ... Picture layer 5 ... Transparent resin layer 6 ... Molding resin layer 10 ... Decoration sheet 20 ... Decoration resin molding

Claims (9)

At least a colored layer, a transparent substrate layer, a pattern layer, a first protective layer, and a laminate comprising a second protective layer in this order,
A decorative sheet, wherein the second protective layer is partially laminated.   The decorative sheet according to claim 1, wherein the pattern formed by the picture layer is a geometric pattern.   The decorative sheet according to claim 1, wherein the first protective layer contains a filler.   The decorative sheet according to any one of claims 1 to 3, wherein the picture layer and the transparent base material layer are in contact with each other.   The decorative sheet according to any one of claims 1 to 4, wherein the picture layer is partially formed on the transparent base material layer.   The transparent resin layer is laminated between the pattern layer and the first protective layer, wherein the pattern of the pattern layer and the second protective layer are synchronized. 6. Decorative sheet described in crab.   The decorative sheet according to any one of claims 1 to 6, wherein a transparent resin layer is laminated between the picture layer and the first protective layer. A step of laminating a colored layer on one side of the transparent base material layer,
A step of laminating at least a picture layer, a first protective layer, and a second protective layer in this order on the side opposite to the colored layer side of the transparent base material layer,
With
The method for manufacturing a decorative sheet, wherein the second protective layer is partially laminated on the first protective layer. At least a molded resin layer, a colored layer, a transparent substrate layer, a pattern layer, a first protective layer, and a laminate comprising a second protective layer in this order,
A decorative resin molded product, wherein the second protective layer is partially laminated.