JP7063344B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

The present invention relates to a decorative sheet capable of imparting high smoothness to the surface of a decorative resin molded product. Further, the present invention relates to a decorative resin molded product using the decorative sheet.

Conventionally, decorative resin molded products in which a decorative sheet is laminated on the surface of a resin molded product have been used for vehicle interior / exterior parts, building material interior materials, home appliance housings, and the like. In the production of such a decorative resin molded product, a molding method or the like is used in which a decorative sheet having a pre-designed design is integrated with the resin by injection molding. As a typical example of such a molding method, a decorative sheet is molded into a three-dimensional shape in advance by a vacuum molding mold, the decorative sheet is inserted into an injection molding mold, and a fluid resin is injected into the mold. By doing so, the insert molding method that integrates the resin and the decorative sheet, and the injection molding that integrates the decorative sheet inserted in the mold during injection molding with the molten resin injected into the cavity at the same time. The decoration method can be mentioned. In addition to the molding method by injection molding, a decorative sheet is also used in a decorative method such as a vacuum crimping method in which a preformed molded body is attached while being heated or pressurized.

In recent years, with the diverse orientations of consumers, there is an increasing need for decorative resin molded products having high-brightness designs and glossy designs. For example, Patent Document 1 proposes a technique for expressing a glossy design by a pearl ink layer formed by using an ink composition containing a pearl pigment and a vinyl chloride-vinyl acetate copolymer as a binder resin. Has been done. However, when the layer containing a pigment such as a metal pigment or a pearl pigment is exposed to light, the binder resin may deteriorate and the weather resistance of the decorative sheet may decrease.

Japanese Unexamined Patent Publication No. 2005-14462

The present inventor has studied to form a pattern layer by using an acrylic resin having excellent weather resistance as a binder resin in a decorative sheet using a pigment as described above. As a result, it was clarified that although the weather resistance was improved, the smoothness of the surface of the decorative resin molded product was lowered after being molded into the decorative resin molded product. As a result of a detailed examination by the present inventor of this cause, an uneven shape is formed on the surface of the decorative resin molded product by a region where the pattern layer is located and a region where the pattern layer is not located. It became clear. In particular, such a problem was remarkable in a decorative sheet manufactured by transferring a pattern layer onto a substrate by using a transfer sheet in which the pattern layer was formed on the transfer substrate. ..
Under such circumstances, the present invention mainly provides a decorative sheet capable of imparting high smoothness to the surface of a decorative resin molded product, and a decorative resin molded product using the decorative sheet. Purpose.

The present inventor has made diligent studies to solve the above problems. As a result, at least, it is a decorative sheet composed of a laminated body in which a pattern layer containing a pigment and a solid layer are laminated, and the pattern layer is partially laminated in the laminated body and is included in the pattern layer. The binder resin contains 80% by mass or more of the acrylic resin, and the binder resin contained in the solid layer contains 80% by mass or more of the acrylic resin, thereby imparting high smoothness to the surface of the decorative resin molded product. I found that I could do it. The present invention is an invention completed by further studies based on such findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. At least, it is a decorative sheet composed of a laminated body in which a pattern layer containing a pigment and a solid layer are laminated.
In the laminated body, the pattern layer is partially laminated, and is
The binder resin contained in the pattern layer contains 80% by mass or more of an acrylic resin, and contains 80% by mass or more.
A decorative sheet in which the binder resin contained in the solid layer contains 80% by mass or more of an acrylic resin.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the pigment is at least one selected from the group consisting of a metal pigment, a pearl pigment, and a titanium oxide pigment.
Item 3. Item 2. The decorative sheet according to Item 1 or 2, wherein a resin layer containing a binder resin containing 30% by mass or more of a chlorine-based resin is further laminated.
Item 4. Item 3. The decorative sheet according to Item 3, wherein the resin layer contains at least one of an organic pigment and an inorganic pigment.
Item 5. Item 2. The decorative sheet according to any one of Items 1 to 4, wherein the pattern layer and the solid layer are laminated on a base material layer.
Item 6. Item 2. The decorative sheet according to any one of Items 1 to 5, further comprising a surface protective layer on the outermost surface. Item 7. Item 6. The decorative sheet according to Item 6, wherein the surface protective layer has a thickness of 30 μm or less.
Item 8. A step of partially laminating a binder resin containing 80% by mass or more of acrylic resin and a pattern layer containing a pigment on a transfer substrate, and a solid layer containing a binder resin containing 80% by mass or more of acrylic resin are laminated. The transfer sheet preparation process, in which the transfer sheet is produced by performing the steps,
A transfer step of transferring the pattern layer and the solid layer laminated on the transfer sheet onto a substrate,
A method of manufacturing a decorative sheet.
Item 9. Item 8. The method for manufacturing a decorative sheet according to Item 8, further comprising a step of laminating a surface protective layer after the transfer step.
Item 10. At least, it is a decorative resin molded product composed of a laminated body in which a pattern layer containing a pigment and a solid layer are laminated on a molding resin layer.
In the laminated body, the pattern layer is partially laminated, and is
The binder resin contained in the pattern layer contains 80% by mass or more of an acrylic resin, and contains 80% by mass or more.
A decorative resin molded product in which the binder resin contained in the solid layer contains 80% by mass or more of an acrylic resin.

According to the present invention, it is possible to provide a decorative sheet capable of imparting high smoothness to the surface of a decorative resin molded product. Further, according to the present invention, it is possible to provide a decorative resin molded product having a high surface smoothness.

It is a schematic diagram of the cross-sectional structure of an example of the decorative sheet of this invention. It is a schematic diagram of the cross-sectional structure of an example of the decorative sheet of this invention. It is a schematic diagram of the cross-sectional structure of an example of the decorative sheet of this invention. It is a schematic diagram for demonstrating the manufacturing process of the decorative sheet of this invention. It is a schematic diagram of the cross-sectional structure of an example of the decorative resin molded article of this invention.

1. 1. Decorative sheet The decorative sheet of the present invention is a decorative sheet composed of a laminated body in which at least a pattern layer containing a pigment and a solid layer are laminated, and the pattern layer is partially laminated in the laminated body. The binder resin contained in the pattern layer contains 80% by mass or more of acrylic resin, and the binder resin contained in the solid layer contains 80% by mass or more of acrylic resin. By having such a structure, the decorative sheet of the present invention can impart high smoothness to the surface of the decorative resin molded product. Hereinafter, the decorative sheet of the present invention will be described in detail.

Laminated structure of decorative sheet The decorative sheet of the present invention is composed of at least a laminated body in which a pattern layer 2 and a solid layer 3 are laminated. The decorative sheet of the present invention may have a base material layer 1, if necessary, for the purpose of enhancing the shape retention of the decorative sheet. Further, as described later, the resin layer 4 having a binder resin composition different from that of the pattern layer 2 and the solid layer 3 may be provided. Further, the decorative sheet of the present invention may be provided with the surface protective layer 5 as the outermost layer, if necessary, for the purpose of protecting the surface of the decorative sheet. Further, a primer layer 6 may be provided under the surface protective layer 5 as necessary for the purpose of enhancing the adhesion between the surface protective layer 5 and the layer adjacent thereto. Further, the adhesive layer 8 may be provided, if necessary, for the purpose of enhancing the adhesion between the decorative sheet and the molded resin layer 9.

As shown in FIG. 1 or 2, the pattern layer 2 is partially laminated in the horizontal direction x (direction perpendicular to the stacking direction y) in the laminated body constituting the decorative sheet of the present invention. .. Further, the solid layer 3 is laminated on the entire surface in the horizontal direction x in the laminated body constituting the decorative sheet of the present invention.

A plurality of the pattern layer 2, the solid layer 3, and the resin layer 4 may be laminated. The stacking order of the pattern layer 2, the solid layer 3, and the resin layer 4 is not particularly limited, but the solid layer 3 is more than the pattern layer 2 from the viewpoint of further improving the smoothness of the surface of the decorative resin molded product. Is also preferably laminated on the outermost layer side (visible side).

The resin layer 4 may be laminated on at least a part of the horizontal direction x. That is, the resin layer 4 may be partially laminated in the horizontal direction x, or may be laminated on the entire surface. For example, in FIG. 3, the pattern layer 2 partially formed in the horizontal direction x is one layer, the solid layer 3 formed on the entire surface is one layer, and the partially formed resin layers 41 and 42 are two. It is layered.

In addition, FIGS. It is described as if there is a space in which none of these layers are formed, but in an actual decorative sheet, such a place does not substantially exist, and the layers stacked in order do not exist. It is buried.

As the laminated structure of the decorative sheet of the present invention, a laminated structure in which a pattern layer / a solid layer is laminated in this order; a laminated structure in which a base material layer / a pattern layer / a solid layer are laminated in this order; a base material layer / a solid layer / Laminated structure in which the pattern layers are laminated in this order; Laminated structure in which the base material layer / pattern layer / solid layer / surface protection layer are laminated in this order; the base material layer / solid layer / pattern layer / surface protection layer are laminated in this order. Laminated structure; Substrate layer / Solid layer / Picture layer / Resin layer / Surface protection layer are laminated in this order; Base material layer / Solid layer / Picture layer / Resin layer / Primer layer / Surface protection layer Examples thereof include a laminated structure in which the layers are laminated in this order. In the example of the laminated structure, the ones described as the pattern layer, the solid layer, and the resin layer may be a plurality of pattern layers, a plurality of solid layers, and a plurality of resin layers, respectively. FIG. 1 shows a schematic cross-sectional view of an example of a decorative sheet in which a base material layer / solid layer / pattern layer / surface protection layer are laminated in this order as one aspect of the laminated structure of the decorative sheet in the present invention. FIG. 2 shows a schematic cross-sectional view of an example of a decorative sheet in which a base material layer / a pattern layer / a solid layer / a surface protection layer are laminated in this order as one aspect of the laminated structure of the decorative sheet in the present invention. FIG. 3 shows, as one aspect of the laminated structure of the decorative sheet in the present invention, the decorative sheet in which the base material layer / solid layer / pattern layer / resin layer / resin layer / primer layer / surface protection layer are laminated in this order. A schematic cross-sectional view of an example is shown.

Composition of each layer forming the decorative sheet

[Picture layer 2]
In the decorative sheet of the present invention, the pattern layer 2 containing the pigment is partially laminated in the horizontal direction x of the laminated body, and the binder resin contained in the pattern layer 2 is 80% by mass of the acrylic resin. Includes% or more. In the present invention, although the pattern layer 2 using such a binder resin is partially laminated to form a pattern, the solid layer 3 described later is laminated to form a decorative resin. It is possible to impart high smoothness to the surface of the molded product.

Specifically, as a result of repeated studies by the present inventor, as shown in FIG. 5, a binder containing 80% by mass or more of acrylic resin on the surface of the decorative resin molded product on which the decorative sheet is laminated. The region 5a (the region on the surface of the decorative resin molded product and corresponding to the region in which the pattern layer 2 is located in the stacking direction y of the laminated body) where the pattern layer 2 containing the resin is located is the decorative resin molding. It was clarified that the flatness was maintained by the heat and pressure in the manufacturing process of the product. On the other hand, when the solid layer 3 in the present invention is not formed on the decorative sheet, the region 5b where the pattern layer 2 is not located is the decorative sheet due to the heat and pressure of the manufacturing process of the decorative resin molded product. It was clarified that the flatness was not maintained and the protrusions were convex. Therefore, on the surface of the decorative resin molded product which does not have the solid layer 3 of the present invention, the uneven shape is formed by the region 5a where the pattern layer 2 is located and the region 5b where the pattern layer 2 is not located. On the other hand, as described later, in the decorative sheet of the present invention, since the solid layer 3 containing the binder resin containing 80% by mass or more of the acrylic resin is laminated, such an uneven shape is formed. This can be effectively suppressed, and high smoothness can be imparted to the surface of the decorative resin molded product.

The pattern layer 2 may be formed by using an ink composition in which a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like are appropriately mixed in addition to the pigment and the binder resin, if necessary. can. Since the solvent volatilizes in the process of forming the pattern layer 2, the pattern layer 2 is formed by a solid content such as a pigment and a binder resin. The pattern layer 2 may be formed substantially only of the pigment and the binder resin.

The proportion of the acrylic resin contained in the binder resin in the pattern layer 2 is not particularly limited as long as it is 80% by mass or more, but is preferably about 80 to 100% by mass, more preferably about 90 to 100% by mass. Be done. The ratio of the acrylic resin in the binder resin forming the pattern layer 2 may be 100% by mass. That is, the binder resin may be substantially composed of only an acrylic resin. One type of acrylic resin may be used alone, or two or more types may be used in combination.

Specific examples of the acrylic resin include acrylic resin, acrylic polyol resin and the like. As the acrylic resin, at least an acrylic resin containing a (meth) acrylic acid ester monomer as a constituent unit is preferable. Specifically, a homopolymer of a (meth) acrylic acid ester monomer, a copolymer of two or more different (meth) acrylic acid ester monomers, and a copolymer of a (meth) acrylic acid ester monomer and another monomer. And so on. One type of acrylic resin may be used alone, or two or more types may be used in combination. In addition, in this specification, "(meth) acrylic" means "acrylic or methacrylic", and other similar ones have the same meaning.

Examples of the (meth) acrylic acid ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, normal butyl (meth) acrylate, and (meth). ) Isobutyl acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, isobonyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) ) Acrylate and the like are preferable, and among these, methyl (meth) acrylate is more preferable. Examples of the copolymer of two or more different (meth) acrylic acid ester monomers include copolymers of two or more (meth) acrylic acid esters selected from the above-exemplified ones, and these copolymers are exemplified. May be a random copolymer or a block copolymer.

The other monomer that forms a copolymer with the (meth) acrylic acid ester monomer is not particularly limited as long as it can be copolymerized with the (meth) acrylic acid ester, but in the present invention, the (meth) acrylic acid, Styrene, (maleic) maleic anhydride, fumaric acid, divinylbenzene, vinylbiphenyl, vinylnaphthalene, diphenylethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl alcohol, acrylonitrile, acrylamide, butadiene, isoprene, isobutene, 1-butene, Alicyclic olefin monomers such as 2-butene, N-vinyl-2-pyrrolidone, dicyclopentadiene, etilidennorbornene, norbornenes, vinylcaprolactam, citraconic anhydride, maleimides such as N-phenylmaleimide, vinyl ethers, etc. Preferred are mentioned, and styrene and (maleic anhydride) maleic anhydride are particularly suitable as the copolymerization component. That is, a binary copolymer of (meth) acrylic acid ester and styrene or (maleic anhydride) maleic acid, and a ternary copolymer of (meth) acrylic acid ester and styrene and (maleic anhydride) maleic anhydride are suitable. The copolymer of the (meth) acrylic acid ester and the other monomer may be a random copolymer or a block copolymer.

The acrylic polyol resin is not particularly limited, and is, for example, (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate. ) Acrylic acid alkyl ester and (meth) acrylic acid having a hydroxyl group in molecules such as 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. Examples thereof include those obtained by copolymerizing with an ester.

The weight average molecular weight of the acrylic resin is not particularly limited, but 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 resin in the present specification is a value measured by a gel permeation chromatography method using polystyrene as a standard substance.

In the pattern layer 2, the binder resin other than the acrylic resin that can be contained in the binder resin is not particularly limited, but is preferably chlorine-based resin, polyurethane, polyester, polyamide, butyral resin, polystyrene, nitrocellulose resin, acetic acid. Examples thereof include cellulose resins, and preferably chlorine-based resins. Preferred chlorine-based resins include those exemplified in the resin layer 4 described later. These other binder resins may be used alone or in combination of two or more.

The pattern layer 2 contains a pigment for the purpose of imparting decorativeness to the decorative sheet. The pigment is not particularly limited, but preferably a metal pigment, a pearl pigment, a titanium oxide pigment, or the like. In the present invention, the binder resin contained in the pattern layer 2 contains 80% by mass or more of the acrylic resin, so that the weather resistance is good even when the above pigment is used. In addition, examples of the pigment contained in the pattern layer 2 include organic pigments and inorganic pigments exemplified in the solid layer 3 described later. One type of pigment may be used alone, or two or more types may be used in combination.

The metal pigment is not particularly limited, and is, for example, aluminum powder, brass powder, stainless steel powder, tin powder, zinc powder, bronze powder, nickel powder, copper powder, gold powder, silver powder, etc., a mixed powder thereof, and the like. Examples thereof include pigments made of metal alloy powder and the like.

Examples of the pearl pigment include particles containing a metal oxide on the surface portion. Examples of such pearl pigments include pigments in which the surface of scaly particles such as mica is coated with a metal oxide. The metal oxide contained in the pearl pigment is not particularly limited as long as it can impart a brilliant design to the decorative sheet, but for example, oxidation of metals such as titanium, iron, zirconium, silicon, aluminum, and cerium. Things can be mentioned. As the metal oxide, one type may be contained alone, or two or more types may be contained. Specific examples of the pearl pigment include titanium dioxide-coated mica, iron oxide-coated mica, and titanium dioxide-iron oxide-coated mica.

The average particle size of the pigment is not particularly limited, but is usually about 1 to 500 μm, preferably about 5 to 100 μm. In the present invention, the average particle size of the pigment means the median size of the volume-based particle size distribution measured by the laser diffraction / scattering method.

In the decorative sheet of the present invention, the pattern expressed on the decorative sheet by the pattern layer 2, the solid layer 3 described later, and the resin layer 4 described later is not particularly limited, but is, for example, a wood grain pattern or a marble pattern (for example). There are stone grain patterns that imitate the surface of rocks such as Travachin marble pattern, fabric patterns that imitate cloth texture and cloth-like patterns, tiled patterns, brick pile patterns, etc. It may be a pattern. These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, but they can also be printed with special colors by preparing plates of the individual colors that make up the pattern. Can be formed.

The thickness of the pattern layer 2 is not particularly limited, but is preferably about 1.0 to 5.0 μm, more preferably about 1.5 to 3.0 μm, and further preferably about 2.0 to 3.0 μm. .. As described above, a plurality of pattern layers 2 may be laminated, and when a plurality of pattern layers 2 are laminated, the total thickness of the pattern layers 2 is preferably in this range.

The pattern layer 2 is partially formed on, for example, a base material layer 1, a solid layer 3, and a resin layer 4 formed as needed, which will be described later, by printing with an ink composition. As will be described later, the pattern layer 2 is laminated on the transfer base material 7 together with the solid layer 3 and the resin layer 4 formed as needed, and then the base material 7 is used as the base material. It is preferable to transfer it onto layer 1 or the like and laminate it on a decorative sheet. The pattern layer 2 can be formed by partially printing the laminated body in the horizontal direction x. The printing method for forming the pattern layer 2 is not particularly limited, and examples thereof include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and inkjet printing.

[Solid layer 3]
In the decorative sheet of the present invention, the solid layer 3 is laminated together with the above-mentioned pattern layer 2, and the binder resin contained in the solid layer 3 contains 80% by mass or more of an acrylic resin. As described above, in the decorative sheet of the present invention, since the solid layer 3 containing 80% by mass or more of the acrylic resin in the binder resin is laminated on the front surface of the laminated body, the above-mentioned pattern layer 2 is partially laminated. Despite this, it is possible to impart high smoothness to the surface of the decorative resin molded product.

The solid layer 3 may be formed by using an ink composition in which a pigment, a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like are appropriately mixed in addition to the binder resin, if necessary. can. Since the solvent volatilizes in the process of forming the solid layer 3, the solid layer 3 is formed of a solid content such as a binder resin. The solid layer 3 may be formed substantially only of the binder resin.

The proportion of the acrylic resin contained in the binder resin in the solid layer 3 is not particularly limited as long as it is 80% by mass or more, but is preferably about 80 to 100% by mass, more preferably about 90 to 100% by mass. Be done. The ratio of the acrylic resin in the binder resin forming the solid layer 3 may be 100% by mass. That is, the binder resin may be substantially composed of only an acrylic resin. One type of acrylic resin may be used alone, or two or more types may be used in combination.

Specific examples of the acrylic resin are not particularly limited, and examples thereof include those exemplified in the above-mentioned pattern layer 2.

Further, in the solid layer 3, the binder resin other than the acrylic resin that can be contained in the binder resin is not particularly limited, and can be the same as the above-mentioned pattern layer 2.

The solid layer 3 may contain a pigment, if necessary, for the purpose of imparting decorativeness and concealing property to the decorative sheet. The pigment is not particularly limited, but preferably an inorganic pigment and an organic pigment. One type of pigment may be used alone, or two or more types may be used in combination. The inorganic pigment is not particularly limited, and examples thereof include carbon black (black), iron black, titanium white, antimony white, chrome yellow, titanium yellow, petal handle, cadmium red, ultramarine blue, and cobalt blue. Examples of the organic pigment include quinacridone red, isoindolenone yellow, phthalocyanine blue and the like.

The average particle size of the organic pigment and the inorganic pigment is not particularly limited, but is usually about 1 to 500 μm, preferably about 5 to 100 μm, respectively. In the present invention, the average particle size of the Yuki pigment and the inorganic pigment means the median diameter of the volume-based particle size distribution measured by the laser diffraction / scattering method, respectively. The solid layer 3 may contain a metal pigment, a pearl pigment, a titanium oxide pigment, or the like exemplified for the pattern layer 2.

The thickness of the solid layer 3 is not particularly limited, but is preferably 0.5 μm or more, more preferably 1.0 to 5.0 μm, and further preferably 1.0 to 3.0 μm. When the pattern layer 2 has such a thickness, it is possible to more effectively impart high smoothness to the surface of the decorative resin molded product. As described above, a plurality of solid layers 3 may be laminated, and when a plurality of solid layers 3 are laminated, the total thickness of the solid layers 3 is preferably in this range.

The solid layer 3 is partially formed on, for example, a base material layer 1, a pattern layer 2, a resin layer 4 formed as needed, and the like, which will be described later, by printing with an ink composition. As will be described later, the solid layer 3 is laminated on the transfer base material 7 together with the pattern layer 2 and the resin layer 4 formed as needed, and then the base material 7 is used as the base material. It is preferable to transfer it onto layer 1 or the like and laminate it on a decorative sheet. The solid layer 3 can be formed by printing on the entire surface of the laminated body in the horizontal direction x. The printing method for forming the solid layer 3 is not particularly limited, and examples thereof include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and inkjet printing.

[Resin layer 4]
In the decorative sheet of the present invention, the resin layer 4 may be laminated together with the above-mentioned pattern layer 2 and solid layer 3, if necessary. The resin layer 4 is a layer formed of an ink composition having a binder resin composition different from that of the pattern layer 2 and the solid layer 3. That is, the binder resin contained in the resin layer 4 has an acrylic resin content of less than 80% by mass. The third resin layer can be the same as the above-mentioned pattern layer 2 or solid layer 3 except that the composition of the resin constituting the binder resin is different. Further, the resin layer 4 may be partially provided or may be provided on the entire surface to form a solid layer.

The binder resin contained in the resin layer 4 is not particularly limited as long as the content of the acrylic resin is less than 80% by mass. The binder resin contained in the resin layer 4 preferably has a chlorine-based resin content of 30% by mass or more, more preferably about 40 to 100% by mass, and further preferably about 50 to 100% by mass. By setting the content of the chlorine-based resin in the binder resin contained in the resin layer 4 within the above range, the printability when the resin layer 4 is formed by printing can be improved. Therefore, when the resin layer 4 contains a colorant to form a decorative layer as described later, the decorative sheet of the present invention can be particularly suitable in terms of design. The proportion of the chlorine-based resin in the binder resin forming the resin layer 4 may be 100% by mass. That is, the binder resin may be substantially composed of only chlorine-based resin. One type of chlorine-based resin may be used alone, or two or more types may be used in combination.

Specific examples of the chlorine-based resin include polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate- (meth) acrylic copolymer weight. Examples thereof include polyvinyl chloride-based resins such as coalesced products, polyvinyl chloride, chlorinated polypropylene, etc., but particularly preferably polyvinyl chloride-based resins such as polyvinyl chloride, ethylene-vinyl chloride copolymer, and vinyl chloride-vinyl acetate copolymer. Resin is mentioned.

The weight average molecular weight of the chlorine-based resin is not particularly limited, but is preferably about 50,000 to 200,000, and more preferably about 50,000 to 100,000. The weight average molecular weight of the chlorine-based resin in the present specification is a value measured by a gel permeation chromatography method using polystyrene as a standard substance.

In the resin layer 4, the binder resin other than the chlorine-based resin that can be contained in the binder resin is not particularly limited, but is preferably acrylic resin, polyurethane, polyester, polyamide, butyral resin, polystyrene, nitrocellulose resin, acetic acid. Examples thereof include cellulose resins, and preferably acrylic resins. Preferred acrylic resins include those exemplified in the above-mentioned pattern layer 2. These other binder resins may be used alone or in combination of two or more.

The resin layer 4 may contain a colorant, if necessary, for the purpose of imparting decorativeness to the decorative sheet. That is, the resin layer 4 may form a decorative layer. The colorant is not particularly limited, and examples thereof include the pigments exemplified in the pattern layer 2 or the solid layer 3. Further, the pattern expressed on the decorative sheet by at least one layer of the pattern layer 2, the solid layer 3, and the resin layer 4 is as described above.

The thickness of the resin layer 4 is not particularly limited, but is preferably about 1 to 7 μm, more preferably about 2 to 5 μm, and further preferably about 3 to 4 μm. As described above, a plurality of resin layers 4 may be laminated, and when a plurality of resin layers 4 are laminated, the total thickness of the resin layers 4 is preferably in this range.

The resin layer 4 is formed on the base material layer 1, the pattern layer 2, the solid layer 3, and the like, which will be described later, by printing with, for example, an ink composition. As will be described later, the resin layer 4 is laminated on the transfer base material 7 together with the pattern layer 2 and the solid layer 3, and then transferred onto the base material layer 1 or the like using the transfer base material 7. It is preferable to laminate it on the decorative sheet. The resin layer 4 may be printed on at least a part of the laminated body in the horizontal direction x. That is, the resin layer 4 may be partially printed in the horizontal direction x, or may be printed on the entire surface. When printing a plurality of layers of the resin layer 4, a partially printed layer and a layer printed on the entire surface may be combined. The printing method for forming the resin layer 4 is not particularly limited, and examples thereof include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and inkjet printing.

[Base material layer 1]
The base material layer 1 is a layer provided as needed for the purpose of serving as a support in the decorative sheet of the present invention. The base material layer 1 is formed of a resin sheet (resin film). The resin component used for the base material layer 1 is not particularly limited and may be appropriately selected depending on the three-dimensional moldability, compatibility with the molding resin layer, etc., but a thermoplastic resin is preferable. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"); acrylonitrile-styrene-acrylic acid ester resin; acrylic resin; polyolefin-based resins such as polypropylene and polyethylene. Examples thereof include resin; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET) resin and the like. Among these, 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 of these resins, or may be formed of a multi-layer sheet of the same or different resins.

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

Further, the base material layer 1 may be colored by blending a colorant or the like, painted to adjust the color, or formed a pattern to impart designability.

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

[Surface protection layer 5]
The surface protective layer 5 is a layer provided as necessary so as to be located on the outermost surface of the decorative resin molded product in order to improve the chemical resistance and scratch resistance of the decorative sheet. In the present invention, the resin forming the surface protective layer 5 is not particularly limited, and examples thereof include a thermosetting resin, a thermoplastic resin, and an ionizing radiation curable resin. Among these, ionizing radiation curable resins are preferable from the viewpoint of more effectively improving the smoothness of the surface of the decorative resin molded product, further enhancing the scratch resistance, and imparting excellent surface characteristics. The resin forming the protective layer 5 can be appropriately selected depending on the use of the decorative sheet. Further, the surface protective layer 5 may be formed of a resin film. Examples of the resin film include a resin film film formed of a thermoplastic resin or a thermosetting resin described later. The surface protective layer 5 may be formed of, for example, one layer of an ionizing radiation curable resin or a resin film, or may be formed of two or more of these layers.

The thermosetting resin is not particularly limited, and for example, epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl group functional acrylic resin, and carboxyl functional acrylic. Examples thereof include resins, amide functional copolymers, and urethane resins. The thermoplastic resin is not particularly limited, and acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; vinyl chloride resins; polyethylene terephthalates (PET). ), Polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and other polyester resins; acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic acid ester resin; and the like.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the surface protective layer 5 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. Examples thereof include those obtained by appropriately mixing at least one of a prepolymer, an oligomer, a monomer, and the like having the above. Here, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet rays (UV) or electron beams (EB) are used, but in addition, X It also includes electromagnetic waves such as rays and γ rays, and charged particle beams such as α rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin is suitable for forming the surface protective layer 5 because it can be made solvent-free, does not require a photopolymerization initiator, and stable curing characteristics can be obtained. Used for.

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

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

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

(Other additive ingredients)
In addition to the above-mentioned inorganic particles and organic particles, various additives can be added to the ionizing radiation curable resin composition forming the surface protective layer 5 depending on the desired physical properties to be provided in the surface protective layer 5. .. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesive improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a coloring agent, a matting agent and the like. These additives can be appropriately selected from commonly used additives, and examples of the matting agent include silica particles and aluminum hydroxide particles. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used.

(Thickness of surface protective layer 5)
The thickness of the surface protective layer 5 is not particularly limited, but is preferably 30 μm or less, more preferably about 5 to 20 μm, and more preferably about 7 to 15 μm. According to the findings of the present inventors, the problem that the smoothness of the decorative resin molded product is impaired by using the acrylic resin as the binder resin of the pattern layer 2 is that the thickness of the surface protective layer 5 is, for example, 30 μm or less. Although it tends to occur when it is thin as described above, the decorative sheet of the present invention is provided with the solid layer 3, so that even when the thickness of the surface protective layer 5 is within the above range, the decorative resin molded product can be used. The surface can be smoothed. Further, when the thickness in such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance and weather resistance can be obtained, and when the surface protective layer 5 is formed by using an ionizing radiation curable resin. Since it is possible to uniformly irradiate ionizing radiation, it is possible to cure the ionizing radiation uniformly, which is economically advantageous. Further, when the thickness of the surface protective layer 5 after curing satisfies the above range, the three-dimensional moldability of the decorative sheet is further improved, so that high followability to a complicated three-dimensional shape such as an automobile interior application can be achieved. Obtainable. As described above, even if the decorative sheet of the present invention has a thicker surface protective layer 5 than the conventional one, sufficiently high three-dimensional moldability can be obtained. Therefore, particularly the surface protective layer 5 has a high film thickness. It is also useful as a decorative sheet for required members such as vehicle exterior parts. When the surface protective layer 5 is formed by using a curable resin such as an ionizing radiation curable resin, the above thickness indicates the thickness after curing.

(Formation of surface protective layer 5 when ionizing radiation curable resin is used)
The surface protective layer 5 is formed, for example, by preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, applying the same, and cross-linking and curing the composition. The viscosity of the ionizing radiation curable resin composition is not set on the surface of layers such as the pattern layer 2, the solid layer 3, the resin layer 4, and the primer layer 6 located under the surface protective layer 5 by the coating method described later. Any viscosity may be used as long as it can form a cured resin layer.

In the present invention, the prepared coating liquid is applied onto a layer located under the surface protective layer 5 so as to have the above-mentioned thickness, such as a gravure coat, a bar coat, a roll coat, a reverse roll coat, and a comma coat. It is applied by a known method, preferably a gravure coat, to form an uncured resin layer.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer to form the surface protective layer 5. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface protection layer 5, the electron beam transmission depth and surface protection are used. The acceleration voltage is selected so that the thicknesses of the layers 5 are substantially equal. As a result, it is possible to suppress the irradiation of the layer located below the surface protective layer 5 with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam.

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

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

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

By adding various additives to the surface protective layer 5 thus formed, a hard coat function, an anti-fog coat function, an anti-fouling coat function, an anti-glare coat function, an anti-reflection coat function, an ultraviolet ray shielding coat function, A process for imparting a function such as an infrared shielding coat function may be performed.

When the surface protective layer 5 is formed of a resin film, the resin film may be laminated on a layer located below the surface protective layer 5. As the resin film, a resin film containing the above-mentioned other additives or a resin film having undergone surface treatment such as sandblasting can also be used.

[Primer layer 6]
The primer layer 6 is a layer included as necessary for the purpose of enhancing the adhesion between the surface protective layer 5 and the layers such as the pattern layer 2, the solid layer 3, and the resin layer 4 located below the surface protective layer 5. .. The primer layer 6 can be formed of a resin.

The resin forming the primer layer 6 is not particularly limited, and examples thereof include a urethane resin, an acrylic resin, a (meth) acrylic-urethane copolymer resin, a polyester resin, and a butyral resin. Among these resins, urethane resin, acrylic resin, and (meth) acrylic-urethane copolymer resin are preferable. These resins may be used alone or in combination of two or more.

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

Among the above urethane resins, from the viewpoint of improving adhesion after cross-linking, a combination of an acrylic polyol or a polyester polyol as a polyol and a hexamethylene diisocyanate or a 4,4-diphenylmethane diisocyanate as a cross-linking material is preferable; more preferably. Is a combination of an acrylic polyol and a hexamethylene diisocyanate.

The acrylic resin is not particularly limited, and is, for example, a homopolymer of a (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a (meth) acrylic acid ester and others. Examples thereof include a copolymer with the monomer of. More specifically, the (meth) acrylic resin includes methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and (meth) acrylic acid. Methyl- (meth) butyl acrylate copolymer, ethyl (meth) acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl acrylate- (meth) acrylate Examples thereof include (meth) acrylic acid esters such as polymers. These acrylic resins may be used alone or in combination of two or more.

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

The thickness of the primer layer 6 is not particularly limited, but may be, for example, about 0.1 to 10 μm, preferably about 1 to 10 μm. By satisfying such a thickness of the primer layer 6, the weather resistance of the decorative sheet can be further enhanced, and cracking, breaking, whitening and the like of the surface protective layer 5 can be effectively suppressed.

The primer layer 6 is 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 solid coat with a silk screen, using the resin forming the primer layer 6. It is formed by a usual coating method such as wire bar coat, flow coat, comma coat, flow coat, brush coat, spray coat, or transfer coating method. Here, the transfer coating method is a method in which a coating film of a primer layer or an adhesive layer is formed on a thin sheet (film base material), and then the surface of the target layer in the decorative sheet is coated.

[Adhesive layer 8]
The adhesive layer 8 is a layer provided on the back surface of the base material layer 1 as needed for the purpose of improving the adhesion and adhesiveness between the decorative sheet and the molding resin layer 9. The resin forming the adhesive layer 8 is not particularly limited as long as it can improve the adhesion and adhesiveness between the decorative sheet and the molded resin layer 9, and is, for example, a thermoplastic resin or a thermosetting resin. Resin is used. Examples of the thermoplastic resin include acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, rubber resin and the like. .. One type of thermoplastic resin may be used alone, or two or more types may be used in combination. Examples of the thermosetting resin include urethane resin and epoxy resin. One type of thermosetting resin may be used alone, or two or more types may be used in combination.

Although the adhesive layer 8 is not necessarily a necessary layer, 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 crimping method described later. Is preferably provided. When used in the vacuum crimping method, it is preferable to form the adhesive layer 8 by using a conventional resin that develops adhesiveness by pressurization or heating among the various resins described above.

The thickness of the adhesive layer 8 is not particularly limited, and examples thereof include about 0.1 to 30 μm, preferably about 0.5 to 20 μm, and more preferably about 1 to 8 μm.

Method for Manufacturing Decorative Sheet The decorative sheet of the present invention can be manufactured, for example, by a method including the following steps.
Transfer sheet preparation step: A step of partially laminating a binder resin containing 80% by mass or more of acrylic resin and a pattern layer containing a pigment on a transfer substrate, and a binder resin containing 80% by mass or more of acrylic resin are included. A transfer sheet is produced by performing the steps of laminating the solid layer.
Transfer step: The pattern layer and the solid layer laminated on the transfer sheet are transferred onto the substrate.

(Transfer sheet manufacturing process)
As shown in FIG. 4, in the method for manufacturing a decorative sheet of the present invention, first, a transfer sheet manufacturing step is performed. In the transfer sheet manufacturing step, a step of partially laminating the pattern layer 2 on the transfer base material 7 and a step of laminating the solid layer 3 are performed. Further, in the transfer sheet manufacturing step, a step of laminating the resin layer 4 is performed, if necessary. As described above, the pattern layer 2, the solid layer 3, and the resin layer 4 can be laminated by printing or the like. In the transfer sheet manufacturing step, the pattern layer 2, the solid layer 3, and the resin layer 4 are laminated on the transfer base material 7 so as to have a desired decorative sheet laminated structure. Further, in the case of manufacturing a decorative sheet provided with the primer layer 6, the primer layer 6 may be formed on the transfer base material 7 prior to the formation of the pattern layer 2 and the like in the transfer sheet manufacturing step, which will be described later. After the transfer step, the primer layer 6 may be formed in the surface protective layer forming step.

[Transfer substrate 7]
In the present invention, the transfer base material 7 is used for laminating the pattern layer 2, the solid layer 3, the resin layer 4 and the primer layer 6 provided as needed on the base material layer 1. As the transfer base material 7 used in the present invention, a resin sheet made of a thermoplastic resin is typically used. Examples of the thermoplastic resin include polyester resin; acrylic resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; acrylonitrile-butadiene-styrene resin (ABS resin); vinyl chloride resin and the like.

As the transfer base material 7, it is preferable to use a polyester sheet among these from the viewpoint of the peelability of the pattern layer 2, the solid layer 3, and the resin layer 4 provided as needed. The polyester resin constituting the polyester sheet indicates a polymer containing an ester group obtained by polycondensation from a polyvalent carboxylic acid and a polyvalent alcohol, and is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or polyethylene naphthalate. (PEN) and the like can be preferably mentioned, and polyethylene terephthalate (PET) is particularly preferable.

The thickness of the transfer substrate 7 is usually 10 to 150 μm, preferably 10 to 125 μm, more preferably 10 to 80 μm. Further, as the transfer base material 7, a single-layer sheet of these resins or a multi-layer sheet made of the same or different resins can be used.

[Release layer]
The release layer is transferred as necessary for the purpose of enhancing the releasability between the transfer base material 7, the pattern layer 2, the solid layer 3, the resin layer 4 and the primer layer 6 provided as needed. It is provided on the surface of the base material 7 on the side where the pattern layer 2, the solid layer 3, the resin layer 4 and the primer layer 6 provided as needed are laminated. The release layer may be a solid release layer that covers the entire surface (the entire surface is solid), or may be provided on a part of the release layer. Usually, a solid release layer is preferable in consideration of peelability.

The release layer includes a silicone resin, a fluororesin, an acrylic resin (for example, an acrylic-melamine resin is included), a polyester resin, a polyolefin resin, a polystyrene resin, a polyurethane resin, and a cellulose resin. Vinyl chloride-vinyl acetate copolymer resin, thermoplastic resin such as vitrified cotton, copolymer of the monomer forming the thermoplastic resin, or these resins modified with (meth) acrylic acid or urethane. It can be formed by using a resin composition alone or by mixing a plurality of them. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified products thereof are preferable, and more specifically, acrylic-melamine. A resin composition alone, an acrylic-melamine resin-containing composition, a resin composition obtained by mixing a polyester resin with a urethane-modified copolymer of ethylene and acrylic acid, and a copolymer of an acrylic resin and styrene and acrylic. Examples thereof include a resin composition mixed with the above emulsion. Of these, it is particularly preferable to form the release layer with a composition containing acrylic-melamine resin alone or acrylic-melamine resin in an amount of 50% by mass or more.

The thickness of the release layer is usually about 0.01 to 5 μm, preferably about 0.05 to 3 μm.

(Transfer process)
Next, a transfer step is performed as shown in FIG. In the transfer step, the pattern layer 2 and the solid layer 3 laminated on the transfer sheet, and the resin layer 4 and the primer layer 6 provided as needed are transferred onto the substrate. That is, the side of the transfer sheet opposite to the transfer base material 7 is laminated on the surface of the base material layer 1. At this time, the surface of the base material layer 1 is melted and the side opposite to the transfer base material 7 of the transfer sheet is laminated on the surface of the base material layer 1, so that the transfer sheet is placed on the base material layer 1. Can be heat fused. Next, by peeling off the transfer base material 7 located on the surface of the obtained laminate, the pattern layer 2, the solid layer 3, the resin layer 4 and the primer provided as necessary on the base material layer 1 are provided. A decorative sheet to which the layer 6 is transferred is obtained.

(Surface protective layer forming process)
When the surface protective layer 5 is provided on the decorative sheet of the present invention, a surface protective layer forming step of laminating the surface protective layer 5 may be performed after the above transfer step. The surface protective layer 5 can be laminated as described above. Further, for the purpose of enhancing the adhesion between the surface protective layer 5 and the layer located below the surface protective layer 5, the primer layer 6 may be laminated if necessary before laminating the surface protective layer 5. Similar to the primer layer 6, the surface protective layer 5 may be provided on the transfer substrate 1 before forming the pattern layer 2, the solid layer 3, and the like.

2. 2. Decorative Resin Molded Product The decorative resin molded product of the present invention is formed by integrating a molding resin into the decorative sheet of the present invention. That is, the decorative resin molded product of the present invention is composed of a laminated body in which a pattern layer and a solid layer are laminated on at least the molded resin layer, and the pattern layer is partially laminated in the laminated body. The binder resin contained in the pattern layer contains 80% by mass or more of the acrylic resin, and the binder resin contained in the solid layer contains 80% by mass or more of the acrylic resin. In the decorative resin molded product of the present invention, at least one layer such as the above-mentioned base material layer 1, resin layer 4, surface protection layer 5, primer layer 6, and adhesive layer 8 is further provided on the decorative sheet, if necessary. It may have been.

The decorative resin molded product of the present invention is produced by various injection molding methods such as an insert molding method, an injection molding simultaneous decoration method, a blow molding method, and a gas injection molding method, for example, using the decorative sheet of the present invention. To. Among these injection molding methods, an insert molding method and an injection molding simultaneous decoration method are preferably mentioned. Further, the decorative resin molded product of the present invention is prepared by a decorative method such as a vacuum crimping method in which a decorative sheet of the present invention is attached onto a three-dimensional resin molded body (molded resin layer) prepared in advance. Can also be produced.

In the insert molding method, first, in the vacuum forming step, the decorative sheet of the present invention is vacuum-formed (offline pre-molding) into the surface shape of the molded product in advance by a vacuum forming mold, and then the excess portion is trimmed if necessary. Obtain a molded sheet. This molding sheet is inserted into an injection molding mold, the injection molding mold is molded, the fluid resin is injected into the mold and solidified, and the decorative sheet is integrated on the outer surface of the resin molded product at the same time as the injection molding. By making it a decorative resin molded product, 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 using a vacuum forming mold.
The trimming process to obtain a molded sheet by trimming the excess part of the vacuum-formed decorative sheet, and the molding sheet is inserted into the injection molding mold, the injection molding mold is closed, and the fluid resin is injected into the injection molding mold. An integration process that integrates the resin and the molded sheet.

In the vacuum forming step in the insert molding method, the decorative sheet may be heated and molded. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, but is usually about 120 to 200 ° C. Further, in the integration step, the temperature of the resin in the flowing state is not particularly limited, but can usually be about 180 to 320 ° C.

Further, in the injection molding simultaneous decoration method, the decoration sheet of the present invention is placed in a female mold that also serves as a vacuum molding mold provided with a suction hole for injection molding, and pre-molding (in-line pre-molding) is performed with this female mold. After that, the injection molding mold is molded, the fluid resin is injection-filled in the mold and solidified, and at the same time as the injection molding, the decorative sheet of the present invention is integrated on the outer surface of the resin molded product. As a result, a decorative resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is produced by an injection molding simultaneous decoration method including the following steps.
After installing the decorative sheet of the present invention so that the surface of the decorative sheet faces the molded surface of the movable mold having a molded surface of a predetermined shape, the decorative sheet is heated and softened, and at the same time, the decorative sheet is heated and softened. Pre-molding step of pre-molding a decorative sheet by vacuum suctioning from the movable mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable mold.
After the movable mold having the decorative sheet adhered along the molding surface and the fixed mold are molded, a fluid resin is injected, filled and solidified in the cavity formed by both molds. As a result, a resin molded body is formed, and an integration step of laminating and integrating the resin molded body and the decorative sheet, and resin molding in which all layers of the decorative sheet are laminated by separating the movable mold from the fixed mold. Extraction process to take out the body.

In the preforming process of the injection molding simultaneous decoration method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. Usually, it can be about 70 to 130 ° C. Further, in the injection molding step, the temperature of the resin in the fluid state is not particularly limited, but can usually be about 180 to 320 ° C.

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

In the vacuum crimping method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve the moldability before the step of pressing the molded body against the decorative sheet. The vacuum crimping method including this step may be particularly called a vacuum heating crimping method. The heating temperature in the step may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, but is usually about 60 to 200 ° C.

In the decorative resin molded product of the present invention, the molded resin layer may be formed by selecting a resin according to the intended use. The molding resin forming the molding resin layer 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. These thermoplastic resins may be used alone or in combination of two or more.

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

As described above, since the decorative resin molded product of the present invention has high smoothness, for example, interior or exterior materials of vehicles such as automobiles; fittings such as window frames and door frames; walls, floors, ceilings, etc. It can be used as an interior material for buildings; housings for home appliances such as television receivers and air conditioners; and containers.

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.

(Making a decorative sheet)
<Example 1>
A decorative sheet was prepared by the following procedure.
1. 1. Transfer sheet manufacturing process
A primer layer made of acrylic urethane resin was formed on the surface of a polyethylene terephthalate (PET) film (thickness 25 μm) as a transfer substrate. The thickness of the primer layer was about 1 μm. Next, an ink composition using a mixed resin of 50% by mass of a vinyl chloride-vinyl acetate copolymer and 50% by mass of an acrylic resin as a binder resin was partially printed four times to form four resin layers. The thickness of each resin layer was about 1.0 μm. Next, an ink composition containing a binder resin made of an acrylic resin and a pearl pigment was partially printed so as to have a thickness of about 2.0 μm to form a pattern layer. Next, an ink composition containing a binder resin made of an acrylic resin and a pearl pigment was printed on the entire surface so as to have a thickness of about 1.5 μm to form a solid layer. An ink composition using a binder resin composed of a mixed resin of 50% by mass of a vinyl chloride-vinyl acetate copolymer and 50% by mass of an acrylic resin was printed twice on the entire surface of the solid layer, and the resin layer was printed on the entire surface twice. Formed. At this time, the thickness of each resin layer was set to about 1.5 μm. As described above, a transfer substrate / a partially formed resin layer (4 layers) / a partially formed pattern layer / a solid layer formed on the entire surface / a resin layer formed on the entire surface (2). A transfer sheet in which layers) were laminated in order was produced.

2. 2. One side of the ABS film (thickness 400 μm) as the transfer step substrate layer was heated to about 170 ° C. and melted. The transfer sheet obtained above was laminated on this molten surface from the side opposite to the transfer substrate and heat-fused, and then cooled to room temperature (25 ° C.). Next, the transfer substrate was peeled off from the obtained laminate, and the pattern layer, the solid layer, and the resin layer were transferred onto the substrate.

3. 3. Surface protective layer forming step On the surface of the resin layer located on the surface of the laminate obtained in the transfer step, 80 parts by mass of bifunctional polycarbonate acrylate (weight average molecular weight 10,000) and hexafunctional urethane acrylate (weight average molecular weight 6,) 000) An electron beam curable resin containing 20 parts by mass was coated with a bar coat so that the thickness after curing was 10 μm to form a surface protective layer made of an uncured electron beam curable resin. Next, the uncured surface protective layer was irradiated with an electron beam having an acceleration voltage of 195 kV and an irradiation dose of 50 kGy (5Mrad) to cure the electron beam curable resin to form a surface protective layer. A decorative sheet was obtained by the above procedure.

<Example 2>
A decorative sheet was obtained in the same manner as in Example 1 except that a solid layer was formed and then a pattern layer was formed in the above transfer sheet manufacturing step.

<Example 3>
A decorative sheet was obtained in the same manner as in Example 2 except that the pearl pigment was not blended in the ink composition forming the solid layer.

<Comparative Example 1>
A decorative sheet was obtained in the same manner as in Example 1 except that the solid layer was not formed.

(Manufacturing of decorative resin molded products)
Each of the decorative sheets obtained above was placed in a vacuum forming machine (“VPF-T1” manufactured by Fuse Vacuum Co., Ltd.) and heated with a heater until the surface temperature reached 170 ° C. to perform vacuum forming. .. The vacuum formed product was taken out, trimmed, and then injection molded. As the molding resin, a mixture of polycarbonate and ABS resin (trade name: Psycholoy IP1000BK GE plastic) was used.

(Evaluation of smoothness)
The surface of the decorative resin molded product obtained from the decorative sheets of Examples 1 to 3 and Comparative Example 1 was irradiated with oblique light, and the smoothness when the surface was visually observed was evaluated according to the following criteria. .. The results are shown in Table 1.
⊚: The uneven shape synchronized with the pattern formed by the pattern layer is not observed at all, and the mirror surface is high.
◯: The uneven shape synchronized with the pattern formed by the pattern layer is not observed.
Δ: The uneven shape synchronized with the pattern formed by the pattern layer is slightly observed, but it is not observed when the observation angle is changed.
X: The uneven shape synchronized with the pattern formed by the pattern layer is observed from any angle.

1 ... Base material layer 2 ... Picture layer 3 ... Solid layer 4 ... Resin layer 41 ... Resin layer 42 ... Resin layer 5 ... Surface protection layer 6 ... Primer layer 7 ... Transfer base material 8 ... Adhesive layer 9 ... Molding resin layer

Claims (6)

At least, a surface protective layer located on the outermost surface, a pattern layer containing a pigment (excluding those containing a compound having at least two or more acryloyl groups in one molecule), a solid layer, and a base material layer are formed. It is a decorative sheet composed of laminated bodies laminated in this order.
In the laminated body, the pattern layer is partially laminated, and is
The binder resin contained in the pattern layer contains 80% by mass or more of an acrylic resin, and the acrylic resin is at least one of an acrylic resin and an acrylic polyol resin.
The pigment is a pearl pigment,
The binder resin contained in the solid layer contains 80% by mass or more of the acrylic resin, and the acrylic resin is at least one of the acrylic resin and the acrylic polyol resin.
A decorative sheet for three-dimensional molding, wherein the surface protective layer has a thickness of 30 μm or less. The decorative sheet for three-dimensional molding according to claim 1, wherein a resin layer containing a binder resin containing 30% by mass or more of a chlorine-based resin is further laminated between the base material layer and the surface protective layer. .. The decorative sheet for three-dimensional molding according to claim 2, wherein the resin layer contains at least one of an organic pigment and an inorganic pigment. The decorative sheet for three-dimensional molding according to any one of claims 1 to 3, wherein the pattern layer and the solid layer are laminated on a base material layer. A step of partially laminating a binder resin containing 80% by mass or more of acrylic resin and a pattern layer containing a pigment on a transfer substrate, and a solid layer containing a binder resin containing 80% by mass or more of acrylic resin are laminated. The transfer sheet preparation process, in which the transfer sheet is produced by performing the steps,
A transfer step of transferring the pattern layer and the solid layer laminated on the transfer sheet onto a substrate,
After the transfer step, a step of laminating a surface protective layer located on the outermost surface having a thickness of 30 μm or less is provided.
A method for manufacturing a decorative sheet for three-dimensional molding, wherein the pigment is a pearl pigment. At least, on the molding resin layer, a surface protective layer located on the outermost surface, a pattern layer containing a pigment (excluding a cured product containing a compound having at least two or more acryloyl groups in one molecule). It is a three-dimensional decorative resin molded product composed of a laminated body in which a solid layer and a base material layer are laminated in this order.
In the laminated body, the pattern layer is partially laminated, and is
The binder resin contained in the pattern layer contains 80% by mass or more of an acrylic resin, and the acrylic resin is at least one of an acrylic resin and an acrylic polyol resin.
The pigment is a pearl pigment,
The binder resin contained in the solid layer contains 80% by mass or more of the acrylic resin, and the acrylic resin is at least one of the acrylic resin and the acrylic polyol resin.
A three-dimensional decorative resin molded product having a surface protective layer having a thickness of 30 μm or less.

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