JP2015189043A - decorative sheet and decorative resin molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet capable of displaying a design with fine uneven shapes on a resin molded product without mechanically providing an uneven shape on the surface or inside the decorative sheet.SOLUTION: There is provided a decorative sheet formed by laminating at least a first resin layer and a second resin layer. In the laminate, the first resin layer ia partially laminated, a binder resin contained in the first resin contains 80 mass% or more of an acrylic resin and a binder resin contained in the second resin layer contains 30 mass% or more of a chlorine-containing resin.

Description

  The present invention relates to a decorative sheet that allows a resin molded product to exhibit a design with a fine uneven shape. Furthermore, the present invention relates to a decorative resin molded product using the decorative sheet.

  Conventionally, a decorative resin molded product in which a decorative sheet is laminated on the surface of a resin molded product is used for an interior / exterior part of a vehicle, a building material interior material, a home appliance housing, and the like. In the production of such a decorated resin molded product, a molding method or the like is used in which a decorative sheet to which a design has been applied in advance is integrated with a resin by injection molding. As a typical example of such a molding method, a decorative sheet is formed in a three-dimensional shape in advance by a vacuum mold, the decorative sheet is inserted into an injection mold, and a resin in a fluid state is injected into the mold. The injection molding method that integrates the resin and the decorative sheet, and the injection molding that integrates the decorative sheet inserted into the mold during the injection molding with the molten resin injected into the cavity The decoration method is mentioned. In addition to a molding method by injection molding, a decorative sheet is also used in a decoration method in which a pre-molded molded body is attached with heating or pressurization, such as a vacuum pressure bonding method.

  In the decorative sheet as described above, various designs may be applied to the surface of the decorative resin molded product by forming a fine uneven shape on the surface of the decorative sheet. As a method for forming a fine uneven shape on the surface of a decorative sheet, embossing using a mold is known (for example, Patent Document 1). However, it is difficult to provide a fine concavo-convex shape with a depth of about several hundred nm to several μm by a method of mechanically providing a concavo-convex shape on the surface or inside of the decorative sheet such as embossing. . Further, the uneven shape provided mechanically has a problem that the uneven shape is easily restored to a flat surface by the action of heat and stress at the time of injection molding or preliminary molding (vacuum forming) prior thereto.

JP 2008-137216 A

  In view of the problems of the prior art as described above, the present invention allows a resin molded product to exhibit a design with fine uneven shapes without mechanically providing uneven shapes on the surface or inside of the decorative sheet. The main object is to provide a decorative sheet that can be used, and a decorative resin molded product using the decorative sheet.

  The present inventor has intensively studied to solve the above problems. As a result, in the decorative sheet made of a laminate in which at least the first resin layer and the second resin layer are laminated, the first resin layer is partially laminated, and the binder contained in the first resin layer When the resin contains 80% by mass or more of the acrylic resin and the binder resin contained in the second resin layer contains 30% by mass or more of the chlorine-based resin, the surface of the decorative sheet and the inside thereof are mechanically uneven. It has been found that even if it is not provided, a design with a fine uneven shape can be exposed on the resin molded product. The present invention has been completed by further studies based on such findings.

That is, this invention provides the invention of the aspect hung up below.
Item 1. At least a decorative sheet made of a laminate in which a first resin layer and a second resin layer are laminated,
In the laminate, the first resin layer is partially laminated,
The binder resin contained in the first resin layer contains 80% by mass or more of an acrylic resin,
The decorative sheet, wherein the binder resin contained in the second resin layer contains 30% by mass or more of a chlorine-based resin.
Item 2. Item 2. The decorative sheet according to Item 1, wherein at least one of the first resin layer and the second resin layer contains a colorant.
Item 3. Item 3. The decorative sheet according to Item 1 or 2, wherein a plurality of the second resin layers are laminated.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the first resin layer has a thickness of 1.0 µm or more.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the first resin layer and the second resin layer are laminated on a base material layer.
Item 6. Item 6. 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 7. 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 first resin layer containing a binder resin containing 80% by mass or more of an acrylic resin on a transfer substrate, and a second resin layer containing a binder resin containing 30% by mass or more of a chlorine-based resin And a step of laminating a transfer sheet to produce a transfer sheet,
A transfer step of transferring the first resin layer and the second resin layer laminated on the transfer sheet onto a base material layer;
A method for producing a decorative sheet.
Item 9. Item 9. The method for producing 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 a decorative resin molded product comprising a laminate in which a first resin layer and a second resin layer are laminated on a molded resin layer,
In the laminate, the first resin layer is partially laminated,
The binder resin contained in the first resin layer contains 80% by mass or more of an acrylic resin,
The decorative resin molded product, wherein the binder resin contained in the second resin layer contains 30% by mass or more of a chlorine-based resin.
Item 11. An uneven shape is formed on the surface of the decorative resin molded product,
Item 11. The decorative resin molded product according to Item 10, wherein the concave-convex concave portion on the surface is formed in a region corresponding to a region where the first resin layer is located in the stacking direction of the stacked body.

  ADVANTAGE OF THE INVENTION According to this invention, even if it does not provide uneven | corrugated shape mechanically on the surface and inside of a decorating sheet, the decorative sheet which can make the design by a fine uneven | corrugated shape express to a resin molded product is provided. it can. Furthermore, according to this invention, the decorative resin molded product which has the design by the fine uneven | corrugated shape on the surface can be provided.

It is a schematic diagram of the cross-sectional structure of an example of the decorating sheet of this invention. It is a schematic diagram of the cross-sectional structure of an example of the decorating sheet of this invention. It is a schematic diagram for demonstrating the manufacturing process of the decorating sheet of this invention. It is a schematic diagram of the cross-sectional structure of an example of the decorative resin molded product of the present invention. It is an observation image (magnification 100 times) by the optical microscope about the surface of the decorative resin molded product of Example 1. It is an observation image (magnification 100 times) by the optical microscope about the surface of the decorative resin molded product of Comparative Example 1. It is an observation image (magnification 100 times) by the optical microscope about the surface of the decorative resin molded product of Comparative Example 2.

1. Decorative sheet The decorative sheet of the present invention is a decorative sheet composed of a laminate in which at least a first resin layer and a second resin layer are laminated, and the first resin layer is a part of the laminate. The binder resin contained in the first resin layer contains 80% by mass or more of acrylic resin, and the binder resin contained in the second resin layer contains 30% by mass or more of chlorine resin. Features. By having such a configuration, the decorative sheet of the present invention allows a resin molded product to exhibit a design with a fine uneven shape without mechanically providing an uneven shape on the surface or inside of the decorative sheet. be able to. As will be described later, the decorative sheet of the present invention may not have a pattern layer or the like, and may be transparent, for example. Hereinafter, the decorative sheet of the present invention will be described in detail.

Laminated structure of the decorative sheet The decorative sheet of the present invention comprises at least a laminated body in which the first resin layer 2 and the second resin layer 3 are laminated. The decorative sheet of the present invention may have a base material layer 1 as necessary for the purpose of improving the shape retention of the decorative sheet. Moreover, you may have the 3rd resin layer which has a binder resin composition different from the 1st resin layer 2 and the 2nd resin layer 3 as mentioned later. Moreover, the decorative sheet of this invention may provide the surface protective layer 4 as an outermost layer as needed for the purpose of protecting the surface of a decorative sheet. Moreover, you may provide the primer layer 5 under the surface protective layer 4 as needed for the purpose of improving the adhesiveness of the surface protective layer 4 and the layer adjacent to this. Moreover, you may have the contact bonding layer 7 as needed for the purpose of improving the adhesiveness of a decorating sheet and the shaping | molding resin layer 8, etc.

  As shown in FIG. 1 or FIG. 2, the first resin layer 2 is partially laminated in the horizontal direction x (direction perpendicular to the lamination direction y) in the laminate constituting the decorative sheet of the present invention. ing. Moreover, the 2nd resin layer 3 should just be laminated | stacked on at least one part of the horizontal direction x in the laminated body which comprises the decorating sheet of this invention. That is, the second resin layer 3 may be partially laminated in the horizontal direction x or may be laminated on the entire surface.

  A plurality of first resin layers 2 and second resin layers 3 may be laminated. Further, the order of stacking the first resin layer 2 and the second resin layer 3 is not particularly limited. For example, in FIG. 2, one first resin layer partially formed in the horizontal direction x and three second resin layers 31, 32, and 33 partially formed are stacked. A laminated structure in which one resin layer 2 is located between two second resin layers 31 and 32 is illustrated.

  1 to 4 are schematic views for showing a laminated structure of a decorative sheet and a decorative resin molded product, and for convenience of drawing, a layer in which the first resin layer 2 and the second resin layer 3 are laminated and Although it is depicted as if there is a space in which any of these layers are not formed on the same plane, in an actual decorative sheet, such a portion does not substantially exist and is sequentially laminated. Is buried by layers.

  As a laminated structure of the decorative sheet of the present invention, a laminated structure in which a first resin layer / second resin layer is laminated in this order; a laminated structure in which a base material layer / first resin layer / second resin layer are laminated in this order A laminated structure in which a base material layer / second resin layer / first resin layer are laminated in this order; a laminated structure in which base material layer / first resin layer / second resin layer / surface protective layer are laminated in this order; Laminated structure in which material layer / second resin layer / first resin layer / surface protective layer are laminated in this order; base material layer / second resin layer / first resin layer / second resin layer / surface protective layer in this order Examples include a laminated structure in which a base material layer / second resin layer / first resin layer / second resin layer / primer layer / surface protective layer are laminated in this order. In the example of the laminated structure, the first resin layer and the second resin layer may be a plurality of first resin layers and a plurality of second resin layers, respectively. FIG. 1 is a schematic cross-sectional view of an example of a decorative sheet in which a base material layer / first resin layer / second resin layer / surface protective layer are laminated in this order as an embodiment of the laminated structure of the decorative sheet in the present invention. The figure is shown. FIG. 2 shows a decorative sheet in which a base material layer / second resin layer / first resin layer / second resin layer / surface protective layer are laminated in this order as an aspect of the laminated structure of the decorative sheet in the present invention. 1 shows a schematic cross-sectional view of an example.

Composition of each layer forming the decorative sheet

[First resin layer 2]
In the decorative sheet of the present invention, the first resin layer 2 is partially laminated in the horizontal direction x of the laminate, and the binder resin contained in the first resin layer 2 is an acrylic resin. Contains at least mass%. In the present invention, the first resin layer 2 having such a configuration and the second resin layer 3 to be described later are laminated so that the surface of the decorative sheet and the inside thereof are not mechanically provided with an uneven shape. However, it is possible to make the resin molded product exhibit a design with a fine uneven shape.

  Specifically, as shown in FIGS. 1, 2, and 4, on the surface of the decorative resin molded product on which the decorative sheet of the present invention is laminated, a binder resin containing 80% by mass or more of an acrylic resin. The region 4a where the first resin layer 2 including the region is located (the region on the surface of the decorative resin molded product and corresponding to the region where the first resin layer 2 is located in the stacking direction y of the laminate) is Flatness is also maintained by heat and pressure during the manufacturing process of the decorative resin molded product. On the other hand, in the region 4b in which the first resin layer 2 is not located, the flatness of the decorative sheet is not maintained due to the heat and pressure in the manufacturing process of the decorative resin molded product, the surface shape becomes rough, and the entire region 4b Projecting into a convex shape. For this reason, an uneven | corrugated shape is formed by the area | region 4a in which the 1st resin layer 2 of the surface of a decorative resin molded product is located, and the area | region 4b which is not located (refer FIG. 4). Thus, by partially laminating the first resin layer 2 with a fine interval in the horizontal direction x of the laminate, the region 4a where the first resin layer 2 is located on the surface of the decorative resin molded product A fine concavo-convex shape corresponding to the non-positioned region 4b can be formed. Since such uneven shape is formed in the process of applying heat and pressure to the decorative sheet and integrating with the molding resin, the uneven shape is difficult to become a flat surface due to heat and pressure during molding, A design with a fine uneven shape can be displayed on the decorative resin molded product.

  The first resin layer 2 uses an ink composition in which a binder resin is appropriately mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent as necessary. Can be formed. Since the solvent volatilizes during the formation process of the first resin layer 2, the first resin layer 2 is formed of a binder resin and a solid content such as the colorant. The 1st resin layer 2 may be formed only with binder resin substantially.

  In the 1st resin layer 2, as a ratio of the acrylic resin contained in binder resin, if it is 80 mass% or more, it will not restrict | limit, Preferably it is about 80-100 mass%, More preferably, it is about 90-100 mass%. Is mentioned. The ratio of the acrylic resin in the binder resin that forms the first resin layer 2 may be 100% by mass. That is, the binder resin may be substantially composed only of 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 preferably include an acrylic resin and an acrylic polyol resin. As the acrylic resin, an acrylic resin having at least a (meth) acrylic acid ester monomer as a structural unit is preferable. Specifically, homopolymers of (meth) acrylate monomers, copolymers of two or more different (meth) acrylate monomers, copolymers of (meth) acrylate monomers and other monomers Etc. One type of acrylic resin may be used alone, or two or more types may be used in combination. In the present specification, “(meth) acryl” means “acryl or methacryl”, and other similar ones have the same meaning.

  Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, normal butyl (meth) acrylate, (meth ) Isobutyl acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, isobornyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) ) Acrylate and the like are preferred, and methyl (meth) acrylate is more preferred among these. Examples of the copolymer of two or more different (meth) acrylic acid ester monomers include a copolymer of two or more (meth) acrylic acid esters selected from those exemplified above, and these copolymers 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 is copolymerizable with the (meth) acrylic acid ester, but in the present invention, (meth) acrylic acid, Styrene, 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, ethylidene norbornene, norbornene, vinylcaprolactam, citraconic anhydride, maleimides such as N-phenylmaleimide, vinyl ethers, etc. It is preferably exemplified, in particular styrene and (anhydrous) maleic acid is preferable as a copolymerization component. That is, a binary copolymer of (meth) acrylic acid ester and styrene or (anhydrous) maleic acid, or a terpolymer of (meth) acrylic acid ester, styrene and (anhydrous) maleic acid is preferable. In addition, the copolymer of (meth) acrylic acid ester and another monomer may be a random copolymer or a block copolymer.

  In addition, the acrylic polyol resin is not particularly limited, but examples thereof include (meth) acrylates 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 the molecule such as 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate What is obtained by copolymerizing with ester is mentioned.

  Although it does not restrict | limit especially as a weight average molecular weight of the said acrylic resin, Preferably it is about ~, More preferably, about ~ 150,000 is mentioned. In addition, the weight average molecular weight of the acrylic resin in this specification is a value obtained by measuring polystyrene as a standard substance by gel permeation chromatography.

  In the first resin layer 2, the binder resin other than the acrylic resin that can be included in the binder resin is not particularly limited, but is preferably a chlorine resin, polyurethane, polyester, polyamide, butyral resin, polystyrene, nitrocellulose resin. , Cellulose acetate resin, and the like, preferably a chlorine-based resin. Preferred examples of the chlorine-based resin include those exemplified in the second resin layer 3 described later. These other binder resins may be used alone or in combination of two or more.

  The 1st resin layer 2 may contain the coloring agent as needed for the purpose of providing the decorating property to a decorating sheet. That is, the first resin layer 2 may form a pattern layer. Although it does not restrict | limit especially as a coloring agent, For example, inorganic pigments, such as a pearl pigment, carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine blue, cobalt blue Organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue;

  As a pearl pigment, the particle | grains which contain a metal oxide in a surface part are mentioned, for example. 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 glittering design to the decorative sheet. For example, oxidation of metals such as titanium, iron, zirconium, silicon, aluminum, and cerium is possible. Things. As a metal oxide, 1 type may be included independently and 2 or more types may be included. Specific examples of the pearl pigment preferably include titanium dioxide-coated mica, iron oxide-coated mica, mica coated with titanium dioxide and iron oxide, and the like.

  When at least one of the first resin layer 2 and the second resin layer 3 described later contains a colorant, the pattern expressed on the decorative sheet by at least one of the first resin layer 2 and the second resin layer 3 Although not particularly limited, for example, a grain pattern simulating the surface of a rock such as a wood pattern, marble pattern (for example, travertine marble pattern), a fabric pattern simulating a texture or cloth pattern, a tiled pattern, a brickwork pattern, etc. It may be a pattern such as a parquet or patchwork that combines these. These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, but also by multicolor printing with special colors prepared by preparing individual color plates constituting the pattern. Can be formed.

  When at least one of the first resin layer 2, the second resin layer 3 described later, and the third resin layer contains a colorant, the pattern formed by these layers is synchronized with the fine uneven shape described above. Thus, it becomes possible to express high designability. From the viewpoint of further improving the design by synchronizing the pattern and the uneven shape, at least the first resin layer 2 preferably contains a colorant, and at least the first resin layer 2 and the second resin layer 3 contain a colorant. Is more preferable.

  Although it does not restrict | limit especially as thickness of the 1st resin layer 2, Preferably it is 1.0 micrometer or more, More preferably, it is about 1.5-3.0 micrometers, More preferably, about 2.0-3.0 micrometers is mentioned. When the first resin layer 2 has such a thickness, the effect of flattening the region 4a where the first resin layer 2 is located on the surface of the decorative resin molded product is enhanced, and the above unevenness is more effectively achieved. A shape can be formed. As described above, a plurality of first resin layers 2 may be laminated. When a plurality of first resin layers 2 are laminated, the total thickness of the first resin layers 2 is preferably within this range. .

  The 1st resin layer 2 is partially formed on the below-mentioned base material layer 1, the 2nd resin layer 3, etc. by printing using an ink composition, for example. As will be described later, the first resin layer 2 is laminated on the transfer substrate 6 together with the second resin layer 3 and then transferred onto the substrate layer 1 using the transfer substrate 6. And it is preferable to laminate | stack on a decorating sheet. The 1st resin layer 2 can be formed by printing partially in the horizontal direction x of a laminated body. The printing method for forming the first resin 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 ink jet printing.

[Second resin layer 3]
In the decorative sheet of the present invention, the second resin layer 3 is laminated together with the first resin layer 2 described above, and the binder resin contained in the second resin layer 3 contains 30% by mass or more of chlorine-based resin. . In the decorative sheet of the present invention, the binder resin includes the first resin layer 2 containing 80% by mass or more of the acrylic resin and the second resin layer 3 containing 30% by mass or more of the chlorine-based resin. In the decorative resin molded product obtained using the decorative sheet of the present invention, the above uneven shape is effectively formed. This is because in the region 4a where the first resin layer 2 is formed, the surface is more likely to protrude due to the heat and pressure at the time of molding the decorative sheet by forming a layer containing a large amount of chlorine-based resin. Since the flatness of the surface is maintained even when the second resin layer 3 is laminated, the unevenness difference is large between the region 4a where the first resin layer 2 is located and the region 4b where it is not located. Therefore, it is considered that the uneven shape is formed more effectively.

  The second resin layer 3 uses an ink composition in which a binder resin is appropriately mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent as necessary. Can be formed. Since the solvent volatilizes during the formation process of the second resin layer 3, the second resin layer 3 is formed of a binder resin and a solid content such as the above-described colorant. The 2nd resin layer 3 may be formed only with binder resin substantially.

  In the second resin layer 3, the ratio of the chlorine-based resin contained in the binder resin is not particularly limited as long as it is 30% by mass or more, but is preferably about 40 to 100% by mass, more preferably about 50 to 100% by mass. Is mentioned. The ratio of the chlorine-based resin in the binder resin that forms the second resin layer 3 may be 100% by mass. That is, the binder resin may be substantially composed only of a chlorine resin. Chlorine resins may be used alone or in combination of two or more.

  Specific examples of the chlorinated resin include polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate- (meth) acrylic copolymer. Polyvinyl chloride resins such as coalescence, polypropylene chloride, chlorinated polypropylene, etc. are mentioned, but particularly preferred are polyvinyl chlorides such as polyvinyl chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, etc. Resin.

  Although it does not restrict | limit especially as a weight average molecular weight of the said chlorine-type resin, Preferably it is about 50000-200000, More preferably, about 50000-100000 is mentioned. In addition, the weight average molecular weight of the chlorinated resin in the present specification is a value obtained by measuring polystyrene as a standard substance by gel permeation chromatography.

  In the second resin layer 3, the binder resin other than the chlorine resin that can be included in the binder resin is not particularly limited, but is preferably an acrylic resin, polyurethane, polyester, polyamide, butyral resin, polystyrene, nitrocellulose resin. , Cellulose acetate resin and the like, preferably acrylic resin. Preferred acrylic resins include those exemplified for the first resin layer 2 described above. These other binder resins may be used alone or in combination of two or more.

  The 2nd resin layer 1 may contain the coloring agent as needed for the purpose of providing the decorating property to a decorating sheet. That is, the second resin layer 3 may form a pattern layer. As a coloring agent, it does not restrict | limit in particular, What was illustrated by the 1st resin layer 2 is mentioned. Moreover, the pattern expressed on the decorative sheet by at least one of the first resin layer 2 and the second resin layer 3 is as described above.

  Although it does not restrict | limit especially as thickness of the 2nd resin layer 3, Preferably it is about 1-10 micrometers, More preferably, it is about 2-7 micrometers, More preferably, about 3-5 micrometers is mentioned. When the first resin layer 2 has such a thickness, the uneven shape can be more effectively formed. As described above, a plurality of second resin layers 3 may be laminated. When a plurality of second resin layers 3 are laminated, the total thickness of the second resin layers 3 is preferably within this range. .

  The 2nd resin layer 3 is formed on the below-mentioned base material layer 1, the 1st resin layer 2, etc. by printing using an ink composition, for example. As described later, the second resin layer 3 is laminated on the transfer substrate 6 together with the first resin layer 2 and then transferred onto the substrate layer 1 or the like using the transfer substrate 6. And it is preferable to laminate | stack on a decorating sheet. The second resin layer 3 may be printed on at least a part of the laminated body in the horizontal direction x. That is, the second resin layer 3 may be printed partially in the horizontal direction x or may be printed on the entire surface. When printing the second resin layer 3 in a plurality of layers, a partially printed layer and a layer printed on the entire surface may be combined. The printing method for forming the second resin 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 ink jet printing.

[Third resin layer]
The decorative sheet of the present invention may include a third resin layer other than the first resin layer 2 and the second resin layer 3 as necessary. That is, in the binder resin contained in the first resin layer 2, a third resin layer in which the acrylic resin content is less than 80 mass% and the chlorine resin content is less than 30 mass% is laminated. It may be. The third resin layer can be the same as the second resin layer 3 except that the composition of the resin constituting the binder resin is different.

[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 according to the three-dimensional moldability, compatibility with the molded resin layer, and the like, and preferably a thermoplastic resin. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”); acrylonitrile-styrene-acrylic ester resin; acrylic resin; polyolefins such as polypropylene and polyethylene Resin; Polycarbonate resin; Vinyl chloride resin; Polyethylene terephthalate (PET) resin. Among these, ABS resin is preferable from the viewpoint of three-dimensional moldability. As a resin component which forms the base material layer 1, only 1 type may be used and 2 or more types may be mixed and used. Moreover, the base material layer 1 may be formed with the single layer sheet | seat of these resin, and may be formed with the multilayer sheet | seat by the same kind or different kind | species resin.

  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 as necessary in order to improve the adhesion between adjacent layers. . Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method. Moreover, as the uneven | corrugated method performed as surface treatment of the base material layer 1, a sandblasting method, a solvent processing method, etc. are mentioned, for example. These surface treatments are appropriately selected according to the type of the resin component constituting the base material layer 1, and preferably a corona discharge treatment method from the viewpoints of effects and operability.

  In addition, the base material layer 1 may be colored with a colorant or the like, painted for adjusting the color, formation of a pattern for imparting design properties, or the like.

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

[Surface protective layer 4]
The surface protective layer 4 is a layer provided as necessary so as to be positioned on the outermost surface of the decorative resin molded product in order to improve the chemical resistance, scratch resistance and the like of the decorative sheet. In the present invention, the resin for forming the surface protective layer 4 is not particularly limited, and examples thereof include a thermosetting resin, a thermoplastic resin, and an ionizing radiation curable resin. Among these, from the viewpoint of effectively forming the fine uneven shape on the surface of the decorative resin molded product, further improving scratch resistance, and imparting excellent surface properties, ionizing radiation curable resins are used. Although preferable, resin which forms the surface protective layer 4 can be suitably selected according to the use of a decorating sheet. Further, the surface protective layer 4 may be formed of a resin film. As a resin film, the resin film formed with the below-mentioned thermoplastic resin or thermosetting resin is mentioned. The surface protective layer 4 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 layers thereof.

  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 functional acrylic resin, carboxyl functional acrylic. Examples include resins, amide functional copolymers, and urethane resins. Moreover, it does not restrict | limit especially as a thermoplastic resin, Acrylic resin, such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Polyolefin resin, such as a polypropylene and polyethylene; Polycarbonate resin; Vinyl chloride resin; Polyethylene terephthalate (PET ), Polyester resins such as polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN); acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylic ester resin;

(Ionizing radiation curable resin)
The ionizing radiation curable resin used to form the surface protective layer 4 is a resin that crosslinks and cures when irradiated with ionizing radiation. Specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. And a mixture of at least one of prepolymers, oligomers, monomers, and the like, as appropriate. Here, ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin can be made solvent-free, does not require an initiator for photopolymerization, and provides stable curing characteristics, and thus is suitable for forming the surface protective layer 4. Used for.

  As the monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (bifunctional or more), preferably three or more (trifunctional or more) 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, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di ( (Meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, 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 Examples include hexa (meth) acrylate. These monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  The oligomer used as the ionizing radiation curable resin is preferably a (meth) acrylate oligomer having a radical polymerizable unsaturated group in the molecule, and more than two polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is 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, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomer having a cationic polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) . Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or 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 can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and hydroxy (meth) acrylate. The acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of 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 relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Also, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can be used. Polyester (meth) acrylate is obtained 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, for example, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. Silicone (meth) acrylate can be obtained by adding (meth) (meth) acrylic acid to the terminal or side chain of 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 individually by 1 type, and may be used in combination of 2 or more type.

  Among the ionizing radiation curable resins described above, polycarbonate (meth) acrylate is preferably used from the viewpoint of obtaining excellent three-dimensional formability. Moreover, it is more preferable to use combining a polycarbonate (meth) acrylate and urethane (meth) acrylate from a viewpoint which makes three-dimensional moldability and scratch resistance compatible.

(Other additive ingredients)
The ionizing radiation curable resin composition forming the surface protective layer 4 can be blended with various additives in addition to the above-mentioned inorganic particles and organic particles, depending on the desired physical properties to be provided in the surface protective layer 4. . 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, Examples include a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a colorant, and a matting agent. These additives can be appropriately selected from commonly used ones. Examples of the matting agent include silica particles and aluminum hydroxide particles. In addition, 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 be used.

(Thickness of the surface protective layer 4)
The thickness of the surface protective layer 4 after curing is not particularly limited, but is preferably 30 μm or less, more preferably about 5 to 20 μm, and more preferably 7 from the viewpoint of effectively forming the fine uneven shape. About 15 μm. Furthermore, when the thickness within such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance and weather resistance can be obtained, and the surface protective layer 4 is formed using an ionizing radiation curable resin. Can be uniformly irradiated with ionizing radiation, so that it can be cured uniformly, which is economically advantageous. Moreover, since the thickness after hardening of the surface protective layer 4 satisfies the above range, the three-dimensional formability of the decorative sheet is further improved, so that it has a high followability with respect to complicated three-dimensional shapes such as automobile interior use. Can be obtained. Thus, even if the decorative sheet of the present invention has a sufficiently high three-dimensional formability even when the thickness of the surface protective layer 4 is made thicker than the conventional one, the surface protective layer 4 has a particularly high film thickness. It is also useful as a decorative member for required members such as vehicle exterior parts.

(Formation of surface protective layer 4 when using ionizing radiation curable resin)
The surface protective layer 4 is formed, for example, by preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, applying it, and crosslinking and curing it. The viscosity of the ionizing radiation curable resin composition is not applied to the surface of the layers such as the first resin layer 2, the second resin layer 3, and the primer layer 5 located below the surface protective layer 4 by a coating method described later. Any viscosity that can form a cured resin layer may be used.

  In the present invention, the prepared coating solution is formed on the layer positioned below the surface protective layer 4 so as to have the thickness, such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat, etc. The uncured resin layer is formed by applying a known method, preferably gravure coating.

  The uncured resin layer thus formed is irradiated with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer, thereby forming the surface protective layer 4. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but usually includes an acceleration voltage of about 70 to 300 kV.

  In the electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface protective layer 4, the electron beam transmission depth and the surface protection are used. The acceleration voltage is selected so that the thicknesses of the layers 4 are substantially equal. Thereby, irradiation of the extra electron beam to the layer located under the surface protective layer 4 can be suppressed, and deterioration of each layer due to the excess electron beam can be minimized.

  The irradiation dose is preferably such that the crosslinking density of the surface protective layer 4 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).

  Furthermore, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant 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 the ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet ray source is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

  By adding various additives to the surface protective layer 4 thus formed, a hard coat function, an antifogging coat function, an antifouling coating function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, You may perform the process which provides functions, such as an infrared shielding coat function.

  In addition, what is necessary is just to laminate | stack a resin film on the layer located under the surface protective layer 4, when forming the surface protective layer 4 with a resin film. In addition, as a resin film, the resin film containing the above-mentioned other additive and the resin film which gave surface treatments, such as sandblasting, can also be used.

[Primer layer 5]
The primer layer 5 is a layer that is included as needed for the purpose of improving the adhesion between the surface protective layer 4 and the layers such as the first resin layer 2 and the second resin layer 3 located therebelow. . The primer layer 5 can be formed of a resin.

  Although it does not restrict | limit especially as resin which forms the primer layer 5, For example, a urethane resin, an acrylic resin, (meth) acryl-urethane copolymer resin, a polyester resin, a butyral resin etc. are mentioned. Among these resins, a urethane resin, an acrylic resin, and a (meth) acryl-urethane copolymer resin are preferable. These resins may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

  Although it does not restrict | limit especially as said acrylic resin, For example, the homopolymer of (meth) acrylic acid ester, the copolymer of 2 or more types of different (meth) acrylic acid ester monomers, or (meth) acrylic acid ester and others And a copolymer with the above monomer. More specifically, as a (meth) acrylic resin, poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, (meth) acrylic acid Methyl- (meth) butyl acrylate copolymer, (meth) ethyl acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl (meth) acrylate copolymer Examples include (meth) acrylic acid esters such as polymers. These acrylic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although it does not restrict | limit especially as (meth) acryl-urethane copolymer resin, For example, acrylic-urethane (polyester urethane) block copolymer resin is mentioned. Further, as the curing agent, the above-described various isocyanates are used. The ratio of the acrylic to urethane ratio in the acrylic-urethane (polyester urethane) block copolymer resin is not particularly limited. For example, the acrylic / urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8 / 2 to 2/8.

  Although it does not restrict | limit especially about the thickness of the primer layer 5, For example, about 0.1-10 micrometers, Preferably about 1-10 micrometers is mentioned. When the primer layer 5 satisfies such a thickness, the weather resistance of the decorative sheet can be further increased, and cracking, breakage, whitening, and the like of the surface protective layer 4 can be effectively suppressed.

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

[Adhesive layer 7]
The adhesive layer 7 is a layer provided on the back surface of the base material layer 1 as necessary for the purpose of improving the adhesion and adhesion between the decorative sheet and the molded resin layer 8. The resin that forms the adhesive layer 7 is not particularly limited as long as it can improve the adhesion and adhesion between the decorative sheet and the molded resin layer 8. For example, a thermoplastic resin or a thermosetting resin can be used. 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, and rubber-based resin. . A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the thermosetting resin include a urethane resin and an epoxy resin. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  Although the adhesive layer 7 is not necessarily a necessary layer, it is assumed that the decorative sheet of the present invention is applied to a decoration method by sticking on a resin molded body prepared in advance, such as a vacuum pressure bonding method described later. Is preferably provided. When used in the vacuum pressure bonding method, it is preferable to form the adhesive layer 8 using a conventional resin that exhibits adhesiveness by pressurization or heating among the various resins described above.

  Although the thickness in particular of the contact bonding layer 7 is not restrict | limited, For example, about 0.1-30 micrometers, Preferably it is about 0.5-20 micrometers, More preferably, about 1-8 micrometers is mentioned.

Production method of decorative sheet The decorative sheet of the present invention can be produced, for example, by a method comprising the following steps.
A step of partially laminating a first resin layer containing a binder resin containing 80% by mass or more of an acrylic resin on a transfer substrate, and a second resin layer containing a binder resin containing 30% by mass or more of a chlorine-based resin A transfer sheet manufacturing step for transferring the first resin layer and the second resin layer stacked on the transfer sheet onto the base material layer.

(Transfer sheet production process)
As FIG. 3 shows, in the manufacturing method of the decorating sheet | seat of this invention, a transfer sheet preparation process is performed first. In the transfer sheet manufacturing step, a step of partially laminating the first resin layer 2 and a step of laminating the second resin layer 3 are performed on the transfer substrate 6. Further, in the transfer sheet manufacturing step, a step of laminating the third resin layer is performed as necessary. The lamination of the first resin layer 2, the second resin layer 3, and the third resin layer can be performed by printing or the like as described above. In the transfer sheet manufacturing process, the first resin layer 2, the second resin layer 3, and, if necessary, the third resin layer are formed on the transfer substrate 6 so as to have a desired laminated structure of decorative sheets. Laminate. Moreover, when manufacturing a decorating sheet provided with the primer layer 4, the primer layer 4 may be formed on the transfer substrate 6 prior to the formation of the first resin layer 2 in the transfer sheet manufacturing step, which will be described later. After the transfer step, the primer layer 4 may be formed in the surface protective layer forming step.

[Transfer Substrate 6]
In the present invention, the transfer substrate 6 is used for laminating the first resin layer 2, the second resin layer 3, and a third resin layer provided as necessary on the substrate layer 1. As the transfer substrate 6 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.

  As the transfer substrate 6, it is preferable to use a polyester sheet among them from the viewpoint of the peelability of the first resin layer 2, the second resin layer 3, and the third resin layer provided as necessary. . The polyester resin constituting the polyester sheet refers to a polymer containing an ester group obtained by polycondensation from a polyvalent carboxylic acid and a polyhydric alcohol. Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) can be mentioned preferably, and polyethylene terephthalate (PET) is particularly preferred.

  The thickness of the transfer substrate 6 is usually 10 to 150 μm, preferably 10 to 125 μm, and more preferably 10 to 80 μm. Moreover, as the base material 1 for transfer, a single layer sheet of these resins or a multilayer sheet made of the same or different resins can be used.

[Release layer]
The release layer is used for the purpose of enhancing the peelability between the transfer substrate 6 and the first resin layer 2, the second resin layer 3, and the third resin layer provided as necessary. The first resin layer 2 and the second resin layer 3 of the transfer base 6 are provided on the surface on the side where the third resin layer provided as necessary is laminated. The release layer may be a solid release layer covering the entire surface (entirely solid), or may be provided in part. In general, a solid release layer is preferable in consideration of peelability.

  The release layer is made of silicone resin, fluorine resin, acrylic resin (for example, acrylic-melamine resin is included), polyester resin, polyolefin resin, polystyrene resin, polyurethane resin, cellulose resin, A vinyl chloride-vinyl acetate copolymer resin, a thermoplastic resin such as nitrified cotton, a copolymer of monomers that form the thermoplastic resin, or those resins modified with (meth) acrylic acid or urethane, It can be formed by using a resin composition alone or in combination. Among these, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers that form these resins, and those obtained by urethane modification thereof are more preferable. More specifically, acrylic-melamine Resin, acrylic-melamine resin-containing composition, polyester resin and ethylene / acrylic acid copolymer modified with urethane, acrylic resin / styrene / acrylic copolymer And a resin composition mixed with the above emulsion. Among these, it is particularly preferable that the release layer is composed of an acrylic-melamine resin alone or a composition containing 50% by mass or more of the acrylic-melamine resin.

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

(Transfer process)
Next, as shown in FIG. 3, a transfer process is performed. In the transfer step, the first resin layer 2, the second resin layer 3, and the third resin layer provided as necessary are transferred onto the base material layer. That is, the opposite side of the transfer sheet to the transfer substrate 6 is laminated on the surface of the substrate layer 1. At this time, the surface of the base material layer 1 is melted, and the transfer sheet is laminated on the surface of the base material layer 1 by laminating the transfer sheet opposite to the transfer base material 6 on the surface of the base material layer 1. It can be heat-sealed. Next, the first resin layer 2 and the second resin layer 3 are provided on the base material layer 1 as needed by peeling the transfer base material 6 located on the surface of the obtained laminate. A decorative sheet to which the three resin layers are transferred is obtained.

(Surface protection layer forming process)
When providing the surface protective layer 4 in the decorating sheet of this invention, you may perform the surface protective layer formation process which laminates | stacks the surface protective layer 4 after said transfer process. Lamination of the surface protective layer 4 can be performed as described above. In addition, the primer layer 5 may be laminated as necessary before the surface protective layer 4 is laminated for the purpose of improving the adhesion between the surface protective layer 4 and the layer located therebelow. Like the primer layer 5, the surface protective layer 4 may be provided on the transfer substrate 6 before forming the first resin layer 2 and the second resin layer 3.

2. Decorated resin molded product The decorated resin molded product of the present invention is formed by integrating a molded resin with the decorated sheet of the present invention. That is, the decorative resin molded product of the present invention comprises a laminate in which a first resin layer and a second resin layer are laminated on at least a molded resin layer, and in the laminate, the first resin layer Are partially laminated, the binder resin contained in the first resin layer contains 80% by mass or more of the acrylic resin, and the binder resin contained in the second resin layer contains 30% by mass or more of the chlorine-based resin. It is characterized by that. In the decorative resin molded product of the present invention, if necessary, at least one layer such as the base material layer 1, the third resin layer, the surface protective layer 4, the primer layer 5, and the adhesive layer 7 is further provided on the decorative sheet. It may be provided.

  The decorative resin molded product of the present invention is produced, for example, by various injection molding methods such as insert molding, simultaneous injection molding, blow molding, and gas injection molding using the decorative sheet of the present invention. The Among these injection molding methods, an insert molding method and an injection molding simultaneous decorating method are preferable. In addition, the decorative resin molded product of the present invention can be obtained by a decorative method of sticking the decorative sheet of the present invention on a three-dimensional resin molded body (molded resin layer) prepared in advance, such as a vacuum pressure bonding method. Can also be made.

  In the insert molding method, first, in the vacuum forming step, the decorative sheet of the present invention is vacuum formed (off-line pre-molding) into a molded product surface shape in advance by a vacuum forming die, and then an excess portion is trimmed as necessary. A molded sheet is obtained. This molded sheet is inserted into an injection mold, the injection mold is clamped, the resin in a fluid state is injected into the mold and solidified, and the decorative sheet is integrated on the outer surface of the resin molding simultaneously with the injection molding. By decorating, 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 to trim the excess part of the vacuum-decorated decorative sheet to obtain the molded sheet, and insert the molded sheet into the injection mold, close the injection mold, and inject the fluid resin into the injection mold Integration process to integrate the resin and the molded sheet.

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

  In addition, in the simultaneous injection molding decoration method, the decorative sheet of the present invention is placed in a female mold that also serves as a vacuum forming mold provided with a suction hole for injection molding, and preliminary molding (in-line preliminary molding) is performed with this female mold. After performing, the injection mold is clamped, the resin in a fluid state is injected into the mold, solidified, and the decorative sheet of the present invention is integrated on the outer surface of the resin molding 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 the simultaneous injection molding method including the following steps.
After the decorative sheet of the present invention is installed so that the surface of the decorative sheet faces the molding surface of the movable mold having a molding surface of a predetermined shape, the decorative sheet is heated and softened, A vacuum forming from the movable mold side, and a softening decorative sheet is adhered along the molding surface of the movable mold, thereby preforming the decorative sheet,
After the movable mold and the fixed mold having the decorative sheet adhered along the molding surface are clamped, the fluidized resin is injected into the cavity formed by both molds, and is solidified by filling. Forming a resin molded body, integrating the resin molded body and the decorative sheet, and integrating the decorative sheet, separating the movable mold from the fixed mold and resin molding Extraction process to remove the body.

  In the preforming step of the simultaneous injection molding 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, etc. Usually, it can be about 70-130 degreeC. Moreover, in the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but can usually be about 180 to 320 ° C.

  In the vacuum bonding method, first, the decorative sheet and the resin molded body of the first pressure chamber located on the upper side and the second vacuum chamber located on the lower side in the vacuum pressure bonding machine, the decorative sheet is the first. The two vacuum chambers are placed in a vacuum state by being installed in a vacuum pressure bonding machine so that the vacuum chamber side and the resin molded body are on the second vacuum chamber side. The resin molding is installed on a lifting platform that is provided on the second vacuum chamber side and can be moved up and down. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using an elevator, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Adhere to the surface. Finally, the two vacuum chambers are opened to the atmospheric pressure, and the decorative resin molded product of the present invention can be obtained by trimming the excess portion of the decorative sheet as necessary.

  In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve the formability before the step of pressing the molded body against the decorative sheet. The vacuum pressure bonding method provided with the said process may be especially called a vacuum thermocompression bonding method. Although the heating temperature in the said process should just be suitably selected with the kind of resin which comprises a decorating sheet, the thickness of a decorating sheet, etc., it can usually be about 60-200 degreeC.

  In the decorative resin molded product of the present invention, the molded resin layer may be formed by selecting a resin according to the application. The molding resin that forms 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, and vinyl chloride resins. These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as a thermosetting resin, a urethane resin, an epoxy resin, etc. are mentioned, for example. These thermosetting resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  As described above, in the decorative resin molded product of the present invention, in the process of forming the decorative resin molded product from the decorative sheet of the present invention, the first resin layer 2 and the second resin layer 3 are finely processed. An uneven shape is formed on the surface. Further, in the decorative resin molded product of the present invention, the surface is rough at the convex portion and the surface is smooth at the concave portion, and when the surface is touched by hand, the first resin layer 2 is also caused by these differences. It is possible to give a tactile sensation in tune with. The difference of the ten-point average roughness RzJIS between the concavo-convex convex portion and the concave portion that can be formed on the surface of the decorative resin molded product by using the decorative sheet of the present invention (RzJIS of the convex portion−RzJIS of the concave portion) is The thickness of the first resin layer 2 and the second resin layer 3 in the decorative sheet of the invention, the type and composition of the resin contained, the thickness of the surface protective layer 4 and the type of the resin, the manufacturing conditions of the decorative sheet, For example, it is about 1 to 2 μm, although it depends on molding conditions when producing a decorative resin molded product. The ten-point average roughness RzJIS is a ten-point average roughness RzJIS defined in JIS B 0601: 2001.

  Since the decorative resin molded product of the present invention has a design with a fine concavo-convex shape, for example, interior materials or exterior materials of vehicles such as automobiles; fittings such as window frames and door frames; walls, floors, It can be used as an interior material of a building such as a ceiling; a housing of a home appliance such as a television receiver or an air conditioner; a container or the like.

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

(Preparation of decorative sheet)
<Example 1>
A decorative sheet was prepared by the following procedure.
1. Transfer Sheet Preparation Step A primer layer made of an 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 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 partially printed four times to form four second resin layers. Formed. The thickness of each second resin layer was about 1.0 μm. Next, an ink composition using a binder resin made of an acrylic resin was partially printed to a thickness of about 2 μm to form a first resin layer. At this time, the ink composition forming the first resin layer contains a pearl pigment. Next, an ink composition using a binder resin composed of a mixed resin of 50% by mass of vinyl chloride-vinyl acetate copolymer and 50% by mass of acrylic resin is printed on the entire surface of the first resin layer twice, Two second resin layers were formed. At this time, the thickness of each second resin layer was about 1.5 μm. As described above, transfer substrate / partially formed second resin layer (four layers) / partially formed first resin layer / second resin layer formed on the entire surface (two layers) A transfer sheet laminated in this order was prepared.

2. One surface of an ABS film (thickness 400 μm) as a transfer process base material layer was heated to about 170 ° C. and melted. The transfer sheet obtained above was laminated on the melted surface from the side opposite to the transfer substrate and thermally fused, and then cooled to room temperature (25 ° C.). Next, the transfer substrate was peeled from the obtained laminate, and the first resin layer and the second resin layer were transferred onto the substrate.

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

<Comparative Example 1>
Example except that in the transfer sheet production process, the binder resin of the ink composition forming the first resin layer was a mixed resin of 50% by mass of vinyl chloride-vinyl acetate copolymer and 50% by mass of acrylic resin. In the same manner as in Example 1, a decorative sheet was obtained.
<Comparative Example 2>
In the transfer sheet manufacturing step, a decorative sheet was obtained in the same manner as in Example 1 except that the binder resin of the ink composition forming each second resin layer was an acrylic resin.

(Production of decorative resin molded products)
Each decorative sheet 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 molded product was taken out and trimmed, and then injection molding was performed to obtain a decorative resin molded product. As a molding resin, a mixture of polycarbonate and ABS resin (trade name: manufactured by Psycholoy IP1000BK GE Plastic) was used.

(Surface observation with an optical microscope)
5, 6, and 7 show the observation images (magnification 100 times), respectively, of the surfaces of the decorative resin molded products of Example 1, Comparative Example 1, and Comparative Example 2 using an optical microscope. As is clear from the image shown in FIG. 5, in Example 1, the region where the first resin layer was provided was flat, while the region where the first resin layer was not provided formed irregularities, The region where the first resin layer was not provided as a whole formed a convex portion with respect to the region where the first resin layer was provided. On the other hand, as shown in FIG. 6, irregularities are formed on the entire surface in the comparative example 1, and the entire surface is flat in the comparative example 2 as shown in FIG. It was.

(Evaluation of tactile sensation)
The surface of each decorative resin molded product was evaluated for hand touch. In the decorative resin molded product of Example 1, the feeling that the area (pearl pattern) provided with the first resin layer is recessed with respect to the area (non-pearl pattern) provided with the first resin layer is obtained. It was. Further, it was felt that the region where the first resin layer was provided was smooth, and the region where the first resin layer was not provided was rough. As described above, in the decorative resin molded product of Example 1, a tactile sensation synchronized with the pattern was obtained, and the design was excellent. On the other hand, as in Comparative Example 1, the whole was rough, and in Comparative Example 2, the whole was felt smooth, and in either case, no tactile sensation according to the pattern was obtained.

(Measurement of surface roughness)
About the convex part and the concave part on the surface of the decorative resin molded product of Example 1, the 10-point average roughness RzJIS was measured. The convex part was 2.30 μm and the concave part was 1.03 μm. The difference was confirmed. The measurement was performed using a surface roughness measuring machine “Handy Surf E-35A” (manufactured by Tokyo Seimitsu Co., Ltd.) according to JIS B 0601: 2001.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... 1st resin layer 3 ... 2nd resin layer 31 ... 2nd resin layer 32 ... 2nd resin layer 33 ... 2nd resin layer 4 ... Surface protective layer 5 ... Primer layer 6 ... Base material for transcription | transfer 7 ... Adhesive layer 8 ... Molded resin layer

Claims (11)

At least a decorative sheet made of a laminate in which a first resin layer and a second resin layer are laminated,
In the laminate, the first resin layer is partially laminated,
The binder resin contained in the first resin layer contains 80% by mass or more of an acrylic resin,
The decorative sheet, wherein the binder resin contained in the second resin layer contains 30% by mass or more of a chlorine-based resin.   The decorative sheet according to claim 1, wherein at least one of the first resin layer and the second resin layer includes a colorant.   The decorative sheet according to claim 1 or 2, wherein a plurality of the second resin layers are laminated.   The decorative sheet according to any one of claims 1 to 3, wherein a thickness of the first resin layer is 1.0 µm or more.   The decorative sheet according to any one of claims 1 to 4, wherein the first resin layer and the second resin layer are laminated on a base material layer.   The decorative sheet according to any one of claims 1 to 5, further comprising a surface protective layer on the outermost surface.   The decorative sheet according to claim 6, wherein the surface protective layer has a thickness of 30 μm or less. A step of partially laminating a first resin layer containing a binder resin containing 80% by mass or more of an acrylic resin on a transfer substrate, and a second resin layer containing a binder resin containing 30% by mass or more of a chlorine-based resin And a step of laminating a transfer sheet to produce a transfer sheet,
A transfer step of transferring the first resin layer and the second resin layer laminated on the transfer sheet onto a base material layer;
A method for producing a decorative sheet. The manufacturing method of the decorating sheet of Claim 8 provided with the process of laminating | stacking a surface protective layer further after the said transfer process. At least a decorative resin molded product comprising a laminate in which a first resin layer and a second resin layer are laminated on a molded resin layer,
In the laminate, the first resin layer is partially laminated,
The binder resin contained in the first resin layer contains 80% by mass or more of an acrylic resin,
The decorative resin molded product, wherein the binder resin contained in the second resin layer contains 30% by mass or more of a chlorine-based resin. An uneven shape is formed on the surface of the decorative resin molded product,
The decorative resin molded product according to claim 10, wherein the concave-convex concave portion on the surface is formed in a region corresponding to a region where the first resin layer is located in the stacking direction of the stacked body.