JP6331546B2 - Decorative sheet manufacturing method - Google Patents

Description

  The present invention relates to a method for manufacturing a decorative sheet having a high-luminance metallic design.

  Conventionally, a decorative sheet has been used for decoration of vehicle interior and exterior parts, building material interior materials, home appliance housings, and the like. As a decorative sheet used for such a purpose, a sheet having a metallic design is known. As a method for imparting a metallic design to a decorative sheet, for example, a method of vacuum-depositing a metal is known. However, the vacuum deposition method has a problem that the cost is high and, when the decorative sheet is used after being formed into a three-dimensional shape, the followability at a portion where it is excessively stretched is low.

  As another method for imparting a metallic design to a decorative sheet, a method of forming a high-luminance ink layer containing a pigment on the decorative sheet is known. In this method, it is necessary to use a high-brightness ink. For example, such a high-brightness ink is printed on a smooth original film such as polyethylene terephthalate (PET). By printing on a smooth surface, the luminance can be maximized. However, since it is usual to provide the decorative sheet with other layers such as a surface protective layer in addition to the high-brightness ink layer, when a conventional manufacturing method is adopted, the decorative sheet has a high height directly above the PET film. It is extremely rare to adopt a layer structure in which a luminance ink layer is laminated.

  Thus, for example, Patent Document 1 proposes a method of transferring a high-intensity silver ink printed on a PET film to a substrate having good adhesion to the high-intensity ink by thermal transfer. According to this method, since the high-brightness ink on the PET film is transferred to the base material while maintaining its flat orientation, the high-brightness ink layer transferred onto the base material has a high brightness equivalent to that on the PET film. It is thought that it keeps.

  However, even if a highly bright ink layer with good orientation is formed on the substrate by the method of Patent Document 1, a layer such as a surface protective layer is formed on the high brightness ink layer by, for example, printing a resin composition. When a decorative sheet is produced by laminating, the smoothness of the surface of the high-brightness ink layer is impaired due to the influence of a solvent or the like contained in the resin composition. Therefore, even when the method of Patent Document 1 is adopted, it is possible to express a high-brightness metallic design to a decorative sheet having other layers on the high-brightness ink layer and having excellent practicality. It was difficult.

JP 2012-166470 A

  In view of the problems of the prior art as described above, it is a main object of the present invention to provide a method for manufacturing a decorative sheet having a high-brightness metallic design.

The present inventor has intensively studied to solve the above problems. As a result, it has been found that according to the method for producing a decorative sheet including at least the following steps 1 to 3, a decorative sheet having a high-brightness metallic design can be obtained. The present invention has been completed by further studies based on such findings.
Step 1: A step of obtaining a sheet A in which a high-brightness ink layer containing a pigment is laminated on the surface of a first carrier film having a smooth surface, and at least the first carrier film and the high-brightness ink layer are laminated. 2: After laminating the high-brightness ink layer of the sheet A on the base film, the first carrier film is peeled off, and the sheet B having at least the high-brightness ink layer laminated on the base film. Obtaining first transfer step Step 3: After preparing a sheet C in which a resin layer is laminated on the surface of the second carrier film, and laminating the opposite side of the sheet C to the second carrier film on the sheet B, A second transfer step of peeling the second carrier film to obtain a sheet D in which at least the high-brightness ink layer and the resin layer are laminated on the base film.

That is, this invention provides the invention of the aspect hung up below.
Item 1. A method for producing a decorative sheet, comprising at least the following steps 1 to 3.
Step 1: A step of obtaining a sheet A in which a high-brightness ink layer containing a pigment is laminated on the surface of a first carrier film having a smooth surface, and at least the first carrier film and the high-brightness ink layer are laminated. 2: After laminating the high-brightness ink layer of the sheet A on the base film, the first carrier film is peeled off, and the sheet B having at least the high-brightness ink layer laminated on the base film. Obtaining first transfer step Step 3: After preparing a sheet C in which a resin layer is laminated on the surface of the second carrier film, and laminating the opposite side of the sheet C to the second carrier film on the sheet B, 2. Second transfer step in which the second carrier film is peeled to obtain a sheet D in which at least the high brightness ink layer and the resin layer are laminated on the base film. Item 2. The method for producing a decorative sheet according to Item 1, wherein in the step 3, a sheet in which a surface protective layer is laminated as the resin layer on the surface of the second carrier film is used as the sheet C.
Item 3. Item 2. The method for producing a decorative sheet according to Item 1, wherein in the step 3, a sheet in which a surface protective layer and a primer layer are laminated in this order as the resin layer on the surface of the second carrier film is used as the sheet C.
Item 4. In the step 3, after the sheet C having the resin layer laminated on the surface of the second carrier film is laminated on the high-brightness ink layer of the sheet B, the second carrier film is peeled off, and the substrate Item 1 comprises a step of forming a second resin layer on the primer layer of the sheet D after obtaining a sheet D in which at least the high brightness ink layer and the resin layer are laminated on the film. The manufacturing method of the decorating sheet of description.
Item 5. Any one of Items 1-4, wherein in the step 3, a sheet in which a surface protective layer, a primer layer, and a pattern layer are laminated in this order as the resin layer on the surface of the second carrier film is used as the sheet C. The manufacturing method of the decorating sheet of description.
Item 6. Item 6. The method for producing a decorative sheet according to any one of Items 1 to 5, wherein at least one of the first carrier film and the second carrier film is composed of a laminate having a release layer on a transfer base film.
Item 7. The said 1st carrier film in any one of claim | item 1 -6 whose arithmetic mean roughness Ra prescribed | regulated to JIS B 0601: 2001 in the surface which laminates | stacks the said high-intensity ink layer is 0.5 micrometer or less. Manufacturing method of the decorative sheet.
Item 8. Item 8. The method for producing a decorative sheet according to any one of Items 1 to 7, wherein the pigment contained in the high-brightness ink layer is a metal pigment having a particle size of 15 µm or less and a thickness of 50 nm or less.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the decorating sheet | seat which has a high brightness metallic design can be provided. Furthermore, according to this invention, the manufacturing method of the decorating resin molded product using the decorating sheet obtained by the manufacturing method of the said decorating sheet can be provided.

It is a schematic sectional drawing of the sheet | seat for demonstrating an example of the sheet | seat A obtained by the process 1 of this invention. It is a schematic sectional drawing of the sheet | seat for demonstrating an example of the process 2 of this invention. It is schematic-drawing sectional drawing of the sheet | seat for demonstrating an example of the sheet | seat B obtained by the process 2 of this invention. It is schematic-drawing sectional drawing of the sheet | seat for demonstrating an example of the sheet | seat C used in the process 3 of this invention. It is schematic-drawing sectional drawing of the sheet | seat for demonstrating the process 3 of this invention. It is schematic-drawing sectional drawing of the sheet | seat for demonstrating an example of the sheet | seat D (here decorative sheet) obtained by the process 3 of this invention. It is a schematic sectional drawing of an example of the decorative resin molded product obtained using the decorating sheet manufactured by this invention. It is schematic-drawing sectional drawing of the sheet | seat for demonstrating an example of the sheet | seat C used in the process 3 of this invention. It is a schematic sectional drawing of the sheet | seat for demonstrating an example of the process 3 of this invention. It is schematic-drawing sectional drawing of the sheet | seat for demonstrating an example of the sheet | seat D (here the precursor of a decoration sheet) obtained by the process 3 of this invention. It is a schematic sectional drawing of an example of the decorating sheet manufactured by this invention.

1. The manufacturing method of a decorating sheet The manufacturing method of the decorating sheet of this invention is equipped with the following processes 1-3 at least, It is characterized by the above-mentioned.
Step 1: A step of obtaining a sheet A in which a high-brightness ink layer containing a pigment is laminated on the surface of a first carrier film having a smooth surface, and at least the first carrier film and the high-brightness ink layer are laminated. 2: After laminating the high-brightness ink layer of the sheet A on the base film, the first carrier film is peeled off, and the sheet B having at least the high-brightness ink layer laminated on the base film. Obtaining first transfer step Step 3: After preparing a sheet C in which a resin layer is laminated on the surface of the second carrier film, and laminating the opposite side of the sheet C to the second carrier film on the sheet B, A second transfer step of peeling the second carrier film to obtain a sheet D in which at least the high-brightness ink layer and the resin layer are laminated on the base film.

  The decorative sheet produced by the production method of the present invention is used by laminating on the surface of various adherends, but is used for producing a decorative resin molded product by laminating on the surface of the resin molded product. It is typically mentioned that. Hereinafter, the manufacturing method of the present invention, the decorative sheet manufactured by the manufacturing method, the decorative resin product using the decorative sheet, and the manufacturing method thereof will be described in detail.

Process 1
In step 1, a sheet A in which a high-brightness ink layer 2 containing a pigment is laminated on the surface of a first carrier film 11 having a smooth surface, and at least the first carrier film 11 and the high-brightness ink layer 2 are laminated. Get. The sheet A has a layer structure as shown in FIG.

(First carrier film 11)
The first carrier film 11 is formed of a transfer base film 11a and a release layer 11b provided as necessary.

[Transfer Substrate Film 11a]
The transfer base film 11a is not particularly limited, but is usually formed of a resin film. Although it does not restrict | limit especially as a resin film which forms the base film 1a for transcription | transfer, Preferably a polyethylene terephthalate, polyethylene, a polypropylene, etc. are mentioned. Moreover, paper sheets etc. are mentioned other than a resin film. Among these, since the smoothness is particularly high, polyethylene terephthalate is preferable, and biaxially stretched polyethylene terephthalate is more preferable.

  Although it does not restrict | limit especially as thickness of the base film 11a for transfer, Preferably it is about 30-1000 micrometers, Preferably about 30-500 micrometers is mentioned.

[Release layer 11b]
The release layer 11b is provided on the transfer base film 11a as necessary in the first carrier film 11, and has a role of enhancing the peelability between the first carrier film 11 and the high-brightness ink layer 2. It is.

  The release layer 11b may be a solid release layer covering the entire surface of the transfer base film 11a (entirely solid), or may be provided in a part. In general, a solid release layer is preferable in consideration of peelability.

  The release layer 11b is made of a silicone resin, a fluorine resin, an acrylic resin (for example, an acrylic-melamine resin is included), a polyester resin, a polyolefin resin, a polystyrene resin, a polyurethane resin, or a cellulose resin. , Vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as nitrified cotton, copolymers of monomers forming the thermoplastic resins, or those resins modified with (meth) acrylic acid or urethane It can be formed by using a single or a plurality of mixed resin compositions. 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 1b is composed of an acrylic-melamine resin alone or a composition containing 50% by mass or more of an acrylic-melamine resin.

  Although it does not restrict | limit especially as thickness of the mold release layer 11b, Usually, about 0.01-5 micrometers, Preferably it is about 0.05-3 micrometers.

  The first carrier film 11 is required to have a smooth surface on the side on which the high-brightness ink layer 2 described later is laminated, and the surface is, for example, an arithmetic average roughness defined in JIS B 0601: 2001. Ra is preferably 0.5 μm or less, more preferably 0.1 μm or less, and still more preferably 0.05 μm or less. In addition, in this invention, arithmetic mean roughness Ra uses the surface roughness measuring device (product surface "Handy Surf E-35A" by Tokyo Seimitsu Co., Ltd., JIS B0601: 2001, length L A value obtained by folding the roughness curve from the center line and dividing the total area obtained by each roughness curve and the center line by the length L is expressed in micrometers (μm). The surface of the film 11 on the side where the high-brightness ink layer 2 is not laminated may be smooth or non-smooth, and when the first carrier film 11 does not have the release layer 11b, It is necessary that the surface of the transfer base film 11a on the side on which the high-brightness ink layer 2 is laminated is smooth, and when the release layer 11b is provided, the high-brightness ink layer in the release layer 11b. 2 is laminated It is necessary that the surface of the side is smooth to.

[High brightness ink layer 2]
The high-brightness ink layer 2 is a layer provided in order to impart a high-brightness metallic design to the decorative sheet. The high-brightness ink layer 2 contains a pigment in order to develop a high-brightness metallic design. The high-brightness ink layer 2 includes a high-brightness ink composition, which usually contains a binder resin and a solvent in addition to the pigment, and optionally mixed with extender pigments, stabilizers, plasticizers, catalysts, curing agents, and the like. It can be formed by printing on one carrier film 11. In the present invention, the high brightness ink layer 2 can be formed smoothly by forming the high brightness ink layer 2 on the first carrier film 11 having a smooth surface.

  The pigment contained in the high-brightness ink layer 2 is not particularly limited as long as it exhibits a metallic design, but preferably a metal pigment. Although it does not restrict | limit especially as a metal pigment, Preferably, aluminum powder, brass powder, stainless steel powder, tin powder, zinc powder, bronze powder, nickel powder, copper powder, gold powder, silver powder etc., these mixed powders, these Examples thereof include pigments made of metal alloy powders. Among these, aluminum powder is preferably used from the viewpoint of developing even higher brightness by applying the method for producing a decorative sheet of the present invention. A pigment may be used individually by 1 type and may be used in combination of 2 or more types.

  The particle diameter of the pigment is not particularly limited, but is preferably 20 μm or less, more preferably about 10 to 15 μm from the viewpoint of developing a higher brightness by applying the method for producing a decorative sheet of the present invention. Is mentioned. From the same viewpoint, the thickness of the pigment is preferably 100 nm or less, more preferably 50 nm or less. In the present invention, the particle diameter of the pigment is a value measured by a laser diffraction scattering method.

  The shape of the pigment in the high-brightness ink layer 2 is not particularly limited, and examples thereof include flakes and particles. By applying the method for producing a decorative sheet of the present invention, even higher brightness is expressed. From the viewpoint, a flake shape is preferable.

  Although it does not restrict | limit especially as content of the pigment in the high-intensity ink layer 2, Preferably it is about 50-100 mass parts with respect to 100 mass parts of binder resins in the high-intensity ink layer 2, More preferably, it is 60-80. About a mass part is mentioned.

  The binder resin is not particularly limited, and examples thereof include chlorine-based resins, acrylic resins, polyurethanes, polyesters, polyamides, butyral resins, polystyrenes, nitrocellulose resins, and cellulose acetate resins, preferably chlorine-based resins and acrylic resins. Is mentioned. These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  From the viewpoint of further improving the transferability of the high-brightness ink composition, the binder resin is preferably a mixed resin of an acrylic resin and a chlorine resin. From the same viewpoint, the mass ratio of the acrylic resin and the chlorine-based resin in the binder resin is not particularly limited, but is preferably in the range of about 3/7 to 8/2, more preferably about 5/5 to 8/2. More preferably, it is the range of about 5/5 to 7/3.

  Although it does not restrict | limit especially as a chlorine-type resin, For example, a polyvinyl chloride, chlorinated polyethylene, a polyvinylidene chloride, an ethylene-vinyl chloride copolymer, a vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate- (meta ) Polyvinyl chloride resins such as acrylic copolymers, polypropylene chloride, chlorinated polypropylene and the like. From the viewpoint of enhancing the transferability of the ink composition, the chlorine resin is preferably a polyvinyl chloride resin, more preferably a vinyl chloride-vinyl acetate copolymer. Chlorine resins may be used alone or in combination of two or more.

  The solvent is not particularly limited as long as it uniformly disperses components such as pigments in the high-brightness ink composition and is suitable for printing, and preferably includes methyl ethyl ketone, toluene, ethyl acetate and the like. A solvent may be used individually by 1 type and may be used in combination of 2 or more types. In particular, from the viewpoint of dispersibility of metal pigments such as aluminum powder, the high-brightness ink layer 2 is preferably formed using a solvent mainly containing methyl ethyl ketone.

  Although it does not restrict | limit especially as thickness of the high-intensity ink layer 2, For example, about 1-20 micrometers, Preferably about 1-10 micrometers is mentioned.

  The high brightness ink layer 2 is formed, for example, by printing on the first carrier film 11 using a high brightness ink composition. Although it does not restrict | limit especially about the printing method for forming the high-intensity ink layer 2, For example, gravure printing, offset printing, silk screen printing, inkjet printing etc. are mentioned.

Process 2
In Step 2, after laminating the high-brightness ink layer 2 of the sheet A obtained in Step 1 above on the base film 3, the first carrier film 11 is peeled off, and at least on the base film 3 A first transfer process is performed to obtain a sheet B on which the high brightness ink layer 2 is laminated. That is, first, a sheet A as shown in FIG. 1 is laminated on the base film 3 to obtain a sheet as shown in FIG. Next, the 1st carrier film 11 is peeled from the said sheet | seat, and the sheet | seat B by which the high-intensity ink layer 2 was laminated | stacked on the base film 3 as shown in FIG. 3 is obtained. As a method for transferring the high-brightness ink layer 2 onto the base film 3, it is preferable to use hot pressing using a mirror plate and embossing using a mirror roll. Specifically, a method of heat-softening the high-brightness ink layer 2 and the base film 3 of the sheet A using a known hot press machine or embossing machine, pressurizing them in a stacked state, and bonding them together can be mentioned.

[Base film 3]
The base film 3 is a layer provided for the purpose of improving the shape retention of the decorative sheet of the present invention. The base film 3 is preferably formed of a resin film.

  The resin component used for the base film 3 is not particularly limited, depending on the shape retention, flexibility, three-dimensional moldability, compatibility with the high-brightness ink layer 2 and the molded resin layer 8 described later, and the like. However, 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 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 film 3, only 1 type may be used and 2 or more types may be mixed and used. Moreover, the base film 3 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 resin.

  The base film 3 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 with the adjacent layer. . Examples of the oxidation method performed as the surface treatment of the base film 3 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 film 3, 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 film 3, and from the viewpoints of effects and operability, a corona discharge treatment method is preferable.

  In addition, the base film 3 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 film 3 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 film 3 is within the above range, the decorative sheet can be provided with more excellent three-dimensional formability, designability, and the like.

Process 3
In step 3, a sheet C in which the resin layer 10 is laminated on the surface of the second carrier film 12 is prepared, and the sheet C obtained in the above step 2 is placed on the side opposite to the second carrier film 12 of the sheet C. After being laminated on B, the second carrier film 12 is peeled off to obtain a sheet D in which at least the high-brightness ink layer and the resin layer 10 are laminated on the base film. Perform the process. That is, first, in step 3, a sheet C as shown in FIG. 4 in which the resin layer 10 is laminated on the surface of the second carrier film 12 is prepared. Next, the side opposite to the second carrier film 12 of the sheet C is laminated on the sheet B obtained in the above step 2 to obtain a sheet as shown in FIG. Next, the second carrier film 12 is peeled from the sheet, and at least the high-brightness ink layer 2 and the resin layer 10 are laminated on the base film 3 to form a sheet D as shown in FIG. obtain.

  As a method of transferring the resin layer 10 of the sheet C onto the high-brightness ink layer of the sheet B, it is preferable to use hot press using a mirror plate and embossing using a mirror roll. Specifically, using a known hot press machine and embossing machine, the resin layer 10 located on the opposite side of the sheet C from the second carrier film 12 and the high-brightness ink layer 2 on the base film 3 A method of softening by heating, pressurizing in a stacked state, and laminating is mentioned.

  Examples of the resin layer 10 of the sheet C in Step 3 include a layer including at least one of a surface protective layer 4, a primer layer 5, a pattern layer 6, and a color clear layer 7 described later. Specifically, as the sheet C, a sheet in which the surface protective layer 4 is laminated as the resin layer 10 on the surface of the second carrier film 12 can be used. That is, in the sheet C, the surface protective layer 4 may be laminated directly on the second carrier film 12. Further, as the sheet C, a sheet in which the primer layer 5 and the surface protective layer 4 as the resin layer 10 are laminated in this order on the surface of the second carrier film 12 may be used.

  Furthermore, in step 3, after laminating the sheet C on which the resin layer 10 is laminated on the surface of the second carrier film 12 on the high brightness ink layer 2 of the sheet B, the second carrier film 12 is peeled off, A step of forming a second resin layer 20 on the resin layer 10 of the sheet D after obtaining the sheet D in which at least the high-luminance ink layer 2 and the resin layer 10 are laminated on the base film 3; Also good. That is, first, a sheet C in which the primer layer 5 is laminated as the resin layer 10 on the surface of the second carrier film 12 as shown in FIG. 8 is prepared. Next, the sheet C as shown in FIG. 9 is obtained by laminating the sheet C on the sheet B in which at least the high-brightness ink layer 2 is laminated on the base film 3. Next, the 2nd carrier film 12 is peeled from the said sheet | seat, and the sheet | seat D as shown in FIG. 10 with which the high-brightness ink layer 2 and the primer layer 5 were laminated | stacked on the base film 3 is obtained. Here, the sheet | seat D becomes a precursor of a decoration sheet. Then, by forming the surface protective layer 4 as the second resin layer 20 on the primer layer 5 of the sheet D, a decorative sheet as shown in FIG. 11 is obtained. Alternatively, for example, after the sheet D is obtained using the sheet C on which the color clear layer 7 is laminated as the resin layer 10, the primer layer 5 and the surface protective layer 4 are sequentially laminated as the second resin layer 20. A decorative sheet can be obtained. According to these methods, even when the second resin layer 20 is formed with an ink containing a solvent, the high brightness is obtained by the interposition of the resin layer 10 laminated on the high brightness ink layer 2. Since it can prevent that the ink which forms the 2nd resin layer 20 directly contacts the ink layer 2, the fall of the brightness | luminance of the high-intensity ink layer 2 can be suppressed. In such an embodiment, the resin layer 10 is preferably formed of a solid layer from the viewpoint of protecting the entire surface of the high brightness ink layer 2 from the ink that forms the second resin layer 20.

  In step 3, as the sheet C, a sheet in which the pattern layer 6 is laminated as the resin layer 10 on the surface protective layer 4 or the primer layer 5 may be used. In this case, the sheet | seat D by which the pattern layer 6 was laminated | stacked on the high-intensity ink layer 2 on the base film 3 by the 2nd transfer process is obtained. By providing the pattern layer 6, the decorativeness by the pattern can be imparted to the decorative sheet.

  Furthermore, for the purpose of improving the adhesion between the base film 3 and the molding resin layer 8 described later, the sheet D has a back surface (the high brightness ink layer 2 and May be formed on the opposite side).

(Second carrier film 12)
The second carrier film 12 is formed of a transfer base film 12a and a release layer 12b provided as necessary. In the second carrier film 12, the transfer base film 12a and the release layer 12b are, for example, the same materials and thickness as those exemplified for the transfer base film 11a and the release layer 11b in the first carrier film 11. Formed with.

  The smoothness of the second carrier film is not particularly limited. When using a material having a smooth surface, for example, the arithmetic average roughness Ra specified in JIS B 0601: 2001 is preferably 0.5 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm. The following are mentioned.

[Surface protective layer 4]
The surface protective layer 4 is a layer provided so that it may be located in the outermost surface of a decorating sheet for the purpose of improving the scratch resistance of a decorating sheet, a weather resistance, etc. as needed. The surface protective layer 4 may be laminated as the resin layer 4 on the second carrier film 12 to form a sheet C, which may be transferred to the sheet B and laminated on the decorative sheet, or a precursor of the decorative sheet and The sheet D may be laminated by printing or the like. Although the material which forms the surface protective layer 4 is not specifically limited, Usually, resin is used, Preferably ionizing radiation curable resin is used. Hereinafter, the ionizing radiation curable resin used for forming the surface protective layer 4 will be described in detail.

(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)
Various additives can be blended in the ionizing radiation curable resin composition forming the surface protective layer 4 according to 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)
Although there is no restriction | limiting in particular about the thickness after hardening of the surface protective layer 4, For example, 1-1000 micrometers, Preferably it is 1-50 micrometers, More preferably, 1-30 micrometers is mentioned. 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 when the surface protective layer 4 is formed using an ionizing radiation curable resin, ionization is performed. Since it is possible to irradiate the radiation uniformly, it is possible to cure uniformly, which is economically advantageous. Furthermore, 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 high followability to complicated three-dimensional shapes such as automobile interior use. Can be obtained.

(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. In addition, the viscosity of ionizing radiation curable resin composition should just be a viscosity which can form a non-hardened resin layer on the surfaces, such as the 2nd carrier film 12 and the primer layer 5, by the below-mentioned application system.

  In the present invention, the prepared coating solution is formed on the second carrier film 12 or the primer layer 5 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 cockroft 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.

  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. Although it does not restrict | limit especially as an ultraviolet source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, an ultraviolet light emitting diode (LED-UV) etc. are mentioned.

  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.

[Primer layer 5]
The primer layer 5 is a layer that is included as necessary for the purpose of improving the adhesion between the surface protective layer 4 and the layer located therebelow. The primer layer 5 can be formed of a resin. The primer layer 5 may be laminated as the resin layer 4 on the second carrier film 12 to form a sheet C, which may be transferred to the sheet B and laminated on the decorative sheet, or may be a precursor of the decorative sheet. It may be laminated on the sheet D by printing or the like.

  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.

[Picture layer 6]
The pattern layer 6 is a layer provided as necessary for the purpose of imparting decorativeness to the decorative sheet, for example. The pattern layer 6 may be laminated as the resin layer 4 on the second carrier film 12 to form a sheet C, which may be transferred to the sheet B and laminated on the decorative sheet, or may be a precursor of the decorative sheet. It may be laminated on the sheet D by printing or the like. The pattern layer 6 is formed using, for example, an ink composition for a pattern layer, and has a desired pattern. As an ink composition for a pattern layer used for forming the pattern layer 6, a binder resin, a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed. Is used.

  Examples of the binder resin of the pattern layer ink composition include chlorinated resins, acrylic resins, polyurethanes, polyesters, polyamides, butyral resins, polystyrenes, nitrocellulose resins, and cellulose acetate resins, preferably chlorinated resins, An acrylic resin is mentioned. These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  From the viewpoint of further improving the transferability of the pattern layer ink composition, the binder resin is preferably a mixed resin of an acrylic resin and a chlorine-based resin. From the same viewpoint, the mass ratio of the acrylic resin and the chlorine-based resin in the binder resin is not particularly limited, but is preferably in the range of about 3/7 to 8/2, more preferably about 5/5 to 8/2. More preferably, it is the range of about 5/5 to 7/3. In addition, as a chlorine resin, what was illustrated by the high-intensity ink layer 2 is mentioned.

  The colorant contained in the pattern layer ink composition is not particularly limited. For example, carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine blue, Inorganic pigments such as cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue.

  The pattern formed by the pattern layer 6 is not particularly limited, but for example, a grain pattern, a texture pattern or a cloth-like pattern imitating the surface of a rock such as a grain pattern, a marble pattern (for example, travertine marble pattern) Examples include fabric patterns, tiled patterns, brickwork patterns, and the like, and patterns such as parquets, patchwork, etc., which are a combination of 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. The pattern layer 6 is also used in combination with a pattern pattern layer that expresses a pattern such as a wood grain pattern and an entire solid layer. The entire solid layer is usually used as a concealing layer, a colored layer, a colored concealing layer, or the like.

  Although it does not restrict | limit especially as thickness of the pattern layer 6, For example, about 1-30 micrometers, Preferably about 1-20 micrometers is mentioned.

  The pattern layer 6 is formed, for example, by printing so as to obtain a desired pattern using the pattern layer ink composition. The printing method for forming the pattern layer 6 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.

  As mentioned above, the manufacturing method of the decorative film of this invention is the 1st transcription | transfer process to the base film 3 of the high-intensity ink layer 2 in the process 2, and at least one of the surface protection layer in the process 3, and a primer layer. The decorative sheet is formed through two transfer steps of the second transfer step to the high brightness ink layer 2. That is, in the present invention, in the first transfer step, the high-brightness ink layer 2 is applied to the base film 3 while maintaining the high smoothness of the high-brightness ink layer 2 formed on the first carrier film 11 with high smoothness. Laminate on top. Furthermore, on the high-brightness ink layer 2 having high smoothness, at least one of the surface protective layer 4 and the primer layer 5 is laminated by transfer instead of printing. At this time, since the surface protective layer 4 and the primer layer 5 to be transferred have already formed a layer in which the solvent is dried, without reducing the smoothness of the surface of the high brightness ink layer 2 by the solvent used for printing, The surface protective layer 4 or the primer layer 5 can be laminated on the high brightness ink layer 2. Therefore, the primer layer 5 or the surface protective layer 4 can be formed on the high luminance ink layer 2 while maintaining the high smoothness of the high luminance ink layer 2. Therefore, the decorative sheet manufactured by the manufacturing method of the present invention has a high-brightness metallic design based on the high-brightness ink layer 2.

[Color clear layer 7]
The color clear layer 7 is a layer provided on the high-brightness ink layer 2 as necessary for the purpose of increasing the glossiness of the decorative sheet. The color clear layer 7 can be laminated on the second carrier film 12 as the resin layer 10 to form a sheet C, which can be transferred to the sheet B and laminated on the decorative sheet. Although it does not specifically limit as a raw material which forms the color clear layer 7, For example, the transparent resin colored with the coloring agent etc. is mentioned. Although there is no restriction | limiting in particular as a coloring agent, For example, a coloring pigment, dye, etc. are mentioned. The transparent resin is not particularly limited, and examples thereof include acrylic resins, polyurethane resins, acrylic-urethane copolymer resins, and polyester resins. The thickness of the color clear layer 7 is not particularly limited, but is usually about 0.5 to 4 μm, preferably about 1 to 3 μm. Although the formation method in particular of the color clear layer 7 is not restrict | limited, For example, the method of apply | coating said resin on the surfaces, such as the 2nd carrier film 12, etc. are mentioned.

[Adhesive layer]
The adhesive layer is a layer provided as necessary for the purpose of, for example, enhancing the adhesion between the decorative sheet such as between the base film 3 and the molded resin layer 8 and the molded resin layer 8. is there. The resin that forms the adhesive layer is not particularly limited as long as it can improve the adhesion and adhesion between the base film 3 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 is not necessarily a necessary layer, when it is assumed that the decorative sheet of the present invention is applied to a decorative method by sticking onto a resin molded body prepared in advance, such as a vacuum pressure bonding method described later. Are preferably provided. In the case of using in the vacuum pressure bonding method, it is preferable to use an ordinary resin as a resin that exhibits adhesiveness by pressurization or heating among the various resins described above to form the adhesive layer.

  Although the thickness in particular of an adhesive layer 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.

2. Decorating sheet The decorating sheet produced by the production method of the present invention comprises at least a base film 3, a high brightness ink layer 2, and a surface protective layer 4. The decorative sheet of the present invention has a primer layer 5 under the surface protective layer 4 as necessary for the purpose of improving the adhesion between the surface protective layer 4 and a layer adjacent thereto. May be. Moreover, you may have the pattern layer 6 etc. as needed for the purpose of providing a decorating property to a decorating sheet. Moreover, you may provide a color clear layer on the high-intensity ink layer 2 as needed for the purpose of improving the glossiness of a decorating sheet, etc. Moreover, you may have an contact bonding layer etc. as needed for the purpose of improving the adhesiveness between the base film 3 and the shaping | molding resin layer 8, etc.

  As a laminated structure of the decorative sheet obtained by the production method of the present invention, a laminated structure in which a base film / high brightness ink layer / surface protective layer are laminated in this order; base film / high brightness ink layer / primer layer / surface Laminated structure in which protective layers are laminated in this order; base film / high brightness ink layer / design layer / surface protective layer in laminated order; base film / high brightness ink layer / design layer / primer layer / Laminated structure in which surface protective layers are laminated in this order; Laminated structure in which adhesive layer / base film / high brightness ink layer / primer layer / surface protective layer are laminated in this order; adhesive layer / base film / high brightness ink layer Examples include a laminated structure in which / color clear layer / primer layer / surface protective layer are laminated in this order. In FIG. 6 and FIG. 11, as an aspect of the laminated structure of the decorative sheet formed by the manufacturing method of the present invention, a decorative film in which a base film / high-brightness ink layer / primer layer / surface protective layer are laminated in this order. 1 shows a schematic cross-sectional view of an example of a sheet.

3. Decorative resin molded product The decorated resin molded product of the present invention is formed by integrating a molded resin with a decorative sheet obtained by the production method of the present invention. That is, the decorative resin molded product of the present invention has at least the molded resin layer 8, the base film 3, the high-brightness ink layer 2, and the surface protective layer 4 in this order. In the decorative resin molded product of the present invention, a primer layer 5 is provided below the surface protective layer 4 as necessary for the purpose of improving the adhesion between the surface protective layer 4 and a layer adjacent thereto. You may do it. Moreover, you may have the pattern layer 6 etc. as needed for the purpose of providing decorating property to a decorative resin molded product. Moreover, you may have an contact bonding layer etc. as needed for the purpose of improving the adhesiveness between the base film 3 and the shaping | molding resin layer 8, etc.

  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. For example, in the case of using an ABS resin film as the base film. If it exists, it can be normally about 120-200 degreeC. 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 base film 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, A pre-molding step of pre-molding the decorative sheet by softening and vacuum-sucking 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 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. If a polyester resin film or an acrylic resin film is used as the base film, the temperature can usually be about 70 to 130 ° C. 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 vacuum chamber side is placed in a vacuum press so that the resin molded body is on the second vacuum chamber side, and the base film 3 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state. To do. 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., if it is a case where a polyester resin film or an acrylic resin film is used as a base film Usually, it can 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 injection resin for forming the molded 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.

  Since the decorative resin molded product of the present invention has a high-luminance metallic design, for example, interior materials or exterior materials for 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. In Examples and Comparative Examples, the surface roughness Ra of the first carrier film and the second carrier film is an arithmetic average roughness Ra. The arithmetic average roughness Ra is a surface roughness measuring instrument (product surface “Handy Surf E-35A” manufactured by Tokyo Seimitsu Co., Ltd., and conforms to JIS B 0601: 2001. A value obtained by dividing the total area obtained by folding back from the center line and the respective roughness curves and the center line by the length L is expressed in micrometers (μm).

(Manufacture of decorative sheets)
<Example 1>
A high-brightness ink composition comprising an aluminum pigment (evaporated flakes, 200 parts by mass) and a vinyl chloride-vinyl acetate copolymer resin (100 parts by mass) having a particle size of about 10 μm and a thickness of about 50 nm on a first carrier film The product was printed by gravure coating to obtain a sheet A having a high-brightness ink layer formed on the first carrier film. In order to improve the concealability, two layers of high-brightness ink were printed (total thickness of the high-brightness ink layer was 2 μm). As the first carrier film, a biaxially stretched PET film (thickness: 15 μm, surface roughness Ra: 0.01 μm) having a silicone-based release layer as a surface layer was used. Next, after placing the high-brightness ink layer on the base film (sheet made of ABS resin, thickness 400 μm), hot pressing was performed by thermal transfer using a hot press machine. The conditions for hot pressing were 10 minutes under a pressure of 150 ° C. and 5 kgf / cm ² . After the hot pressing, the first carrier film was peeled off to obtain a sheet B in which a high brightness ink layer was laminated on the base film.

  Next, an electron beam curable resin composition composed of a bifunctional urethane acrylate (weight average molecular weight; 2000) is printed on the second carrier film by gravure reverse so that the thickness after curing is 6 μm, A surface protective layer was formed by irradiating an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure. As the second carrier film, a biaxially stretched PET film (thickness: 15 μm, surface roughness Ra: 0.01 μm) having a silicone release layer on the surface layer was used. Next, an acrylic-urethane block copolymer resin is printed on the surface protective layer by gravure coating to form a primer layer having a thickness of 2 μm, and the second carrier film, the surface protective layer, and the primer layer are in this order. A laminated sheet C was obtained.

Next, the sheet B and the sheet C obtained above were hot-pressed using a hot press machine in a state where the high-brightness ink layer and the primer layer were in contact with each other to obtain a sheet D. The conditions for hot pressing were 10 minutes under a pressure of 150 ° C. and 5 kgf / cm ² . Finally, the second carrier film was peeled from the sheet D to obtain a decorative sheet. The decorative sheet is laminated with a layer structure of base film / high brightness ink layer / primer layer / surface protective layer.

<Example 2>
First, in the same manner as in Example 1, a sheet B in which a high brightness ink layer was laminated on a base film was obtained. Next, an acrylic-urethane block copolymer resin is printed on the second carrier film by gravure coating to form a primer layer having a thickness of 2 μm, and the second carrier film and the primer layer are laminated in this order. Got. The same second carrier film as in Example 1 was used.

Next, the sheet B and the sheet C obtained above were hot-pressed using a hot press machine in a state where the high-brightness ink layer and the primer layer were in contact with each other to obtain a sheet D. The conditions for hot pressing were 10 minutes under a pressure of 150 ° C. and 5 kgf / cm ² . Next, after peeling the second carrier film from the sheet D, the same electron beam curable resin composition as in Example 1 was printed on the primer layer by gravure reverse so that the thickness after curing was 6 μm. Then, a surface protective layer was formed by irradiating and curing an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to obtain a decorative sheet having the same layer configuration as in Example 1.

<Comparative Example 1>
On the second carrier film, the same electron beam curable resin composition as in Example 1 was printed by gravure reverse so that the thickness after curing was 6 μm, and an electron with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) was obtained. The surface protective layer was formed by irradiating with a line and curing. The same second carrier film as in Example 1 was used. Next, an acrylic-urethane block copolymer resin was printed on the surface protective layer by gravure coating to form a primer layer having a thickness of 2 μm. Next, the same high-brightness ink composition as in Example 1 was printed on the primer layer by gravure coating to form a high-brightness ink layer. In order to improve the concealability, two layers of high-brightness ink were printed (total thickness of the high-brightness ink layer was 2 μm). Next, the high-brightness ink layer was placed on a base film (sheet made of ABS resin, thickness 400 μm), and then hot-pressed by thermal transfer using a hot-press machine. The conditions for hot pressing were 10 minutes under a pressure of 150 ° C. and 5 kgf / cm ² . After the hot pressing, the second carrier film was peeled off to obtain a decorative sheet having the same layer structure as in Example 1.

<Comparative example 2>
First, in the same manner as in Example 1, a sheet B in which a high brightness ink layer was laminated on a base film was obtained. Next, an acrylic-urethane block copolymer resin was printed on the high brightness ink layer by gravure coating to form a primer layer having a thickness of 2 μm. Next, the same electron beam curable resin composition as in Example 1 was printed on the primer layer by gravure reverse so that the thickness after curing was 6 μm, and the acceleration voltage was 165 kV and the irradiation dose was 50 kGy (5 Mrad). The surface protection layer was formed by irradiating and curing the electron beam, and the decorative sheet having the same layer configuration as that of Example 1 was obtained.

(Evaluation of high brightness)
The brightness | luminance of the decorating sheet obtained in Examples 1-2 and Comparative Examples 1-2 was evaluated. Luminance was evaluated by glossiness, and microgloss (60 °) manufactured by BYK Gardner was used for measurement.
The results are shown in Table 1.

  In Example 1 and Example 2, the high-brightness ink layer is formed on a highly smooth carrier film, and the primer layer is not printed on the high-brightness ink layer after the high-brightness ink layer is formed. Since the decorative sheet was manufactured through two transfer steps, the high-brightness ink layer was not dissolved by the solvent of the primer layer, and a decorative sheet having a very high-brightness metallic design was obtained. On the other hand, in Comparative Example 1 and Comparative Example 2, although the decorative sheet having the same layer configuration as Example 1 and Example 2 was obtained, the step of printing the primer layer on the high-brightness ink layer Since it was contained, the decorating sheet with a low brightness | luminance was manufactured compared with the manufacturing method of Example 1 and Example 2. FIG.

11a, 12a ... transfer base films 11b, 12b ... release layer 11 ... first carrier film 12 ... second carrier film 2 ... high brightness ink layer 3 ... base film 4 ... surface protective layer 5 ... primer layer 6 ... Pattern layer 7 ... color clear layer 8 ... molded resin layer 10 ... resin layer 20 ... second resin layer

Claims (5)

A method for producing a decorative sheet, comprising at least the following steps 1 to 3.
Step 1: A step of obtaining a sheet A in which a high-brightness ink layer containing a pigment is laminated on the surface of a first carrier film having a smooth surface, and at least the first carrier film and the high-brightness ink layer are laminated. 2: After laminating the high-brightness ink layer of the sheet A on the base film, the first carrier film is peeled off, and the sheet B having at least the high-brightness ink layer laminated on the base film. Obtaining first transfer step Step 3: After preparing a sheet C in which a resin layer is laminated on the surface of the second carrier film, and laminating the opposite side of the sheet C to the second carrier film on the sheet B, A second transfer step of peeling the second carrier film to obtain a sheet D in which at least the high-brightness ink layer and the resin layer are laminated on the base film.
In the step 3, after the sheet C having the resin layer laminated on the surface of the second carrier film is laminated on the high-brightness ink layer of the sheet B, the second carrier film is peeled off, and the substrate After obtaining the sheet | seat D on which the said high-intensity ink layer and the said resin layer were laminated | stacked on the film at least, the process of forming a 2nd resin layer on the said resin layer of the said sheet | seat D is provided. The decoration according to claim 1, wherein in the step 3, the second resin layer is formed of an ionizing radiation curable resin, and the ionizing radiation curable resin is cured on the resin layer of the sheet D. Sheet manufacturing method. The method for producing a decorative sheet according to claim 1 or 2 , wherein at least one of the first carrier film and the second carrier film comprises a laminate having a release layer on a transfer base film. The arithmetic average roughness Ra prescribed | regulated to JISB0601: 2001 in the surface which laminates | stacks the said high-intensity ink layer as for the said 1st carrier film is 0.5 micrometer or less, In any one of Claims 1-3. The manufacturing method of the decorating sheet of description. The method for producing a decorative sheet according to any one of claims 1 to 4 , wherein the pigment contained in the high-brightness ink layer is a metal pigment having a particle diameter of 15 µm or less and a thickness of 50 nm or less.