JP6687154B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

  The present invention relates to a decorative sheet having a high-luminance metallic design and excellent in moldability. Furthermore, the present invention relates to a decorative resin molded product using the decorative sheet.

  2. Description of the Related Art Conventionally, a decorative resin molded product obtained by laminating a decorative sheet on the surface of a resin molded product has been used for vehicle interior / exterior parts, building material interior materials, home appliance housings, and the like. In the production of such a decorative resin molded product, a molding method or the like in which a decorative sheet having a design given in advance is integrated with a resin by injection molding is used. As a typical example of such a molding method, a decorative sheet is preliminarily molded into a three-dimensional shape by a vacuum molding die, the decorative sheet is inserted into an injection molding die, and a resin in a fluid state is injected into the die. Simultaneous injection molding that integrates the resin and the decorative sheet by using the insert molding method, or integrates the decorative sheet inserted into the mold during injection molding with the molten resin injected into the cavity. The decoration method can be mentioned. Further, other than the molding method by injection molding, the decorative sheet is also used in a decorative method such as a vacuum pressure bonding method, in which a preformed molded body is attached while being heated and pressed.

  As a decorative sheet, one having a metallic design is known. As a method of imparting a metallic design to the decorative sheet, for example, a method of vacuum-depositing metal is known. However, the vacuum vapor deposition method has a problem that the cost is high and the followability to the elongation when the decorative sheet is formed is low.

  As another method of imparting a metallic design to the decorative sheet, a method of forming a high-brightness ink layer containing a pigment on the decorative sheet is known. In this method, it is necessary to use high-brightness ink. Such a high-brightness ink is printed, for example, by printing the high-brightness ink directly on a smooth original film such as polyethylene terephthalate (PET). By printing on a smooth surface, brightness can be maximized. However, in addition to the high-brightness ink layer, the decorative sheet is usually provided with other layers such as a surface protective layer and a design layer for imparting a design property. It is extremely rare that a layer structure in which ink layers are laminated can be adopted.

  Further, since the pattern layer, surface protection layer, etc. formed on the decorative sheet are usually easily dissolved in the solvent used for forming the high-brightness ink layer, it is necessary to form the high-brightness ink layer directly on these layers. However, there is a problem that the smoothness of the surface of these layers is lowered and the luminance of the high-brightness ink layer is lowered. Further, even in the case of a decorative sheet having a layer structure in which a high-brightness ink layer is laminated directly on the original film, it is not possible to use an original film having high smoothness like ABS resin or acrylic resin. In some cases, it is difficult to develop high brightness in the high brightness ink layer.

  For example, in Patent Document 1, a thermosetting epoxy resin or urethane resin having high solvent resistance is printed as an anchor layer immediately before printing the high-brightness ink, thereby smoothing the surface on which the high-brightness ink is laminated. A method of maintaining a property and expressing a high-luminance metallic tone by the high-luminance ink layer is disclosed. However, since the thermosetting resin used for the anchor layer is inferior in moldability, there is a problem that, for example, when the decorative sheet is deep-drawn, it cannot follow the elongation of the decorative sheet and cracks easily occur.

JP, 2004-74442, A

  In view of the problems of the conventional techniques as described above, the main object of the present invention is to provide a decorative sheet having a high-luminance metallic design and excellent in formability.

  The present inventor has diligently studied to solve the above problems. As a result, at least the high-brightness ink layer containing the pigment and the anchor layer containing the thermoplastic resin are laminated so as to be adjacent to each other, and the average acid value of the thermoplastic resin contained in the anchor layer is 60 mgKOH / g or more. It was found that the above-mentioned decorative sheet has high brightness and is excellent in moldability. The present invention has been completed by further studies based on these findings.

That is, the present invention provides the inventions of the following modes.
Item 1. At least a high-brightness ink layer containing a pigment and an anchor layer containing a thermoplastic resin are laminated so as to be adjacent to each other,
A decorative sheet in which the thermoplastic resin contained in the anchor layer has an average acid value of 60 mgKOH / g or more.
Item 2. Item 2. The decorative sheet according to Item 1, 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.
Item 3. Item 3. The decorative sheet according to Item 1 or 2, wherein a pattern layer is laminated so as not to be adjacent to the high-brightness ink layer.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, further comprising a surface protective layer.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, further comprising a base material layer.
Item 6. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the high-brightness ink layer, the anchor layer, and the surface protective layer are laminated in this order.
Item 7. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein a base material layer, the high-brightness ink layer, the anchor layer, and a surface protection layer are laminated in this order.
Item 8. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the base material layer, the anchor layer, the high-brightness ink layer, and the surface protection layer are laminated in this order.
Item 9. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the high-brightness ink layer, the anchor layer, a surface protective layer, and a transfer base material layer are laminated in this order.
Item 10. A high-brightness ink layer containing a pigment, an anchor layer containing a thermoplastic resin, a primer layer, a release layer, and a release substrate layer is a sheet laminated in this order,
The anchor layer and the high-brightness ink layer are laminated so as to be adjacent to each other,
A sheet for producing a decorative sheet, wherein the thermoplastic resin contained in the anchor layer has an average acid value of 60 mgKOH / g or more.
Item 11. Item 10. A method for manufacturing a decorative sheet according to any one of Items 1 to 9,
A decorative sheet comprising a step of forming an anchor layer from a resin composition containing a thermoplastic resin having an average acid value of 60 mgKOH / g or more, and then laminating a high-brightness ink layer containing a pigment on the anchor layer. Production method.
Item 12. At least, on the molded resin layer, a high-brightness ink layer containing a pigment, and an anchor layer formed of a resin composition containing a thermoplastic resin are laminated so as to be adjacent to each other,
A decorated resin molded product, wherein the thermoplastic resin contained in the anchor layer has an average acid value of 60 mgKOH / g or more.

  According to the present invention, it is possible to provide a decorative sheet having high brightness and excellent moldability. Furthermore, according to the present invention, it is possible to provide a decorative resin molded product using the decorative sheet.

It is a schematic sectional drawing of an example (1st aspect) of the decorative sheet of this invention. It is a schematic sectional drawing of an example (1st aspect) of the decorative sheet of this invention. It is a schematic sectional drawing of an example of the decorative resin molded product (1st aspect) of this invention. It is a schematic sectional drawing of an example of the decorative resin molded product (1st aspect) of this invention. It is a schematic sectional drawing of an example (2nd aspect) of the decorative sheet of this invention. It is a schematic sectional drawing of an example of the decorative resin molded product (2nd aspect) with a support body of this invention. It is a schematic sectional drawing of an example (2nd aspect) of the decorative resin molded product of this invention. It is a schematic sectional drawing of an example of the sheet for manufacturing the decoration sheet of the present invention. It is a schematic sectional drawing of the sheet which laminated | stacked the base material layer on the sheet of FIG. It is a schematic sectional drawing of the sheet which peeled the support body from the sheet of FIG. FIG. 11 is a schematic cross-sectional view of a decorative sheet of the present invention in which a surface protective layer is formed on the sheet shown in FIG. 10. FIG. 12 is a schematic cross-sectional view of an example of the decorative resin molded product of the present invention in which a molding resin is laminated on the sheet shown in FIG. 11.

1. Decorative sheet The decorative sheet of the present invention has a high-brightness ink layer containing a pigment and an anchor layer containing a thermoplastic resin laminated so as to be adjacent to each other, and the average acid value of the thermoplastic resin contained in the anchor layer. Is 60 mgKOH / g or more. The decorative sheet of the present invention has high brightness and excellent moldability by having such a structure. Hereinafter, the decorative sheet of the present invention will be described in detail.

Laminated Structure of Decorative Sheet In the decorative sheet of the present invention, at least the high-brightness ink layer 2 containing a pigment and the anchor layer 3 containing a thermoplastic resin are laminated so as to be adjacent to each other. Further, the decorative sheet of the present invention may have a base material layer 1 as necessary for the purpose of enhancing the shape retention of the decorative sheet. Further, the decorative sheet of the present invention may be provided with a surface protective layer 4 as necessary for the purpose of protecting the surface of the decorative sheet. In addition, a primer layer 7 may be provided below the surface protective layer 4, if necessary, for the purpose of enhancing the adhesion between the surface protective layer 4 and a layer adjacent thereto. Further, for the purpose of imparting decorativeness to the decorative sheet, the decorative sheet may have a pattern layer 5 as necessary. Further, between the layers of the decorative sheet (for example, between the base material layer 1 and the high-brightness ink layer 2) or between the decorative sheet and the molding resin layer 9 (for example, the high-brightness ink layer 2 and the molding resin layer). If necessary, the adhesive layer 6 may be provided for the purpose of increasing the adhesiveness between the adhesive layer 6 and the like.

  As described below, in the case of producing a decorative resin molded product using the decorative sheet of the present invention, when the decorative sheet has the base material layer 1, the base material layer 1 is included in the decorative resin molded product. The decorative sheet of the first aspect or the decorative sheet of the second aspect in which the base material layer 1 (may be referred to as the transfer base material layer 1a) is not included in the decorative resin molded article can be used. That is, in the decorative sheet of the first aspect, by forming the molding resin layer 9 on the base material layer 1 side, the base material layer 1 is included in the decorative resin molded product as shown in FIG. 3 or 4. Be done. On the other hand, in the decorative sheet of the second aspect, the molded resin layer 9 is formed on the side opposite to the base material layer 1 to obtain a decorative resin molded product with a support as shown in FIG. Since the support 10 including the transfer base material layer 1a is peeled from the transfer layer 11 including the high-brightness ink layer 2, the base material layer 1 is not included in the decorative resin molded product as shown in FIG. In the decorative sheet of the second aspect, the transfer base material layer 1a, the surface protective layer 4, and the like, if necessary, for the purpose of enhancing the releasability of the base material layer 1 from the decorative resin molded product. The mold release layer 8 may be provided between and.

  As the laminated structure of the decorative sheet of the first aspect of the present invention, a laminated structure in which a base material layer / high brightness ink layer / anchor layer is laminated in this order; base material layer / high brightness ink layer / anchor layer / surface protection. Laminated structure in which layers are laminated in this order; substrate layer / adhesive layer / high-brightness ink layer / anchor layer / surface protection layer laminated in this order; substrate layer / adhesive layer / high-brightness ink layer / anchor Layer structure in which layer / pattern layer / surface protection layer are laminated in this order; Layer structure in which base material layer / anchor layer / high brightness ink layer is laminated in this order; Base material layer / anchor layer / high brightness ink layer / surface Laminated structure in which protective layers are laminated in this order; substrate layer / anchor layer / high brightness ink layer / primer layer / surface protective layer laminated structure in this order; substrate layer / picture layer / anchor layer / high brightness Ink layer / primer layer / surface protection layer Etc. stacked in this order and the like. In FIG. 1, a base material layer / adhesive layer / high-brightness ink layer / anchor layer / design layer / surface protection layer were laminated in this order as one aspect of the laminated structure of the decorative sheet of the first aspect of the present invention. The schematic sectional drawing of an example of a decorative sheet is shown. In FIG. 2, as one aspect of the laminated structure of the decorative sheet of the first aspect of the present invention, a base material layer / a pattern layer / anchor layer / a high-brightness ink layer / a primer layer / a surface protective layer are laminated in this order. The schematic sectional drawing of an example of a decorative sheet is shown. When the decorative sheet of the present invention does not have a base material layer, a laminated structure in which an adhesive layer / high brightness ink layer / anchor layer / picture layer / surface protective layer are laminated in this order is mentioned.

  In the present invention, in the decorative sheet of the second aspect, as shown in FIG. 5, for example, a support having a base material layer 1 (transfer base material layer 1a) and a release layer 8 provided as necessary. On top of 10, a transfer layer 11 including a high-brightness ink layer 2 and an anchor layer 3 is provided. In the second aspect, the base material layer 1 and the release layer 8 that is provided as necessary constitute a support 10, and the support 10 serves as a support member for the transfer layer 11. That is, after the decorative sheet of the second aspect is integrated with a molding resin to obtain a decorative resin molded product with a support as shown in FIG. 6, the decorative resin molded product with the support is changed to a support 10. By peeling off, the decorative resin molded product as shown in FIG. 7 is obtained. As the laminated structure of the decorative sheet of the second aspect of the present invention, a laminated structure in which a high-brightness ink layer / anchor layer / transfer base material layer is laminated in this order; high-brightness ink layer / anchor layer / release layer / Layered structure in which the transfer base material layer is laminated in this order; High-brightness ink layer / Anchor layer / Surface protection layer / Release layer / Layered structure in which the transfer base material layer is laminated in this order; High-brightness ink layer / Anchor layer / primer layer / surface protection layer / release layer / transfer base material layer laminated in this order; high-brightness ink layer / anchor layer / picture layer / primer layer / surface protection layer / release layer / A laminated structure in which a transfer base material layer is laminated in this order; an adhesive layer / high-brightness ink layer / anchor layer / picture layer / primer layer / surface protection layer / release layer / transfer base material layer are laminated in this order. Examples thereof include a laminated structure. FIG. 5 shows an adhesive layer / high-brightness ink layer / anchor layer / pattern layer / primer layer / surface protective layer / release layer / transfer for one embodiment of the laminated structure of the decorative sheet of the second aspect of the present invention. The schematic sectional drawing of an example of the decorative sheet by which the base material layer was laminated | stacked in this order is shown.

Composition of each layer forming the decorative sheet [Base material layer 1]
The base material layer 1 is a layer provided as needed for the purpose of enhancing the shape retention of the decorative sheet of the present invention. The base material layer 1 is preferably formed of a resin sheet (resin film). As described above, in the first aspect of the present invention, the base material layer 1 is included in the decorative resin molded product by forming the molding resin layer 9 on the base material layer 1 side. On the other hand, in the second aspect of the present invention, since the support 10 including the base material layer 1 is peeled from the transfer layer 11 including the later-described pattern layer 5, the base material layer 1 is included in the decorative resin molded product. Absent. In the second aspect, the base material layer 1 functions as a transfer base material layer 1 a for transferring the transfer layer 11 including the high-brightness ink layer 2 and the anchor layer 3 to the molding resin layer 9.

  The resin component used in the base material layer 1 is not particularly limited, and has three-dimensional moldability, compatibility with the molding resin layer 9 in the first aspect, and releasability from the surface protective layer 4 in the second aspect. It may be appropriately selected according to the above, but a thermoplastic resin is preferable. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"); acrylonitrile-styrene-acrylic acid ester resin; acrylic resin; polypropylene-based polyolefin such as polyethylene. Resins; polycarbonate resins; vinyl chloride resins; polyethylene terephthalate (PET) resins and the like. Among these, in the first aspect of the present invention, the ABS resin is preferable from the viewpoint of three-dimensional moldability, and in the second aspect of the present invention, the PET resin is high in smoothness of the transfer base material layer 1 itself. It is preferable from the viewpoint that the orientation of the pigment in the high-brightness ink layer 2 is good and the brightness is easily exhibited. As the resin component forming the base material layer 1, only one kind may be used, or two or more kinds may be mixed and used. The base material layer 1 may be formed of a single-layer sheet of these resins, or may be formed of a multi-layer sheet of the same or different resins.

  The base material layer 1 may be subjected to a physical or chemical surface treatment such as an oxidation method or a roughening method on one side or both sides, if necessary, in order to improve the adhesion with an adjacent layer. . Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, an ozone ultraviolet treatment method, and the like. Further, examples of the surface roughening method performed as the surface treatment of the base material layer 1 include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of resin component constituting the base material layer 1, but from the viewpoint of effects and operability, the corona discharge treatment method is preferable.

  Further, the base material layer 1 may be colored with a coloring agent or the like, coated for adjusting the color, or formed with a pattern for imparting designability.

  The thickness of the base material layer 1 is not particularly limited and is appropriately set depending on the application of the decorative sheet, etc., but is usually about 50 to 800 μm, preferably about 100 to 600 μm in the first aspect of the present invention. And more preferably about 200 to 500 μm. When the thickness of the base material layer 1 is within the above range, the decorative sheet can be provided with more excellent three-dimensional moldability and designability. Further, in the second aspect of the present invention, it is usually about 10 to 250 μm, preferably about 20 to 100 μm. When the thickness of the base material layer 1 is within the above range, both printability of the decorative sheet and cost can be achieved.

[High brightness ink layer 2]
The high-brightness ink layer 2 is a layer provided to give the decorative sheet of the present invention a high-brightness metallic design. The high-brightness ink layer 2 contains a pigment in order to develop a high-brightness metallic design. The high-brightness ink layer 2 usually contains a pigment, a binder resin, and a solvent, and if necessary, a high-brightness ink composition in which an extender pigment, a stabilizer, a plasticizer, a catalyst, a curing agent and the like are appropriately mixed is described below. It can be formed by printing on the layer 3. As described below, in the present invention, by forming the high-brightness ink layer 2 on the anchor layer 3 containing a thermoplastic resin having a high acid value, the high-brightness ink layer 2 has high brightness and is excellent in moldability. It can be a sheet.

  The pigment contained in the high-brightness ink layer 2 is not particularly limited as long as it exhibits a metallic design, but a metallic pigment is preferable. The metal pigment is not particularly limited, but preferably, aluminum powder, brass powder, stainless steel powder, tin powder, zinc powder, bronze powder, nickel powder, copper powder, gold powder, silver powder, and the like, and mixed powders thereof. Examples of the pigment include metal alloy powders of Among these, aluminum powder is preferable from the viewpoint of exhibiting higher brightness and improving moldability by forming the high-brightness ink layer 2 on the anchor layer 3 described later. The pigment may be used alone or in combination of two or more.

  The particle size 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 enhancing the formability while increasing the brightness of the decorative sheet. 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 size of the pigment is a value measured by the laser diffraction scattering method.

  The shape of the pigment in the high-brightness ink layer 2 is not particularly limited, and may be flakes, particles, or the like, and from the viewpoint of further increasing the brightness, flakes are preferable. Of the above-mentioned metal pigments, flaky pigments can be prepared, for example, by forming a metal thin film on a film by vapor deposition, peeling the metal thin film from the film, and then pulverizing the metal thin film.

  The content of the pigment in the high-brightness ink layer 2 is not particularly limited, but is preferably about 50 to 100 parts by mass, more preferably 60 to 80 parts by mass with respect to 100 parts by mass of the binder resin in the high-brightness ink layer 2. The amount is about parts by mass.

  The binder resin is not particularly limited, and examples thereof include chlorine resin, acrylic resin, polyurethane, polyester, polyamide, butyral resin, polystyrene, nitrocellulose resin, cellulose acetate resin, and the like, preferably chlorine resin, acrylic resin. Is mentioned. These binder resins may be used alone or in combination of two or more.

  From the viewpoint of further enhancing 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. Range, and more preferably about 5/5 to 7/3.

  The chlorine-based resin is not particularly limited, and examples thereof include polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate- (meth). ) Polyvinyl chloride resins such as acrylic copolymer, polypropylene chloride, chlorinated polypropylene and the like. From the viewpoint of enhancing the transferability of the ink composition, among these, as the chlorine-based resin, a polyvinyl chloride-based resin is preferable, and a vinyl chloride-vinyl acetate copolymer is more preferable. The chlorine-based resin may be used alone or in combination of two or more. In addition, in this specification, (meth) acryl means acryl or methacryl, and other similar expressions are also the same.

  The solvent is not particularly limited as long as it can disperse components such as pigments uniformly in the high-brightness ink composition and is suitable for printing, but methyl ethyl ketone, ethyl acetate, toluene and the like are preferable. The solvent may be used alone or in combination of two or more. 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 containing mainly methyl ethyl ketone.

  The thickness of the high-brightness ink layer 2 is not particularly limited, but is, for example, about 1 to 20 μm, preferably about 1 to 10 μm.

  The high-brightness ink layer 2 is formed by printing using a high-brightness ink composition, for example. The printing method for forming the high-brightness ink layer 2 is not particularly limited, and examples thereof include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and inkjet printing.

[Anchor layer 3]
In the decorative sheet of the present invention, the anchor layer 3 is provided adjacent to the high-brightness ink layer 2 in order to provide the high-brightness ink layer 2 with a high-brightness metallic tone design and high moldability. It is a layer. The anchor layer 3 contains a thermoplastic resin having an average acid value of 60 mgKOH / g or more. The average acid value of the thermoplastic resin contained in the anchor layer 3 is a value measured according to JIS K2501: 2003. In the anchor layer 3 of the present invention, for example, one kind or plural kinds of thermoplastic resins having an acid value of 60 mgKOH / g or more are mixed, and the average acid value of the whole thermoplastic resin contained in the anchor layer 3 is 60 mgKOH / g. It may be above. Further, for example, one or more kinds of thermoplastic resins having an acid value of 60 mgKOH / g or more and one or more kinds of thermoplastic resins having an acid value of less than 60 mgKOH / g are mixed and contained in the anchor layer 3. The average acid value of the thermoplastic resin as a whole may be 60 mgKOH / g or more. The anchor layer 3 may include components other than the thermoplastic resin having an average acid value of 60 mgKOH / g or more, but is substantially formed only of the thermoplastic resin having an average acid value of 60 mgKOH / g or more. Is preferred.

  In the present invention, since the high-brightness ink layer 2 is formed so as to be adjacent to the anchor layer 3 containing the thermoplastic resin having an average acid value of 60 mgKOH / g or more, the high-brightness ink layer 2 is formed while increasing the brightness of the decorative sheet. Has been enhanced. Although the details of the mechanism by which the brightness of the high-brightness ink layer 2 is increased and the moldability is excellent by adopting such a configuration are not clear, it can be considered as follows, for example. That is, as described above, when producing a decorative sheet, if a high-intensity ink layer is laminated on a pattern layer, a surface protective layer, or the like, usually, by a solvent such as methyl ethyl ketone contained in the high-intensity ink composition, these The surface of the layer is dissolved and the smoothness is reduced. Since the high-brightness ink layer exhibits high brightness by being formed on a smooth surface, when the high-brightness ink layer is formed on the surface with reduced smoothness, the brightness of the decorative sheet becomes low. . On the other hand, in the decorative sheet of the present invention, the anchor layer containing the thermoplastic resin having a high acid value of the specific average acid value or more is also dissolved in a solvent such as methyl ethyl ketone contained in the high-brightness ink composition. Since it is difficult to do so, it is possible to maintain high smoothness when the anchor layer is formed even when the high-brightness ink composition is printed thereon. Further, in particular, in the case of a flake-shaped metal pigment such as aluminum powder, due to the high polarity of the surface of the thermoplastic resin having such a high acid value, the large surface that reflects light is arranged with high orientation so that it faces upward. It is considered that the whitening due to the decrease in the orientation is effectively suppressed. Furthermore, since the anchor layer 3 contains a thermoplastic resin, it has a characteristic of being highly flexible as compared with a thermosetting resin or the like. Due to the above factors, it is considered that the decorative sheet of the present invention realizes a high-luminance metallic tone by the high-luminance ink layer 2 and excellent formability that can be suitably applied to deep drawing. .

  The average acid value of the thermoplastic resin contained in the anchor layer 3 is not particularly limited as long as it is 60 mgKOH / g or more, but it is preferably 80 mgKOH from the viewpoint of enhancing the formability while further increasing the brightness of the decorative sheet. / G or more, more preferably 100 mgKOH / g or more, and further preferably about 120 to 250 mgKOH / g. If the average acid value of the thermoplastic resin contained in the anchor layer 3 exceeds 250 mgKOH / g, the thermoplastic resin becomes difficult to dissolve in the solvent, making it difficult to form the anchor layer 3 by printing.

  The hydroxyl value of the thermoplastic resin contained in the anchor layer 3 is not particularly limited, but is preferably 30 mgKOH / g or more. Since the thermoplastic resin contained in the anchor layer 3 has a hydroxyl value of 30 mgKOH / g or more, the wettability of the thermoplastic resin is enhanced, so that the printability of the anchor layer 3 is improved, and the brightness of the anchor layer 3 is accordingly increased. Can be increased. Therefore, for example, even when the average acid value of the thermoplastic resin contained in the anchor layer 3 is less than 200 mgKOH / g, the brightness of the decorative sheet can be more effectively increased. The hydroxyl value of the thermoplastic resin contained in the anchor layer 3 is more preferably about 50 to 100 mgKOH / g, further preferably about 100 to 150 mgKOH / g. The hydroxyl value (OH value) of the thermoplastic resin contained in the anchor layer is a value measured according to the regulations of JIS K0070: 1992.

  The thermoplastic resin contained in the anchor layer 3 is not particularly limited as long as it is a thermoplastic resin having an average acid value of 60 mgKOH / g or more, but it is preferable to contain an acrylic resin.

  Preferable examples of the acrylic resin include acrylic resin and acrylic polyol resin. As the acrylic resin, an acrylic resin having a (meth) acrylic acid monomer as a constituent unit and an acrylic resin having a (meth) acrylic acid ester monomer as a constituent unit are preferable. In addition, these acrylic resins may be a homopolymer of one kind of monomer, or may be a block copolymer or a random copolymer of two or more kinds of monomers.

  The average acid value of the thermoplastic resin can be increased by increasing the proportion of the acrylic resin having the (meth) acrylic acid monomer as a constituent unit in the thermoplastic resin contained in the anchor layer 3. When an acrylic resin having a (meth) acrylic acid monomer as a structural unit is used as the thermoplastic resin of the anchor layer 3, the proportion of the acrylic resin in the thermoplastic resin is preferably about 50 to 100% by mass, more preferably Is about 80 to 100% by mass.

  Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, normal butyl (meth) acrylate, and (meth) acrylate. ) Isobutyl acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, isobonyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth ) Examples include acrylate.

  The acrylic resin having the (meth) acrylic acid monomer as a constituent unit may be a block copolymer or a random copolymer of a (meth) acrylic acid monomer and a (meth) acrylic acid ester monomer.

  In addition, an acrylic resin having a (meth) acrylic acid monomer as a constituent unit and an acrylic resin having a (meth) acrylic acid ester monomer as a constituent unit are a block copolymer or a random copolymer with another monomer, respectively. It may be. Other monomers are not particularly limited as long as they are copolymerizable with (meth) acrylic acid or (meth) acrylic acid ester, but in the present invention, styrene, (anhydrous) maleic acid, fumaric acid, divinylbenzene, Vinyl biphenyl, vinyl naphthalene, diphenyl ethylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl alcohol, acrylonitrile, acrylamide, butadiene, isoprene, isobutene, 1-butene, 2-butene, N-vinyl-2-pyrrolidone, dicyclo Preferred examples include alicyclic olefin monomers such as pentadiene, ethylidene norbornene and norbornenes, vinylcaprolactam, citraconic anhydride, maleimides such as N-phenylmaleimide, vinyl ethers and the like.

  The acrylic polyol resin is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate. ) Alkyl acrylate and (meth) acrylic acid having a hydroxyl group in the molecule such as 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. The thing obtained by copolymerizing with an ester is mentioned.

  The weight average molecular weight of the acrylic resin is not particularly limited, but preferably 10,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more. The upper limit of the weight average molecular weight of the acrylic resin is usually about 50,000. The weight average molecular weight of the acrylic resin in the present specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

  The thermoplastic resins may be used alone or in combination of two or more. The average acid value and the hydroxyl value of the thermoplastic resin contained in the anchor layer 3 can be adjusted, for example, by combining two or more kinds of thermoplastic resins. As a specific example, when an acrylic resin and an acrylic polyol resin are used together, the average acid value and hydroxyl value can be adjusted appropriately.

  The thickness of the anchor layer 3 is not particularly limited, but is, for example, about 1 to 20 μm, preferably about 1 to 10 μm.

  The anchor layer 3 can be formed using a resin composition containing a thermoplastic resin having an average acid value of 60 mgKOH / g or more. Specifically, it can be formed by printing a resin composition in which the above-mentioned thermoplastic resin forming the anchor layer is dissolved or dispersed in a solvent or the like. The printing method for forming the anchor layer 3 is not particularly limited, and examples thereof include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and inkjet printing.

[Surface protection layer 4]
The surface protective layer 4 may be positioned on the outermost surface of the decorative resin molded product, if necessary, for the purpose of enhancing the scratch resistance, weather resistance, etc. of the decorative resin molded product, and may be used as a decorative sheet. It is a layer provided. The material forming the surface protective layer 4 is not particularly limited, but a resin is usually used, and an ionizing radiation curable resin is preferably used. It is also preferable that the surface protective layer 4 is formed of a resin film. The resin film is not particularly limited, and examples thereof include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and acrylic resin films. Among these, it is particularly preferable to use an acrylic resin film. . The surface protective layer 4 may be formed of, for example, one layer of ionizing radiation curable resin or resin film, or may be formed of two or more layers of these. 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 for forming the surface protective layer 4 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a polymerizable unsaturated bond or an epoxy group is contained in the molecule. And a mixture of at least one of a prepolymer, an oligomer, a monomer, and the like. Here, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays are also included. Among the ionizing radiation curable resins, the electron beam curable resin is suitable for forming the surface protective layer 4 because it can be solvent-free, does not require a photopolymerization initiator, and has stable curing characteristics. Used for.

  As the above-mentioned monomer used as the ionizing radiation-curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more polymerizable unsaturated bonds (two or more functional), preferably three or more (three or more functional) in the molecule. As the polyfunctional (meth) acrylate, specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalic acid 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 (Meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol Hexa (meth) acrylate and the like can be mentioned. These monomers may be used alone or in combination of two or more.

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

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

(Other additives)
Various additives may be added to the ionizing radiation curable resin composition forming the surface protective layer 4, depending on desired physical properties to be provided in the surface protective layer 4. Examples of the additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, defoamers, fillers, solvents, colorants, matting agents and the like. These additives can be appropriately selected and used from commonly used ones, and examples of the matting agent include silica particles and aluminum hydroxide particles. Further, as the ultraviolet absorber or the 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 is not particularly limited, but when the surface protective layer 4 is formed using an ionizing radiation curable resin, for example, 1 to 1000 μm, preferably 1 to 50 μm, and more preferably 1 to 30 μm can be mentioned. When the thickness in this range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance and weather resistance can be obtained, and it is possible to uniformly irradiate with ionizing radiation, so that it should be uniformly cured. It is possible and economically advantageous. When the surface protection layer 4 is formed of a resin film, the thickness is, for example, 25 to 1000 μm, preferably 50 to 200 μm. Furthermore, when the thickness of the surface protective layer 4 satisfies the above range, the three-dimensional formability of the decorative sheet is further improved, and thus high conformability to a complicated three-dimensional shape such as an automobile interior application can be obtained. it can. As described above, in the decorative sheet of the present invention, even if the thickness of the surface protective layer 4 is made thicker than that of the conventional one, a sufficiently high three-dimensional moldability can be obtained. It is also useful as a decorative sheet for required members such as vehicle exterior parts.

(Formation of surface protection 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 this, and crosslinking-curing the composition. The viscosity of the ionizing radiation curable resin composition may be any viscosity as long as an uncured resin layer can be formed on the surface of the pattern layer 5 or the primer layer 7 by the coating method described later.

  In the present invention, the prepared coating solution is applied onto the pattern layer 5 and the primer layer 7 so as to have the above-mentioned thickness by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating and the like. Method, preferably by gravure coating to form an uncured resin layer.

  The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam or an ultraviolet ray to cure the uncured resin layer to form the surface protective layer 4. Here, when an electron beam is used as the ionizing radiation, the accelerating voltage thereof can be appropriately selected depending on the resin used and the thickness of the layer, but usually the accelerating voltage is about 70 to 300 kV.

  In the electron beam irradiation, the higher the accelerating voltage is, the higher the transmissivity is. Therefore, when a resin which is easily deteriorated by the electron beam irradiation is used under the surface protection layer 4, the electron beam penetration depth and the surface protection are reduced. The accelerating voltage is selected so that the thicknesses of the layers 4 are substantially equal. Thereby, the irradiation of the extra electron beam to the layer located under the surface protective layer 4 can be suppressed, and the 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).

  Further, the electron beam source is not particularly limited, and for example, various electron beam accelerators such as Cockloft-Walton type, Van de Graft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. Can be used.

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

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

  When the surface protective layer 4 is formed of a resin film, the resin film may be laminated on the pattern layer 5, the primer layer 7, and the like. As the resin film, it is also possible to use a resin film containing an additive such as a matting agent or a resin film which has been subjected to surface treatment such as sandblasting.

[Primer layer 7]
The primer layer 7 is a layer that is included as necessary for the purpose of enhancing the adhesiveness between the surface protective layer 4 and the layer located thereunder. The primer layer 7 can be formed of resin.

  The resin forming the primer layer 7 is not particularly limited, but examples thereof include urethane resin, acrylic resin, (meth) acrylic-urethane copolymer resin, polyester resin, butyral resin, and the like. Among these resins, urethane resins, acrylic resins, and (meth) acrylic-urethane copolymer resins are preferable. These resins may be used alone or in combination of two or more.

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

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

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

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

  The thickness of the primer layer 7 is not particularly limited, but is, for example, about 0.1 to 10 μm, preferably about 1 to 10 μm. By satisfying such a thickness of the primer layer 7, the weather resistance of the decorative sheet can be further enhanced, and cracking, breakage, whitening, etc. of the surface protective layer 4 can be effectively suppressed.

  The primer layer 7 is a resin for forming the primer layer 7, and is 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 usual coating method such as a wire bar coat, a flow coat, a comma coat, a pouring coat, a brush coat, a spray coat or a transfer coating method. Here, the transfer coating method is a method of forming a coating film of a primer layer or an adhesive layer on a thin sheet (film base material) and then coating the surface of a target layer in a decorative sheet.

[Pattern layer 5]
The pattern layer 5 is a layer provided as necessary for the purpose of imparting decorativeness to the decorative sheet, for example. From the viewpoint of providing a decorative sheet having higher brightness and excellent formability, the pattern layer 5 is preferably laminated so as not to be adjacent to the high brightness ink layer 2. That is, when the high-brightness ink layer 2 is laminated on the pattern layer 5, the pattern layer 5 is dissolved in the solvent for forming the high-brightness ink layer 2 and the smoothness is lowered, and the high-brightness ink layer 2 is formed. The brightness of is likely to decrease. Further, when the pattern layer 5 is laminated on the high-brightness ink layer 2, the high-brightness ink layer 2 is dissolved in the solvent for forming the pattern layer 5 and the smoothness is lowered, resulting in high brightness. The brightness of the ink layer 2 is likely to decrease.

  The pattern layer 5 is formed by using, for example, a pattern layer ink composition, and has a desired pattern. The pattern layer ink composition used for forming the pattern layer 5 is obtained by appropriately mixing a binder resin 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. Is used.

  Examples of the binder resin for the ink composition for the pattern layer include chlorine resins, acrylic resins, polyurethanes, polyesters, polyamides, butyral resins, polystyrenes, nitrocellulose resins, cellulose acetate resins, and the like, preferably chlorine resins, An acrylic resin can be used. These binder resins may be used alone or in combination of two or more.

  From the viewpoint of further enhancing the transferability of the ink composition for a picture layer, 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. Range, and more preferably about 5/5 to 7/3. Examples of the chlorine-based resin include those exemplified for the high-brightness ink layer 2.

  The colorant contained in the pattern layer ink composition is not particularly limited, and examples thereof include carbon black (black ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red pattern, 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 5 is not particularly limited, but for example, a stone pattern imitating the surface of a rock such as a wood pattern, a marble pattern (for example, a travertine marble pattern), a textured or cloth-like pattern is imitated. Examples of the pattern include a fabric pattern, a tile pasting pattern, a brickwork pattern, etc., and a composite pattern of these, such as a parquet or a patchwork, may be used. These patterns are formed by multicolor printing using normal yellow, red, blue, and black process colors, but also by multicolor printing using special colors prepared by preparing individual color plates that make up the pattern. Can be formed. The pattern layer 5 is also used in a combination of a pattern pattern layer that expresses a pattern such as a wood grain pattern and a solid layer. The whole solid layer is usually used as a hiding layer, a coloring layer, a coloring hiding layer, or the like.

  The thickness of the pattern layer 5 is not particularly limited, but is, for example, about 1 to 30 μm, preferably about 1 to 20 μm.

  The pattern layer 5 is formed, for example, by printing using a pattern layer ink composition so as to obtain a desired pattern. The printing method for forming the pattern layer 5 is not particularly limited, and examples thereof include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and inkjet printing.

[Adhesive layer 6]
The adhesive layer 6 is, for example, a layer of the decorative sheet such as between the base material layer 1 and the high-brightness ink layer 2, or a decorative sheet such as between the high-brightness ink layer 2 and the molding resin layer 9. It is a layer provided as needed for the purpose of enhancing the adhesion with the molding resin layer 9. The resin forming the adhesive layer 6 is not particularly limited as long as it can improve the interlayer of the decorative sheet, the adhesion between the decorative sheet and the molding resin layer 9, and the adhesiveness. A thermoplastic resin or a thermosetting resin is used. Examples of the thermoplastic resin include acrylic resin, acryl-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber resin. . The thermoplastic resins may be used alone or in combination of two or more. Further, examples of the thermosetting resin include urethane resin and epoxy resin. The thermosetting resin may be used alone or in combination of two or more.

  Although the adhesive layer 6 is not always a necessary layer, when it is assumed that the decorative sheet of the present invention is applied to a decorative method such as a vacuum pressure bonding method described below, which is adhered onto a resin molded body prepared in advance. Is preferably provided on the surface of the decorative sheet that is in contact with the resin molded body. When used in the vacuum pressure bonding method, it is preferable to form the adhesive layer 6 by using, among the above-mentioned various resins, a resin that is commonly used as a resin that exhibits adhesiveness when pressed or heated.

  The thickness of the adhesive layer 6 is not particularly limited and may be appropriately set depending on the position where the adhesive layer 6 is provided and an adjacent layer, but for example, about 0.1 to 30 μm, preferably about 0.5 to 20 μm, More preferably, it is about 1 to 8 μm.

[Release layer 8]
In the decorative sheet of the second aspect, the release layer 8 is provided on the transfer base material layer 1a as necessary, and constitutes the support 10 together with the transfer base material layer 1a. The release layer 8 is a layer having a role of enhancing the releasability of the transfer base material layer 1 a from the transfer layer 11.

  The release layer 8 may be a solid release layer that covers the entire surface of the transfer base material layer 1a (solid surface), or may be a part of the release layer. Usually, a solid release layer is preferable in consideration of releasability.

  The release layer 8 includes a silicone resin, a fluorine resin, an acrylic resin (including, for example, an acrylic-melamine resin), a polyester resin, a polyolefin resin, a polystyrene resin, a polyurethane resin, and a cellulose resin. , Vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as nitrification cotton, copolymers of monomers forming the thermoplastic resins, or those resins modified with (meth) acrylic acid or urethane. The resin composition may be used alone or in combination of two or more. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified products thereof are preferable, and more specifically, acrylic-melamine. -Based resin alone, acrylic-melamine-based resin-containing composition, resin composition obtained by mixing polyester-based resin with ethylene-modified acrylic acid copolymer modified with urethane, copolymer of acrylic-based resin and styrene and acrylic And a resin composition in which the emulsion is mixed. Of these, it is particularly preferable that the release layer 8 is composed of the acrylic-melamine resin alone or a composition containing 50% by mass or more of the acrylic-melamine resin.

  The thickness of the release layer 8 is usually about 0.01 to 5 μm, preferably about 0.05 to 3 μm.

  The decorative sheet of the present invention can be manufactured by laminating the above layers. In the present invention, in particular, after forming the anchor layer 3 with a resin composition containing a thermoplastic resin having an average acid value of 60 mgKOH / g or more, a high-brightness ink layer 2 containing a pigment is laminated on the anchor layer 3. By adopting the manufacturing method including the step of, a decorative sheet having a high-luminance metallic design and excellent in moldability can be obtained. The details of this mechanism are as described above, for example.

2. Sheet for Manufacturing Decorative Sheet In the present invention, the decorative sheet as described above may be manufactured using a sheet for manufacturing a decorative sheet having the following configuration.
A sheet in which a high-brightness ink layer 2 containing a pigment, an anchor layer 3 containing a thermoplastic resin, a primer layer 7, a release layer 8 and a transfer base material layer 1a are laminated in this order, and the anchor A sheet for producing a decorative sheet in which the layer 3 and the high-brightness ink layer 2 are laminated so as to be adjacent to each other, and the thermoplastic resin contained in the anchor layer 3 has an average acid value of 60 mgKOH / g or more.

  The composition of each layer constituting the sheet is the same as above. As a laminated structure of the sheet, for example, as shown in FIG. 8, a primer layer 7, an anchor layer 3, and a high layer are provided on a support 10 on which a transfer base material layer 1a and a release layer 8 are laminated. A structure in which the brightness ink layer 2 is laminated in this order can be given. For example, as shown in FIG. 8, a pattern layer 5 may be laminated between the primer layer 7 and the anchor layer 3 as required. As a laminated structure of the sheet for producing the decorative sheet of the present invention, a laminated structure in which a transfer base material layer / release layer / primer layer / anchor layer / high brightness ink layer is laminated in this order; A layered structure in which a layer / release layer / primer layer / pattern layer / anchor layer / high-brightness ink layer are laminated in this order is exemplified. FIG. 8 shows, as an embodiment of the laminated structure of the sheet for producing the decorative sheet of the present invention, the transfer base material layer / release layer / primer layer / pattern layer / anchor layer / high-brightness ink layer in this order. FIG. 4 shows a schematic cross-sectional view of an example of laminated sheets. In the sheet, the transfer base material layer 1 a and the release layer 8 form the support 10.

  A method for producing a decorative sheet of the present invention using a sheet for producing such a decorative sheet will be described with reference to FIGS. 8 to 11.

  First, the high-brightness ink layer 2 side of the sheet for producing the decorative sheet of the present invention as shown in FIG. 8 is laminated on the above resin film or the like constituting the base material layer 1. As a laminating method, it is preferable to use hot pressing using a mirror surface plate or embossing using a mirror surface roll. Specifically, a known heat press machine or embossing machine is used to heat and soften the above-mentioned sheet and the resin film constituting the base material layer 1, and press and bond them in a stacked state. As a result, a sheet as shown in FIG. 9 is obtained.

  Next, the support 10 is peeled off from the sheet as shown in FIG. By peeling the support 10 between the release layer 8 and the primer layer 7, the high-brightness ink layer 2, the anchor layer 3, the primer layer 2, etc. are formed on the base material layer 1 as shown in FIG. A sheet laminated in order is obtained.

  Next, the decorative sheet of the present invention as shown in FIG. 11 can be manufactured by forming the surface protective layer 4 on the primer layer 7 of the sheet shown in FIG. The surface protection layer 4 can be formed in the same manner as above.

  The sheet for producing the decorative sheet of the present invention comprises a primer layer 7, an anchor layer 3, a high-brightness ink layer 2, etc. on a support 10 having a transfer base material layer 1a and a release layer 8. Can be manufactured by sequentially stacking.

3. Decorative Resin Molded Article The decorative resin molded article of the present invention is formed by integrating the decorative resin of the present invention with a molding resin. That is, the decorative resin molded article of the present invention is composed of a laminate in which at least a high-brightness ink layer containing a pigment and an anchor layer containing a thermoplastic resin are laminated on a molding resin layer so as to be adjacent to each other. The average acid value of the thermoplastic resin contained in the anchor layer is 60 mgKOH / g or more. In the decorative resin molded product of the present invention, the decorative sheet may be further provided with at least one layer such as the surface protective layer 4, the primer layer 7, the pattern layer 5, and the adhesive layer 6 as necessary. . In the above-mentioned first aspect as shown in FIGS. 3, 4 and 12, the decorative resin molded article may be provided with the base material layer 1. Further, also in the above-described second aspect as shown in FIG. 6, the decorative resin molded article may be provided with the support 10 including the transfer base material layer 1a (decoration in such a state). Resin molded products are also called decorative resin molded products with a support). 3 is a cross-sectional view of a decorative resin molded product obtained by laminating a molding resin on the decorative sheet shown in FIG. 1, and FIG. 4 is a sectional view of a molding resin laminated on the decorative sheet shown in FIG. It is a cross-sectional view of a decorated resin molded product.

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

  In the insert molding method, first, in a vacuum forming step, the decorative sheet of the present invention is vacuum formed (offline preforming) into a surface shape of a formed product in advance by a vacuum forming die, and then an extra portion is trimmed as necessary. Obtain a formed sheet. This molding sheet is inserted into the injection molding die, the injection molding die is clamped, the resin in the fluid state is injected into the mold and solidified, and at the same time as the injection molding, the decorative sheet is integrated on the outer surface of the resin molding. A decorative resin molded product is manufactured by making it into a resin.

More specifically, the decorated resin molded product of the present invention is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance using a vacuum forming die
Trimming process to obtain a molded sheet by trimming the excess part of the vacuum-formed decorative sheet, and insert the molded sheet into the injection mold, close the injection mold, and inject the resin in the fluid state into the injection mold. Then, the integrated process of integrating the resin and the molded sheet.

  In the vacuum forming step in the insert forming method, the decorative sheet may be heated and formed. The heating temperature at this time is not particularly limited and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. For example, in the case of using an ABS resin film as the base material layer. If it exists, it can be usually set to about 120 to 200 ° C. Further, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but can be usually about 180 to 320 ° C.

  In the injection molding simultaneous decoration method, the decorative sheet of the present invention is arranged in a female mold that is also used as a vacuum forming mold having a suction hole for injection molding, and preforming (in-line preforming) is performed with this female mold. After that, the injection molding die is clamped, and the resin in a fluid state is injection-filled in the mold and solidified, and the decorative sheet of the present invention is integrated with the outer surface of the resin molding simultaneously with the injection molding. As a result, a decorated resin molded product is manufactured.

More specifically, the decorative resin molded product of the present invention is manufactured by an injection-molding simultaneous decoration method including the following steps.
After the decorative sheet of the present invention is installed so that 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, and the movable metal sheet is moved. A preforming step of preforming the decorative sheet by vacuum suction from the mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable mold.
After clamping the movable mold and the fixed mold having the decorative sheet adhered along the molding surface, the resin in the fluid state is injected and filled in the cavity formed by both molds to solidify. To form a resin molded body by laminating and integrating the resin molded body and the decorative sheet, and a resin molding in which all layers of the decorative sheet are laminated by separating the movable mold from the fixed mold. Extraction process to remove the body.

  In the preforming step of the injection molding simultaneous decorating method, the heating temperature of the decorating sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorating sheet, the thickness of the decorating sheet, and the like. When a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can usually be about 70 to 130 ° C. In addition, in the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but can be usually about 180 to 320 ° C.

  In the vacuum pressure bonding method, first, the decorative sheet and the resin molded body of the present invention are placed in the first vacuum chamber including the first vacuum chamber located on the upper side and the second vacuum chamber located on the lower side. The vacuum chamber side, the resin molded body is set to the second vacuum chamber side, and the base material layer 1 side of the decorative sheet is installed in the vacuum pressure bonding machine so that it faces the resin molded body side. To do. The resin molded body is installed on a lift table provided on the second vacuum chamber side and capable of moving up and down. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using an elevating table, and the pressure difference between the two vacuum chambers is used to stretch the decorative sheet while stretching the resin molded body. Stick on the surface of. 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 needed.

  In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet before the step of pressing the above-mentioned molded body against the decorative sheet so as to soften the decorative sheet and improve moldability. The vacuum crimping method including the step may be particularly called a vacuum thermocompression bonding method. The heating temperature in the step may be appropriately selected depending on the type of resin forming the decorative sheet, the thickness of the decorative sheet, and the like, but when using a polyester resin film or an acrylic resin film as the base material layer, Usually, it can be about 60 to 200 ° C.

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

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

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

  In the second aspect, the support 10 is peeled and removed from the decorative resin molded product with a support obtained by integrating the decorative sheet and the molding resin by the above-described method, thereby decorating. A resin molded product is obtained. The step of peeling and removing the support 10 can be performed at any time, and for example, the support 10 can be peeled and removed at the same time when the obtained decorative resin molded article with the support is taken out from the molding apparatus. Further, in the decorative resin molded product with a support, the base material layer in the support serves as a protective sheet for the decorative resin molded product, so that it does not peel off after the production of the decorative resin molded product with a support. It may be stored as it is, and the support may be peeled off at the time of use. By using in such an aspect, it is possible to prevent the decorative resin molded product from being scratched due to rubbing during transportation.

  Since the decorative resin molded product of the present invention has a high-luminance metallic design and is formed of a decorative sheet having high moldability, for example, an interior material or exterior material of a vehicle such as an automobile; It can be used as fittings such as window frames and door frames; interior materials for buildings such as walls, floors and ceilings; housings for home electric appliances such as television sets and air conditioners; containers and the like.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples. In addition, in Examples and Comparative Examples, the average acid value of the thermoplastic resin contained in the anchor layer is a value measured in accordance with JIS K2501: 2003. Further, the hydroxyl value (OH value) of the thermoplastic resin contained in the anchor layer is a value measured according to the regulations of JIS K0070: 1992.

(Preparation of decorative sheet)
<Examples 1 to 4 and Comparative Examples 1 to 3>
An acrylic resin film (thickness: 75 μm) is used as a surface protective layer, and a pattern layer forming ink containing a vinyl chloride-vinyl acetate copolymer resin / acrylic resin as a binder resin is printed on the surface of the film by gravure coating, A pattern layer was formed. Next, the resins shown in Tables 1 and 2 were printed as an anchor layer by gravure coating (thickness 1 μm). Next, an aluminum pigment having a particle diameter of about 10 μm and a thickness of about 50 nm (flake-like product made by crushing a metal thin film formed by vapor deposition, 100 parts by mass) and vinyl chloride-vinyl acetate copolymer resin ( A high-brightness ink composition containing 100 parts by mass) was dissolved in a solvent containing mainly methyl ethyl ketone and printed by gravure coating to form a high-brightness ink layer. In order to improve the hiding power, two layers of high-brightness ink were printed (total thickness of high-brightness ink layer: 2 μm). Next, an adhesive agent made of polyester polyol was printed by gravure coating and was laminated by dry lamination with a base material layer made of ABS resin (thickness 400 μm) to obtain a decorative sheet. The layer structure of the decorative sheets of Examples 1 to 4 and Comparative Examples 1 to 3 is as shown in FIG. In Comparative Example 1, no anchor layer was provided.

  Next, with respect to the decorative sheets obtained in Examples 1 to 4 and Comparative Examples 1 to 3, the brightness and the formability were evaluated by the following methods, respectively. The results are shown in Table 2.

(Evaluation of high brightness)
The brightness was evaluated by the glossiness, and a BYK Gardner Microgloss (60 °) was used for the measurement.

(Evaluation of workability)
After the decorative sheet was stretched in one direction by 300% with a tensile tester, the surface of the decorative sheet was visually observed, and the formability was evaluated according to the following criteria.
◯: The decorative sheet is not cracked at all Δ: Microscopic cracks are generated in the decorative sheet ×: Large cracks are generated in the decorative sheet

(Preparation of decorative sheet)
<Examples 5 to 8 and Comparative Examples 4 to 6>
An ABS resin film (thickness 400 μm) is used as the base material layer, and an ink for forming a pattern layer containing a vinyl chloride-vinyl acetate copolymer resin / acrylic resin as a binder resin is printed on the surface of the film by gravure coating to obtain a pattern. Layers were formed. Next, the resins shown in Tables 1 and 3 were printed by gravure coating as an anchor layer (thickness 1 μm). Next, an aluminum pigment having a particle size of about 10 μm and a thickness of about 50 nm (flake-like product made by crushing a metal thin film formed by vapor deposition, 100 parts by mass) and vinyl chloride-vinyl acetate copolymer resin ( A high-brightness ink composition containing 100 parts by mass) was dissolved in a solvent containing mainly methyl ethyl ketone and printed by gravure coating to form a high-brightness ink layer. In order to improve the hiding power, two layers of high-brightness ink were printed (total thickness of high-brightness ink layer: 2 μm). Next, a primer layer made of acrylic resin was printed on the surface of the high-brightness ink layer by gravure coating so as to have a thickness of 3 μm. Next, the following ionizing radiation curable (EB) resin composition was printed on the surface of the primer layer as a surface protective layer by gravure coating so that the thickness of the resin composition after curing was 10 μm, and the uncured resin The layer was irradiated with an electron beam having an accelerating voltage of 165 kV and an irradiation intensity of 50 kGy (5 Mrad) to cure the ionizing radiation curable resin composition to obtain a decorative sheet. The layer structure of the decorative sheets of Examples 5 to 8 and Comparative Examples 4 to 6 is as shown in FIG. In Comparative Example 4, no anchor layer was provided.
[Ionizing radiation curable resin composition]
Acrylic silicone acrylate (weight average molecular weight 20,000): 70 parts by weight Hexafunctional urethane acrylate oligomer (weight average molecular weight 5,000): 30 parts by weight

  Next, each of the decorative sheets obtained in Examples 5 to 8 and Comparative Examples 4 to 6 was evaluated for high brightness and formability by the same method as described above. The results are shown in Table 3.

  As is clear from the results shown in Tables 2 and 3, in the decorative sheets of Examples 1 to 8, in which the anchor layer containing the thermoplastic resin having a high acid value was laminated so as to be adjacent to the high-brightness ink layer, It had specularity, suppressed whitening, and had excellent brightness. Further, in these decorative sheets, even when stretched by 300% (even when stretched three times), cracks were not generated at all and the moldability was high. On the other hand, in Comparative Examples 1 and 4 in which the anchor layer was not provided, the moldability was excellent, but the brightness was significantly inferior to Examples 1 to 8. In addition, the decorative sheets of Comparative Examples 2 and 5 in which the anchor layer containing a thermoplastic resin having a low acid value was laminated so as to be adjacent to the high-brightness ink layer were also excellent in moldability, but Example 1 The brightness was remarkably inferior to that of -8. Further, the decorative sheets of Comparative Examples 3 and 6 in which the anchor layer formed of the thermosetting resin was laminated so as to be adjacent to the high-brightness ink layer, were excellent in brightness, Moldability was significantly inferior to that of No. 8. In addition, for example, from the comparison between Examples 2 and 3 or the comparison between Examples 6 and 7, it was possible to increase the brightness due to the high hydroxyl value even if the acid value was the same.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 1a ... Transfer base material layer 2 ... High brightness ink layer 3 ... Anchor layer 4 ... Surface protection layer 5 ... Picture layer 6 ... Adhesive layer 7 ... Primer layer 8 ... Release layer 9 ... Molding resin layer 10 ... Support 11 ... Transfer layer

Claims (13)

At least, a high-brightness ink layer containing a metal pigment and an anchor layer containing an acrylic resin are laminated so as to be adjacent to each other,
A decorative sheet, wherein the acrylic resin contained in the anchor layer has an average acid value of 60 mgKOH / g or more.   The decorative sheet according to claim 1, wherein the metal 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.   The decorative sheet according to claim 1, wherein a pattern layer is laminated so as not to be adjacent to the high-brightness ink layer.   The decorative sheet according to claim 1, further comprising a surface protective layer.   The decorative sheet according to claim 1, further comprising a base material layer. The high-brightness ink layer, the anchor layer, and a surface protective layer are laminated in this order,
The decorative sheet according to claim 1.   The decorative sheet according to any one of claims 1 to 3, wherein a base material layer, the high-brightness ink layer, the anchor layer, and a surface protective layer are laminated in this order.   The decorative sheet according to claim 1, wherein a base material layer, the anchor layer, the high-brightness ink layer, and a surface protection layer are laminated in this order.   The decorative sheet according to claim 1, wherein the high-brightness ink layer, the anchor layer, the surface protective layer, and the transfer base material layer are laminated in this order.   The decorative sheet according to claim 1, wherein the acrylic resin has a hydroxyl value of 30 mgKOH / g or more. A sheet in which a high-brightness ink layer containing a metal pigment, an anchor layer containing an acrylic resin, a primer layer, a release layer, and a release base material layer are laminated in this order,
The anchor layer and the high-brightness ink layer are laminated so as to be adjacent to each other,
A sheet for producing a decorative sheet, wherein the acrylic resin contained in the anchor layer has an average acid value of 60 mgKOH / g or more. A method for manufacturing a decorative sheet according to any one of claims 1 to 10,
A decorative sheet comprising a step of forming an anchor layer from a resin composition containing an acrylic resin having an average acid value of 60 mgKOH / g or more, and then laminating a high-brightness ink layer containing a metal pigment on the anchor layer. Manufacturing method. At least, on the molded resin layer, a high-brightness ink layer containing a metal pigment, and an anchor layer formed of a resin composition containing an acrylic resin are laminated so as to be adjacent to each other, a laminate.
A decorated resin molded product, wherein the acrylic resin contained in the anchor layer has an average acid value of 60 mgKOH / g or more.