JP2015193244A - Decorative sheet and decorative resin molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having high brightness and excellent molding property.SOLUTION: The decorative sheet includes at least a high-brightness ink layer containing a pigment and an anchor layer containing a thermoplastic resin, stacked to be abutting to each other. The thermoplastic resin included in the anchor layer has an average acid value of 60 mgKOH/g or more.

Description

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

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

  As a decorative sheet, 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 problems such as high cost and low followability to elongation when a decorative sheet is formed.

  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 the decorative sheet is usually provided with other layers such as a surface protective layer and a design layer that imparts designability in addition to the high-brightness ink layer, the high-brightness is directly above the PET film. It is extremely rare that a layer structure in which an ink layer is laminated can be adopted.

  In addition, the pattern layer, the surface protective layer, and the like formed on the decorative sheet are usually easily dissolved in the solvent used for forming the high-brightness ink layer, so when a high-brightness ink layer is formed immediately above these layers, There is a problem that the smoothness of the surface of these layers is lowered, and the brightness of the high brightness ink layer is lowered. Furthermore, 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, just before printing high-brightness ink, the surface of the high-brightness ink is smoothed by printing a thermosetting epoxy resin or urethane resin having high solvent resistance as an anchor layer. A method for expressing a high-brightness metallic tone with a high-brightness ink layer is disclosed. However, since the thermosetting resin used for the anchor layer is inferior in moldability, for example, when the decorative sheet is deep-drawn, there is a problem that it is difficult to follow the elongation of the decorative sheet and cracks are likely to occur.

JP 2004-74442 A

  In view of the above-described problems of the prior art, the main object of the present invention is to provide a decorative sheet having a high-brightness metallic design and excellent moldability.

  The present inventor has intensively 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 The decorative sheet was found to have high brightness and excellent moldability. The present invention has been completed by further studies based on these findings.

That is, this invention provides the invention of the aspect hung up below.
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,
The decorating sheet whose average acid value of the thermoplastic resin contained in the said anchor layer is 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 the base material layer, the high-luminance ink layer, the anchor layer, and the surface protective 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-luminance ink layer, and the surface protective 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, the surface protective layer, and the 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 peeling 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,
The sheet | seat for manufacturing a decorating sheet whose average acid value of the thermoplastic resin contained in the said anchor layer is 60 mgKOH / g or more.
Item 11. It is a manufacturing method of the decorating sheet in any one of claim | item 1-9,
A decorative sheet comprising a step of laminating a high-brightness ink layer containing a pigment on the anchor layer after forming the anchor layer with a resin composition containing a thermoplastic resin having an average acid value of 60 mgKOH / g or more. Production method.
Item 12. At least, on the molded resin layer, consists of a laminate in which a high-brightness ink layer containing a pigment and an anchor layer formed of a resin composition containing a thermoplastic resin are adjacent to each other,
A decorative resin molded product in which an average acid value of a thermoplastic resin contained in the anchor layer is 60 mgKOH / g or more.

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

It is a schematic sectional drawing of an example (1st aspect) of the decorating sheet of this invention. It is a schematic sectional drawing of an example (1st aspect) of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating resin molded product (1st aspect) of this invention. It is a schematic sectional drawing of an example of the decorating resin molded product (1st aspect) of this invention. It is a schematic sectional drawing of an example (2nd aspect) of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorative resin molded product with a support body of this invention (2nd aspect). 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 | seat for manufacturing the decorating sheet | seat of this invention. It is schematic-drawing sectional drawing of the sheet | seat which laminated | stacked the base material layer on the sheet | seat of FIG. FIG. 10 is a schematic cross-sectional view of a sheet obtained by peeling a support from the sheet described in FIG. 9. It is schematic-drawing sectional drawing of the decorating sheet | seat of this invention which formed the surface protective layer in the sheet | seat of FIG. It is schematic-drawing sectional drawing of an example of the decorative resin molded product of this invention which laminated | stacked molding resin on the sheet | seat of FIG.

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

Laminated structure of decorative sheet The decorative sheet of the present invention is laminated so that at least the high-brightness ink layer 2 containing a pigment and the anchor layer 3 containing a thermoplastic resin are adjacent to each other. Moreover, the decorating sheet of this invention may have the base material layer 1 as needed for the purpose of improving the shape retention of a decorating sheet. Moreover, the decorative sheet of this invention may provide the surface protective layer 4 as needed for the purpose of protecting the surface of a decorative sheet. Moreover, you may provide the primer layer 7 under the surface protective layer 4 as needed for the purpose of improving the adhesiveness of the surface protective layer 4 and the layer adjacent to this. Moreover, you may have the pattern layer 5 as needed for the purpose of providing the decorating property to a decorating sheet. In addition, between the decorative sheets (for example, between the base material layer 1 and the high-brightness ink layer 2) or between the decorative sheet and the molded resin layer 9 (for example, the high-brightness ink layer 2 and the molded resin layer). For example, the adhesive layer 6 may be provided for the purpose of improving the adhesiveness between the adhesive layer 9 and the like.

  As described later, 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. It can be set as the decorating sheet of the 2nd aspect in which the decorating sheet of 1 aspect or the base material layer 1 (it may be called the base material layer 1a for transfer) is not contained in a decorating resin molded product. That is, in the decorative sheet of the first aspect, by forming the molded 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 FIG. It is. On the other hand, in the decorative sheet of the second aspect, after forming the molded resin layer 9 on the side opposite to the base material layer 1 to obtain a decorated 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, etc., if necessary, for the purpose of enhancing the peelability of the base material layer 1 from the decorative resin molded product. A release layer 8 may be provided between the two.

  The laminated structure of the decorative sheet according to the first aspect of the present invention is a laminated structure in which a base layer / high brightness ink layer / anchor layer are 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; Laminated structure in which base layer / adhesive layer / high brightness ink layer / anchor layer / surface protective layer are laminated in this order; base layer / adhesive layer / high brightness ink layer / anchor Layer / picture layer / surface protective layer laminated structure in this order; base material layer / anchor layer / high brightness ink layer laminated structure; base material layer / anchor layer / high brightness ink layer / surface Laminated structure in which protective layers are laminated in this order; base layer / anchor layer / high brightness ink layer / primer layer / surface protective layer in this order; base layer / picture layer / anchor layer / high brightness Ink layer / primer layer / surface protective layer Etc. stacked in this order and the like. In FIG. 1, as one aspect of the laminated structure of the decorative sheet of the first aspect of the present invention, a base material layer / adhesive layer / high brightness ink layer / anchor layer / design layer / surface protective layer were laminated in this order. The schematic sectional drawing of an example of a decorating sheet is shown. In FIG. 2, as one aspect of the laminated structure of the decorative sheet of the first aspect in the present invention, a base layer / picture layer / anchor layer / high brightness ink layer / primer layer / surface protective layer were laminated in this order. The schematic sectional drawing of an example of a decorating sheet is shown. In the decorative sheet of the present invention, when the base material layer is not provided, a laminated structure in which an adhesive layer / a high-brightness ink layer / anchor layer / a picture layer / a surface protective layer are laminated in this order is exemplified.

  In the present invention, in the decorative sheet according to the second aspect, for example, as shown in FIG. 5, a support having a base layer 1 (transfer base layer 1a) and a release layer 8 provided as necessary. On 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 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 support 10 is obtained from the decorative resin molded product with a support. As a result, the decorative resin molded product as shown in FIG. 7 is obtained. The laminated structure of the decorative sheet according to the second aspect of the present invention includes a laminated structure in which a high-brightness ink layer / anchor layer / transfer base layer is laminated in this order; a high-brightness ink layer / anchor layer / release layer / Laminated structure in which transfer substrate layers are laminated in this order; High-brightness ink layer / anchor layer / surface protective layer / release layer / laminated structure in which transfer substrate layer is laminated in this order; high-brightness ink layer / Laminated structure in which anchor layer / primer layer / surface protective layer / release layer / transfer base material layer are laminated in this order; high-brightness ink layer / anchor layer / design layer / primer layer / surface protective layer / release layer / Laminated structure in which transfer substrate layers are laminated in this order; adhesive layer / high brightness ink layer / anchor layer / design layer / primer layer / surface protective layer / release layer / transfer substrate layer are laminated in this order Examples include a laminated structure. FIG. 5 shows an adhesive layer / high-brightness ink layer / anchor layer / design layer / primer layer / surface protective layer / release layer / transfer layer as one embodiment of the laminated structure of the decorative sheet according to the second embodiment of the present invention. The schematic sectional drawing of an example of the decorating sheet | seat on 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 improving 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 2nd aspect of this invention, in order to peel the support body 10 containing the base material layer 1 from the transfer layer 11 containing the below-mentioned pattern layer 5, the base material layer 1 is contained in a decorative resin molded product. Absent. In the second embodiment, 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 is three-dimensional moldability, compatibility with the molded resin layer 9 in the first aspect, and peelability from the surface protective layer 4 in the second aspect. Although it may be appropriately selected depending on the above, 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, 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 has high smoothness of the transfer base material layer 1 itself. 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 a resin component which forms the base material layer 1, only 1 type may be used and 2 or more types may be mixed and used. Moreover, the base material layer 1 may be formed with the single layer sheet | seat of these resin, and may be formed with the multilayer sheet | seat by the same kind or different kind | species resin.

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

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

  Although the thickness in particular of the base material layer 1 is not restrict | limited, Although it sets suitably according to the use etc. of a decoration sheet, if it is the 1st aspect of this invention, about 50-800 micrometers normally, Preferably it is about 100-600 micrometers. More preferably, about 200-500 micrometers is mentioned. When the thickness of the base material layer 1 is within the above range, the decorative sheet can be provided with more excellent three-dimensional formability, designability, and the like. Moreover, if it is the 2nd aspect of this invention, about 10-250 micrometers will be normally mentioned, Preferably about 20-100 micrometers is mentioned. When the thickness of the base material layer 1 is within the above range, it is possible to achieve both printing suitability and cost for the decorative sheet.

[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 of the present invention. 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 includes a pigment, a binder resin, and a solvent, and an anchor described later with a high-brightness ink composition in which extender pigments, stabilizers, plasticizers, catalysts, curing agents, and the like are appropriately mixed as necessary. It can be formed by printing on the layer 3. As described later, 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 decoration has high brightness and excellent 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 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 forming a high-luminance ink layer 2 on the anchor layer 3 to be described later to express higher luminance and improve moldability. A pigment may be used individually by 1 type and may be used in combination of 2 or more types.

  Although it does not restrict | limit especially as a particle diameter of a pigment, From a viewpoint which improves a moldability, raising a brightness | luminance of a decorating sheet, Preferably it is 20 micrometers or less, More preferably, about 10-15 micrometers 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. From the viewpoint of further increasing the luminance, flakes are preferable. Of the above-mentioned metal pigments, flakes can be produced, 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 it.

  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. In the present specification, (meth) acryl means acryl or methacryl, and the same applies to other similar expressions.

  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, ethyl acetate, toluene 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 using a high brightness ink composition. The printing method for forming the high brightness ink layer 2 is not particularly limited, and examples include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and ink jet printing.

[Anchor layer 3]
In the decorative sheet of the present invention, the anchor layer 3 is provided adjacent to the high-luminance ink layer 2 in order to provide the high-luminance ink layer 2 with high formability while exhibiting a high-luminance metallic design. Layer. The anchor layer 3 includes a thermoplastic resin having an average acid value of 60 mgKOH / g or more. In addition, the average acid value of the thermoplastic resin contained in the anchor layer 3 is a value measured in accordance with JIS K2501: 2003. In the anchor layer 3 of the present invention, for example, one or more types of thermoplastic resins having an acid value of 60 mgKOH / g or more are mixed, and the average acid value of the entire thermoplastic resin contained in the anchor layer 3 is 60 mgKOH / g. It may be the 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 included 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 contain components other than the thermoplastic resin having an average acid value of 60 mgKOH / g or more, but is substantially formed only of a thermoplastic resin having an average acid value of 60 mgKOH / g or more. Preferably it is.

  In the present invention, since the high-brightness ink layer 2 is formed so as to be adjacent to the anchor layer 3 containing a thermoplastic resin having an average acid value of 60 mgKOH / g or more, molding is performed while increasing the brightness of the decorative sheet. Sexuality is enhanced. 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 is not clear, but can be considered as follows, for example. That is, as described above, when a decorative sheet is produced, when a high-brightness ink layer is laminated on a pattern layer, a surface protective layer, or the like, the solvent is usually used by a solvent such as methyl ethyl ketone contained in the high-brightness ink composition. The surface of the layer is dissolved and the smoothness is lowered. Since the high-brightness ink layer is formed on a smooth surface, the high-brightness ink expresses high brightness. Therefore, when the high-brightness ink layer is formed on the surface having reduced smoothness, the brightness of the decorative sheet is lowered. . On the other hand, in the decorative sheet of the present invention, the anchor layer containing a thermoplastic resin having a high acid value equal to or higher than the specific average acid value is also soluble in a solvent such as methyl ethyl ketone contained in the high-brightness ink composition. Therefore, even when a high-brightness ink composition is printed thereon, high smoothness can be maintained when the anchor layer is formed. In particular, in the case of flaky metal pigments such as aluminum powder, the high polarity of the surface of the thermoplastic resin having such a high acid value is arranged with a high orientation so that the large surface that reflects light faces upward. It is considered that whitening due to a decrease in orientation is effectively suppressed. Furthermore, since the anchor layer 3 includes a thermoplastic resin, the anchor layer 3 has a characteristic that it is more flexible than 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-brightness metallic tone by the high-brightness 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 is preferably 80 mgKOH from the viewpoint of improving the moldability while further increasing the brightness of the decorative sheet. / G or more, More preferably, it is 100 mgKOH / g or more, More preferably, about 120-250 mgKOH / g is mentioned. In addition, when the average acid value of the thermoplastic resin contained in the anchor layer 3 exceeds 250 mgKOH / g, the thermoplastic resin is hardly dissolved in a solvent, so that it is 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 increased, so that the printability of the anchor layer 3 is improved, and accordingly the brightness of the anchor layer 3 is increased. Can be increased. For this reason, 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 further effectively increased. The hydroxyl value of the thermoplastic resin contained in the anchor layer 3 is more preferably about 50 to 100 mgKOH / g, and still more preferably about 100 to 150 mgKOH / g. In addition, the hydroxyl value (OH value) of the thermoplastic resin contained in the anchor layer is a value measured in accordance with JIS K0070: 1992.

  The thermoplastic resin contained in the anchor layer 3 is not particularly limited as long as it has a mean acid value of 60 mgKOH / g or more, but preferably contains an acrylic resin.

  Specific examples of the acrylic resin preferably include an acrylic resin and an acrylic polyol resin. As the acrylic resin, an acrylic resin having a (meth) acrylic acid monomer as a structural unit and an acrylic resin having a (meth) acrylic acid ester monomer as a structural unit are preferable. 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 ratio of the acrylic resin having the (meth) acrylic acid monomer as a structural 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 for 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, (meth ) Isobutyl acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, isobornyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) ) Acrylate and the like.

  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.

  Moreover, the acrylic resin which has a (meth) acrylic acid monomer as a structural unit, and the acrylic resin which has a (meth) acrylic acid ester monomer as a structural unit are block copolymers or random copolymers with other monomers, respectively. There may be. Other monomers are not particularly limited as long as they are copolymerizable with (meth) acrylic acid or (meth) acrylic acid ester. 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 Preferable examples include alicyclic olefin monomers such as pentadiene, ethylidene norbornene and norbornene, vinylcaprolactam, citraconic anhydride, maleimides such as N-phenylmaleimide, and vinyl ethers.

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

  Although it does not restrict | limit especially as a weight average molecular weight of acrylic resin, Preferably it is 10,000 or more, More preferably, it is 15,000 or more, More preferably, 20,000 or more is mentioned. The upper limit of the weight average molecular weight of the acrylic resin is usually about 50,000. In addition, the weight average molecular weight of the acrylic resin in this specification is a value obtained by measuring polystyrene as a standard substance by gel permeation chromatography.

  A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types. The average acid value and 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 in combination, the average acid value and the hydroxyl value can be suitably adjusted.

  Although it does not restrict | limit especially as the thickness of the anchor layer 3, For example, about 1-20 micrometers, Preferably about 1-10 micrometers is mentioned.

  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 obtained by dissolving or dispersing the thermoplastic resin for forming the anchor layer 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 ink jet printing.

[Surface protective layer 4]
For the purpose of enhancing the scratch resistance, weather resistance, etc. of the decorative resin molded product, the surface protective layer 4 is positioned on the outermost surface of the decorative resin molded product as necessary. It is a layer to be provided. 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. The surface protective layer 4 is also preferably formed from 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 films such as acrylic resins. Among these, it is particularly preferable to use acrylic resin films. . The surface protective layer 4 may be formed of, for example, one layer of an ionizing radiation curable resin or a resin film, or may be formed of two or more layers thereof. 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)
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, more preferably 1 to 1 μm. 30 μm may be mentioned. When satisfying the thickness in such a range, sufficient physical properties as a surface protective layer such as scratch resistance and weather resistance can be obtained, and ionizing radiation can be uniformly irradiated, so that it can be cured uniformly. It becomes possible, and it becomes economically advantageous. Moreover, when forming the surface protective layer 4 with a resin film, 25-1000 micrometers is mentioned, for example, Preferably about 50-200 micrometers is mentioned. 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, so that high followability can be obtained for a complicated three-dimensional shape such as an automobile interior application. it can. Thus, even if the decorative sheet of the present invention has a sufficiently high three-dimensional formability even when the thickness of the surface protective layer 4 is made thicker than the conventional one, the surface protective layer 4 has a particularly high film thickness. It is also useful as a decorative member for required members such as vehicle exterior parts.

(Formation of surface protective layer 4 when using ionizing radiation curable resin)
The surface protective layer 4 is formed, for example, by preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, applying it, and crosslinking and curing it. 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 pattern layer 5 and the primer layer 7, by the coating method mentioned later.

  In the present invention, the prepared coating liquid is a known coating such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat on the pattern layer 5 or the primer layer 7 so as to have the thickness. It is applied by a method, preferably a gravure coat, to form an uncured resin layer.

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

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

  The irradiation dose is preferably such that the crosslinking density of the surface protective layer 4 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

  Furthermore, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Can be used.

  When ultraviolet rays are used as the ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. 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.

  In addition, what is necessary is just to laminate | stack a resin film on the pattern layer 5, the primer layer 7, etc., when forming the surface protective layer 4 with a resin film. In addition, as a resin film, the resin film containing additives, such as a mat agent, and the resin film which surface-treated, such as sandblasting, can also be used.

[Primer layer 7]
The primer layer 7 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 7 can be formed of a resin.

  Although it does not restrict | limit especially as resin which forms the primer layer 7, 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 7, For example, about 0.1-10 micrometers, Preferably about 1-10 micrometers is mentioned. When the primer layer 7 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.

  The primer layer 7 is a resin that forms the primer layer 7, 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 5]
The pattern layer 5 is a layer provided as needed, for example, for the purpose of imparting decorativeness to the decorative sheet. From the viewpoint of a decorative sheet having higher brightness and excellent moldability, 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 picture layer 5, the picture layer 5 is dissolved in the solvent for forming the high-brightness ink layer 2, and the smoothness is lowered. The brightness of the is likely to decrease. Further, when the picture layer 5 is laminated on the high brightness ink layer 2, the high brightness ink layer 2 is dissolved in a solvent for forming the picture layer 5, and the smoothness is lowered. The brightness of the ink layer 2 tends to decrease.

  The pattern layer 5 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 5, 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 5 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 5 is also used in combination with a pattern pattern layer that expresses a pattern such as a wood grain pattern, and a solid surface 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 5, For example, about 1-30 micrometers, Preferably about 1-20 micrometers is mentioned.

  The pattern layer 5 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 5 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.

[Adhesive layer 6]
The adhesive layer 6 includes, for example, a decorative sheet 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 molded resin layer 9. It is a layer provided as necessary for the purpose of improving the adhesion between the molded resin layer 9 and the like. The resin that forms the adhesive layer 6 is not particularly limited as long as it can improve the adhesion between the interlayer of the decorative sheet and the decorative sheet and the molded resin layer 9, and the adhesiveness. A thermoplastic resin or a thermosetting 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 6 is not necessarily a necessary layer, it is assumed that the decorative sheet of the present invention is applied to a decorating method by sticking on a resin molded body prepared in advance, such as a vacuum press-bonding method described later. Is preferably provided on the surface of the decorative sheet that contacts the resin molded body. When used in the vacuum pressure bonding method, it is preferable to form the adhesive layer 6 by using a conventional resin that exhibits adhesiveness by pressurization or heating among the various resins described above.

  The thickness of the adhesive layer 6 is not particularly limited and may be appropriately set according to the position where the adhesive layer 6 is provided and the adjacent layer. For example, the thickness is about 0.1 to 30 μm, preferably about 0.5 to 20 μm. More preferably, about 1-8 micrometers is mentioned.

[Release layer 8]
The release layer 8 is provided on the transfer base material layer 1a as necessary in the decorative sheet of the second aspect described above, 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 peelability of the transfer base material layer 1a from the transfer layer 11.

  The release layer 8 may be a solid release layer covering the entire surface of the transfer base material layer 1a (entirely solid), or may be provided in a part. In general, a solid release layer is preferable in consideration of peelability.

  The release layer 8 includes a silicone resin, a fluorine resin, an acrylic resin (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 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 8 is composed of an acrylic-melamine resin alone or a composition containing 50% by mass or more of an 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 produced by laminating the above layers. In the present invention, in particular, after the anchor layer 3 is formed from a resin composition containing a thermoplastic resin having an average acid value of 60 mgKOH / g or more, the high-brightness ink layer 2 containing a pigment is laminated on the anchor layer 3. By adopting a manufacturing method including the step of performing, a decorative sheet having a high-brightness metallic design and excellent moldability can be obtained. As the details of this mechanism, for example, the one described above can be considered.

2. Sheet for producing a decorative sheet In the present invention, the decorative sheet as described above can also be produced using a sheet for producing 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 substrate layer 1a are laminated in this order, 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 average acid value of the thermoplastic resin contained in the anchor layer 3 is 60 mgKOH / g or more.

  About the composition of each layer which comprises the said sheet | seat, it is the same as that of the above. As the laminated structure of the sheet, for example, as shown in FIG. 8, the primer layer 7, the anchor layer 3, and the high layer are formed on the support 10 on which the transfer base material layer 1 a and the release layer 8 are laminated. A structure in which the luminance ink layer 2 is laminated in this order is exemplified. 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 necessary. As a laminated structure of the sheet for producing the decorative sheet of the present invention, a laminated structure in which a transfer base layer / release layer / primer layer / anchor layer / high brightness ink layer are laminated in this order; Examples include a layered structure in which layers / release layers / primer layers / picture layers / anchor layers / high-brightness ink layers are laminated in this order. FIG. 8 shows, as an embodiment of the laminated structure of the sheet for producing the decorative sheet in the present invention, the transfer base layer / release layer / primer layer / design layer / anchor layer / high-brightness ink layer in this order. 1 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 a support 10.

  The manufacturing method of the decorating sheet | seat of this invention using the sheet | seat for manufacturing such a decorating sheet is demonstrated, referring FIGS. 8-11.

  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 the lamination method, it is preferable to use hot pressing using a mirror plate or embossing using a mirror roll. Specifically, using a known hot press machine or embossing machine, the above-mentioned sheet and the resin film constituting the base material layer 1 are heated and softened, and pressed and bonded together in a stacked state. Thereby, a sheet as shown in FIG. 9 is obtained.

  Next, the support 10 is peeled 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. 10. Sheets laminated in order are obtained.

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

  In addition, the sheet | seat for manufacturing the decorating sheet | seat of this invention is the primer layer 7, the anchor layer 3, the high-intensity ink layer 2, etc. on the support body 10 which has the base material layer 1a for transfer, and the mold release layer 8. Can be manufactured by sequentially laminating.

3. Decorated resin molded product The decorated resin molded product of the present invention is formed by integrating a molded resin with the decorated sheet of the present invention. That is, the decorative resin molded product of the present invention is composed of a laminate in which a high-brightness ink layer containing a pigment and an anchor layer containing a thermoplastic resin are laminated on at least a molded resin layer. 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, if necessary, at least one layer such as the surface protective layer 4, the primer layer 7, the pattern layer 5, and the adhesive layer 6 may be further provided on the decorative sheet. . In the above-described first aspect as shown in FIGS. 3, 4, and 12, the base material layer 1 may be provided on the decorative resin molded product. Moreover, also in the above-mentioned 2nd aspect as FIG. 6 shows, the support body 10 containing the base material layer 1a for transcription | transfer may be provided in the decorative resin molded product (decoration of such a state) A resin molded product is also called a decorative resin molded product with a support). 3 is a cross-sectional view of a decorative resin molded product in which a molding resin is laminated on the decorative sheet shown in FIG. 1, and FIG. 4 is a diagram in which the molding resin is laminated on the decorative sheet shown in FIG. It is sectional drawing of the decorative resin molded product.

  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, when an ABS resin film is used as the base material layer 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 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 Vacuum forming from the mold side, and by preliminarily molding the decorative sheet by 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 material layer, 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 material layer 1 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 material layer 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 resin 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.

  In addition, in the 2nd aspect, it decorates by peeling and removing the support body 10 from the decorative resin molded product with a support body obtained by integrating a decorating sheet and molding resin by the above methods. A resin molded product is obtained. The step of peeling and removing the support 10 can be performed at an arbitrary time. For example, the support 10 can be peeled and removed at the same time as the obtained decorated resin molded product with the support is taken out of the molding apparatus. In addition, 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 it is not peeled off after the production of the decorative resin molded product with a support. The support may be peeled off at the time of use. By using in such a mode, it is possible to prevent the decorative resin molded product from being damaged due to rubbing during transportation.

  Since the decorative resin molded product of the present invention has a high-brightness metallic design and is formed of a highly moldable decorative sheet, 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 appliances such as television receivers 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 an Example and a comparative example, the average acid value of the thermoplastic resin contained in an anchor layer is the value measured based on prescription | regulation of JISK2501: 2003. Moreover, the hydroxyl value (OH value) of the thermoplastic resin contained in the anchor layer is a value measured in accordance with JIS K0070: 1992.

(Preparation of decorative sheet)
<Examples 1-4 and Comparative Examples 1-3>
An acrylic resin film (thickness: 75 μm) is used as a surface protective layer, and a pattern layer forming ink containing 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 resin shown in Tables 1 and 2 was 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 (flakes formed by pulverizing a metal thin film formed by vapor deposition, 100 parts by mass) and a vinyl chloride-vinyl acetate copolymer resin ( The high-brightness ink composition containing 100 parts by mass was dissolved in a solvent mainly containing methyl ethyl ketone and printed 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 high-brightness ink layer 2 μm). Next, an adhesive sheet made of polyester polyol was printed by gravure coating, and bonded to a base material layer (thickness 400 μm) made of ABS resin by dry lamination to obtain a decorative sheet. The layer structures of the decorative sheets of Examples 1 to 4 and Comparative Examples 1 to 3 are as shown in FIG. In Comparative Example 1, no anchor layer was provided.

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

(Evaluation of high brightness)
Luminance was evaluated by glossiness, and microgloss (60 °) manufactured by BYK Gardner was used for measurement.

(Processability evaluation)
After extending the decorative sheet 300% in one direction with a tensile tester, the surface of the decorative sheet was visually observed, and the moldability was evaluated according to the following criteria.
○: No cracks are generated in the decorative sheet Δ: Fine cracks are generated in the decorative sheet ×: Large cracks are generated in the decorative sheet

(Preparation of decorative sheet)
<Examples 5-8 and Comparative Examples 4-6>
As the base material layer, an ABS resin film (thickness: 400 μm) is used, and on the surface of the film, a pattern layer forming ink containing vinyl chloride-vinyl acetate copolymer resin / acrylic resin as a binder resin is printed by gravure coating. A layer was formed. Next, the resin shown in Tables 1 and 3 was 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 (flakes formed by pulverizing a metal thin film formed by vapor deposition, 100 parts by mass) and a vinyl chloride-vinyl acetate copolymer resin ( The high-brightness ink composition containing 100 parts by mass was dissolved in a solvent mainly containing methyl ethyl ketone and printed 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 high-brightness ink layer 2 μm). Next, a primer layer made of an 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 is printed on the surface of the primer layer as a surface protective layer by gravure coating so that the cured thickness of the resin composition is 10 μm, and this uncured resin The layer was irradiated with an electron beam having an acceleration 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 structures of the decorative sheets of Examples 5 to 8 and Comparative Examples 4 to 6 are 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 mass Hexafunctional urethane acrylate oligomer (weight average molecular weight 5,000): 30 parts by mass

  Next, for the decorative sheets obtained in Examples 5 to 8 and Comparative Examples 4 to 6, high brightness and moldability were evaluated in the same manner as described above. The results are shown in Table 3.

  As is clear from the results shown in Table 2 and Table 3, in the decorative sheets of Examples 1 to 8 in which the anchor layer containing a 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 luminance. Moreover, in these decorative sheets, cracks did not occur at all even when stretched by 300% (even when stretched by 3 times), and the moldability was high. On the other hand, in Comparative Examples 1 and 4 in which the anchor layer was not provided, although the moldability was excellent, the luminance was remarkably inferior as compared with Examples 1-8. 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 formability, but Example 1 The brightness was remarkably inferior to ˜8. Furthermore, in the decorative sheets of Comparative Examples 3 and 6 in which the anchor layer formed of a thermosetting resin was laminated so as to be adjacent to the high-brightness ink layer, although excellent in terms of luminance, Examples 1 to Compared to 8, the moldability was remarkably inferior. Further, for example, from the comparison between Examples 2 and 3, or the comparison between Examples 6 and 7, even if the acid value was the same, the brightness could be increased due to the high hydroxyl value.

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

Claims (12)

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,
The decorating sheet whose average acid value of the thermoplastic resin contained in the said anchor layer is 60 mgKOH / g or more.   The decorative sheet according to claim 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.   The decorative sheet according to claim 1 or 2, wherein a pattern layer is laminated so as not to be adjacent to the high brightness ink layer.   The decorative sheet according to any one of claims 1 to 3, further comprising a surface protective layer.   The decorative sheet according to any one of claims 1 to 4, further comprising a base material layer.   The decorative sheet according to any one of claims 1 to 3, wherein the high-brightness ink layer, the anchor layer, and a surface protective layer are laminated in this order.   The decorating 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 any one of claims 1 to 3, wherein the base material layer, the anchor layer, the high-luminance ink layer, and the surface protective layer are laminated in this order.   The decorative sheet according to any one of claims 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. A high-brightness ink layer containing a pigment, an anchor layer containing a thermoplastic resin, a primer layer, a release layer, and a peeling 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,
The sheet | seat for manufacturing a decorating sheet whose average acid value of the thermoplastic resin contained in the said anchor layer is 60 mgKOH / g or more. It is a manufacturing method of the decorating sheet in any one of Claims 1-9,
A decorative sheet comprising a step of laminating a high-brightness ink layer containing a pigment on the anchor layer after forming the anchor layer with a resin composition containing a thermoplastic resin having an average acid value of 60 mgKOH / g or more. Production method. At least, on the molded resin layer, consists of a laminate in which a high-brightness ink layer containing a pigment and an anchor layer formed of a resin composition containing a thermoplastic resin are adjacent to each other,
A decorative resin molded product in which an average acid value of a thermoplastic resin contained in the anchor layer is 60 mgKOH / g or more.