JP6205781B2 - Decorative sheet and decorative resin molded product - Google Patents

Description

  The present invention relates to a decorative sheet having a glittering design and excellent weather resistance. 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 the decorative sheet, a glitter ink layer containing a pearl pigment or the like may be provided on the base material layer in order to impart a glitter design (see, for example, Patent Document 1). As the pearl pigment contained in the glitter ink layer, for example, a pearl pigment coated with a scale-like substance such as mica with a metal oxide or the like is widely used.

  The decorative sheet is used as a surface material of a decorative resin molded product. For this reason, the decorative sheet is required to have high weather resistance against light and heat. However, when the glitter ink layer contains a pearl pigment, the metal oxide constituting the pearl pigment exhibits a photocatalytic action, so that the binder resin contained in the glitter ink layer is deteriorated, and the weather resistance of the decorative sheet is reduced. May decrease. As a method for improving the weather resistance of such a decorative sheet, for example, a method of blending a surface layer or the like with an ultraviolet absorber, a light stabilizer or the like can be mentioned (for example, see Patent Document 2).

  However, when a normally assumed amount of an ultraviolet absorber or the like is blended in the surface layer or the like, the decorative sheet containing a pearl pigment in the glitter ink layer may have insufficient weather resistance. On the other hand, when a large amount of an ultraviolet absorber or the like is blended in the surface layer or the like, there is a problem that the ultraviolet absorber or the like bleeds out with time.

JP-A-2005-14462 JP 2004-277725 A

  The main object of the present invention is to provide a decorative sheet that can suppress bleed-out even when the glitter ink layer contains a pearl pigment, has excellent temporal stability, and has high weather resistance.

  The present inventor has intensively studied to solve the above problems. As a result, the base material layer has at least a glittering ink layer and a heat ray shielding layer in this order, the glittering ink layer contains a pearl pigment, and the heat ray shielding layer contains a heat ray shielding agent. It has been found that the decorative sheet can suppress bleed-out even when the glitter ink layer contains a pearl pigment, increase the temporal stability, and improve the weather resistance of the decorative sheet. 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 decorative sheet used for molding a decorative resin molded product having an injection resin layer, a glitter ink layer, and a heat ray shielding layer in this order,
On the base material layer and the base material layer, at least the glitter ink layer and the heat ray shielding layer,
The glitter ink layer contains a pearl pigment,
The decoration sheet in which the said heat ray shielding layer contains a heat ray shielding agent.
Item 2. It is a decorative sheet used for insert molding,
Item 2. The decorative sheet according to Item 1, comprising at least the glitter ink layer and the heat ray shielding layer in this order on the base material layer.
Item 3. It is a decorative sheet used for simultaneous injection molding,
Item 2. The decorative sheet according to Item 1, comprising at least the heat ray shielding layer and the glitter ink layer in this order on the base material layer.
Item 4. Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the heat ray shielding agent is an inorganic heat ray shielding agent.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the heat ray shielding agent is at least one selected from the group consisting of antimony-doped tin oxide, tin-doped indium oxide, zinc oxide, and tungsten bronze.
Item 6. The amount of the heat ray-shielding agent of the heat ray shielding layer included in 1 m ² per when viewed the decorative sheet from the stacking direction, is 0.1 g / m ² or more, according to any one of claim 1-5 Decorative sheet.
Item 7. Any one of Items 1 to 6, wherein the glitter ink layer contains a binder resin, and the content of the pearl pigment in the glitter ink layer is 10 to 90 parts by mass with respect to 100 parts by mass of the binder resin. Decorative sheet according to crab.
Item 8. Item 8. The decorative sheet according to any one of Items 1 to 7, further comprising a metallic luster layer containing a metal pigment.
Item 9. Item 9. The decorative sheet according to any one of Items 1 to 8, wherein the glittering ink layer further contains a metal pigment.
Item 10. Item 10. The decorative sheet according to any one of Items 1 to 9, wherein the glittering ink layer contains a chlorine-based resin.
Item 11. Item 11. The decorative sheet according to Item 10, wherein the glittering ink layer further comprises a (meth) acrylic resin.
Item 12. Item 12. The addition according to Item 11, wherein the mass ratio of (meth) acrylic resin to chlorine-based resin ((meth) acrylic resin / chlorine-based resin) in the glitter ink layer is in the range of 3/7 to 8/2. Decorative sheet.
Item 13. The chlorinated resin is selected from the group consisting of polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, polypropylene chloride, and chlorinated polypropylene. Item 13. The decorative sheet according to any one of Items 10 to 12, which is at least one kind.
Item 14. Item 3. The decorative sheet according to Item 2, further comprising a protective layer on the glitter ink layer, wherein the protective layer is the heat ray shielding layer.
Item 15. Item 4. The decorative sheet according to Item 3, wherein a protective layer is provided between the base material layer and the glitter ink layer, and the protective layer is the heat ray shielding layer.
Item 16. Item 3. The decorative sheet according to Item 2, wherein a primer layer and a protective layer are provided in this order on the glitter ink layer, and at least one of the primer layer and the protective layer is the heat ray shielding layer.
Item 17. Between the base material layer and the glitter ink layer, a protective layer and a primer layer are sequentially provided from the base material layer side, and at least one of the protective layer and the primer layer is the heat ray shielding layer. Item 4. The decorative sheet according to item 3.
Item 18. Item 18. The decorative sheet according to Item 16 or 17, wherein at least one of the primer layer and the protective layer contains at least one of an ultraviolet absorber and a light stabilizer.
Item 19. Item 19. The decorative sheet according to any one of Items 14 to 18, wherein the protective layer is formed of a resin composition containing an ionizing radiation curable resin or a two-component curable resin.
Item 20. It has at least an injection resin layer, a glittering ink layer, and a heat ray shielding layer in this order,
The glitter ink layer contains a pearl pigment,
A decorative resin molded product in which the heat ray shielding layer contains a heat ray shielding agent.
Item 21. Item 21. The decorative resin molded product according to Item 20, which has a base material layer between the injection resin layer and the glitter ink layer.
Item 22. Item 21. The decorative resin molded product according to Item 20, which has a base material layer on the heat ray shielding layer.

  According to the decorative sheet of the present invention, even when the glittering ink layer contains a pearl pigment, it is possible to provide a decorative sheet that can suppress bleed out, has excellent temporal stability, and has high weather resistance. .

It is a schematic sectional drawing of an example of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating resin molded product which uses the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorating resin molded product which uses the decorating sheet of this invention.

1. Decorating sheet The decorating sheet of the present invention is a decorating sheet used for molding a decorated resin molded product having an injection resin layer, a glitter ink layer, and a heat ray shielding layer in this order. That is, the injection resin layer of the resin molded product is decorated by the glittering ink layer and the heat ray shielding layer included in the decorative sheet of the present invention, and the decorative resin molded product is obtained. The decorative sheet of the present invention has a base material layer and at least a glittering ink layer and a heat ray shielding layer on the base material layer, the glittering ink layer contains a pearl pigment, and the heat ray shielding layer comprises And a heat ray shielding agent. Hereinafter, the decorative sheet of the present invention, the decorative resin molded product using the decorative sheet, and the production methods thereof will be described in detail.

Laminated structure of decorative sheet The decorative sheet of the present invention has a laminated structure including at least a base material layer 1, a glittering ink layer 2, and a heat ray shielding layer 3. As described later, when the decorative sheet of the present invention is used for insert molding (hereinafter sometimes referred to as “decorative sheet for insert molding”), the base material layer 1 (hereinafter referred to as insert molding). The base material layer 1 of the decorative sheet is sometimes referred to as “insert-forming base material layer 1a”.) Is located on the glitter ink layer side. That is, in the insert molding decorative sheet, the insert molding substrate layer 1a, the glitter ink layer 2, and the heat ray shielding layer 3 are laminated in this order. When the insert molding decorative sheet is used for molding a decorative resin molded product, it is integrated with the resin molded product on the insert molding base material layer 1a side, so the insert molding base material layer 1a is a decorative resin molded product. Integrated with the product. On the other hand, when the decorative sheet of the present invention is used for simultaneous injection molding (hereinafter, sometimes referred to as “decorative sheet for simultaneous injection molding”), the base layer 1 (hereinafter referred to as “decorative sheet for simultaneous injection molding”). The base material layer 1 of the decorative sheet for simultaneous injection molding is sometimes referred to as “release base material layer 1b”.) Is located on the heat ray shielding layer 3 side. That is, in the decorative sheet for simultaneous injection molding, the glittering ink layer 2, the heat ray shielding layer 3, and the release base material layer 1b are laminated in this order. When a decorative sheet for simultaneous injection molding is used to mold a decorative resin molded product, it is integrated with the resin molded product on the glitter ink layer 2 side, and the decorative sheet is integrated as a decorative resin molded product. Then, the mold release base material layer 1b located on the outermost surface is peeled off from the decorative resin molded product.

  In the decorative sheet of the present invention, on the glitter ink layer 2, a protective layer 3a, a primer layer 3b, a pattern layer 3c, a transparent resin layer 3d, etc., which will be described later, are appropriately provided. At least one of the layers positioned above constitutes the heat ray shielding layer 3. For example, when only the protective layer 3a is provided on the glitter ink layer 2 except for the base material layer 1, in the decorative sheet of the present invention, the protective layer 3a includes a heat ray shielding agent, and the heat ray shielding layer. 3 For example, if the primer layer 3b and the protective layer 3a are provided on the glitter ink layer 2, at least one of the primer layer 3b and the protective layer 3a contains a heat ray shielding agent, Layer 3 is formed. Furthermore, for example, when the pattern layer 3c, the primer layer 3b, and the protective layer 3a are provided on the glitter ink layer 2, at least one of these layers contains a heat ray shielding agent, The shielding layer 3 is formed. That is, the heat ray shielding layer 3 may be a single layer or a multilayer.

  In the decorative sheet of the present invention, a metallic gloss layer 4 or the like may be provided under the glittering ink layer 2.

Composition of each layer forming the decorative sheet [base material layer 1]
The base material layer 1 is formed of a resin sheet (resin film) that plays a role as a support in the decorative sheet of the present invention. As will be described later, when the decorative sheet of the present invention is subjected to insert molding, the base material layer 1 (base material layer 1a for insert molding) in the decorative sheet has a glittering ink layer 2 and heat ray shielding. It is integrated with the injection resin layer 6 together with the layer 3 and the like to constitute a layer of a decorative resin molded product. Further, when the decorative sheet of the present invention is subjected to simultaneous injection molding, the base material layer 1 (base material layer 1b for release) is integrated with the injection resin layer 7. After that, it is peeled from the decorative resin molded product.

  The resin sheet used for the base material layer 1 is not particularly limited, and may be appropriately selected according to the three-dimensional moldability, compatibility with the injection resin, and the like. Preferably, a resin sheet made of a thermoplastic resin is used. Can be mentioned. Specific examples of the thermoplastic resin include polyolefin resins such as acrylonitrile-butadiene-styrene resin (hereinafter also referred to as “ABS resin”), acrylonitrile-styrene-acrylate resin, acrylic resin, polypropylene, polyethylene, and the like. , Polycarbonate resin, vinyl chloride resin, polyethylene terephthalate (PET) and the like. 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 resin sheets preferable as the insert molding base layer 1a and the release base layer 1b are as described later.

  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 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 sheet constituting the base material layer 1, and preferably a corona discharge treatment method from the viewpoints of effects and operability.

  The base material layer 1 may be subjected to a treatment such as forming a known adhesive layer.

  Furthermore, the base material layer 1 may be colored using a coloring agent or may not be colored. Moreover, the base material layer 1 may be any of colorless and transparent, colored and transparent, and translucent. Although it does not restrict | limit especially as a coloring agent used for the base material layer 1, Preferably the coloring agent which does not discolor also under the temperature conditions of 150 degreeC or more is mentioned, Specifically, the existing dry color, paste color, masterbatch resin Examples thereof include compositions.

  The thickness of the base material layer 1 is appropriately set according to the use of the decorative sheet and the like, as described later, for example, the thickness of the base material layer 1a for insert molding is usually about 50 to 1000 μm, and the mold release The thickness of the base material layer 1b for use is usually about 10 to 150 μm.

[Glossy ink layer 2]
The glitter ink layer 2 is a layer provided for the purpose of imparting glitter to the decorative sheet. In the present invention, the “shininess” of the decorative sheet means that the decorative sheet has a bright design.

  The glitter ink layer 2 includes a pearl pigment, a binder resin, and the like. The glitter ink layer 2 is formed using, for example, an ink composition for glitter ink layer, and imparts desired glitter to the decorative sheet. As such an ink composition, for example, a binder resin in which a colorant such as a pearl pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used. In the present invention, the pearl pigment means a pigment that gives a pearly luster. The pearl pigment is not particularly limited as long as it is a pigment capable of imparting a glittering design to the decorative sheet. For example, a known pearl pigment blended in the decorative sheet or the like can be used.

  As a pearl pigment, the particle | grains which contain a metal oxide in a surface part are mentioned, for example. Examples of such pearl pigments include pigments in which the surface of scaly particles such as mica is coated with a metal oxide. The metal oxide contained in the pearl pigment is not particularly limited as long as it can impart a glittering design to the decorative sheet. For example, oxidation of metals such as titanium, iron, zirconium, silicon, aluminum, and cerium is possible. Things. As a metal oxide, 1 type may be included independently and 2 or more types may be included. Specific examples of the pearl pigment preferably include titanium dioxide-coated mica, iron oxide-coated mica, mica coated with titanium dioxide and iron oxide, and the like.

  Although it does not restrict | limit especially as an average particle diameter of a pearl pigment, From a viewpoint of providing the glossiness excellent in the decorating sheet, about 1-500 micrometers normally, Preferably about 5-100 micrometers is mentioned. In the present invention, the average particle diameter of the pearl pigment means the median diameter of the volume-based particle size distribution measured by a laser diffraction scattering method.

  Although it does not restrict | limit especially as content of the pearl pigment in the glitter ink layer 2, Preferably it is about 10-90 mass parts with respect to 100 mass parts of binder resins in the glitter ink layer 2, More preferably, 50- About 80 parts by mass can be mentioned.

The binder resin is not particularly limited, and examples thereof include chlorine-based resins, (meth) acrylic resins, polyurethane resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins. May be chlorinated resin or (meth) acrylic resin. These binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.
In the present invention, “(meth) acryl” means “acryl or methacryl”, and other similar ones have the same meaning.

  When forming the glitter ink layer 2 by printing or the like, it is preferable that a chlorine-based resin is included as a binder resin of the ink composition for the glitter ink layer from the viewpoint of improving the transferability of the ink composition. When a chlorine-based resin is included as a binder resin, when transferring the ink composition to a layer adjacent to the glittering ink layer 2 by printing or the like, transfer failure is unlikely to occur, and the ink composition is transferred accurately. Can do. Since chlorine-based resins are likely to be deteriorated by light or heat, the use of a chlorine-based resin as a binder resin may reduce the weather resistance. However, in the present invention, by having the heat ray shielding layer 3, the weather resistance can be improved even in such a case.

  From the viewpoint of further improving the transferability of the ink composition for glittering ink layer, the binder resin is preferably a mixed resin of a (meth) acrylic resin and a chlorine resin. From the same viewpoint, the mass ratio of the (meth) acrylic resin to the chlorine resin in the binder resin is not particularly limited, but is preferably in the range of about 3/7 to 8/2, more preferably 5/5 to 5. The range is about 8/2, more preferably about 5/5 to 7/3.

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

  The glitter ink layer 2 may further contain a metal pigment. Although it does not restrict | limit especially as a metal pigment, For example, 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 powder.

  The average particle diameter of the metal pigment is not particularly limited, but is usually about 1 to 200 μm, preferably about 5 to 100 μm from the viewpoint of imparting excellent metallic luster to the decorative sheet. In addition, in this invention, the average particle diameter of a metal pigment means the median diameter of the volume reference | standard particle size distribution measured by the laser diffraction scattering method.

  When the glitter ink layer 2 contains a metal pigment, the content of the metal pigment in the glitter ink layer 2 is not particularly limited, but is preferably 100 parts by weight of the binder resin in the glitter ink layer 2. About 10-90 mass parts, More preferably, about 20-80 mass parts is mentioned.

  The thickness of the glitter ink layer 2 is not particularly limited, and for example, about 1 to 30 μm, preferably about 1 to 20 μm.

  The glitter ink layer 2 can be formed by printing on the layer adjacent to the glitter ink layer 2 using the ink composition for glitter ink layer. The printing method for forming the glitter 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 ink jet printing.

[Heat ray shielding layer 3]
The heat ray shielding layer 3 is a layer containing a heat ray shielding agent and having a function of shielding heat rays. The decorative sheet of the present invention is used such that the heat ray shielding layer 3 side is positioned on the surface side of the decorative resin molded product. As described above, the heat ray shielding layer 3 may be a single layer or a multilayer. For example, when the decorative sheet has only a protective layer 3a described later on the glitter ink layer 2, the protective layer 3a becomes the heat ray shielding layer 3, and the heat ray shielding layer 3 becomes a single layer. In addition, for example, even when a primer layer 3b and a protective layer 3a described later are provided on the glitter ink layer 2, and one of these layers includes a heat ray shielding agent, the heat ray shielding layer 3 is a single layer. On the other hand, when both the primer layer 3b and the protective layer 3a contain a heat ray shielding agent, the heat ray shielding layer 3 is a multilayer (two layers). Further, for example, when the glittering ink layer 2 has a pattern layer 3c, a primer layer 3b, and a protective layer 3a, which will be described later, and one of these layers contains a heat ray shielding agent, the heat ray shielding layer 3 is When it becomes a single layer and two of these layers contain a heat ray shielding agent, the heat ray shielding layer 3 becomes a multilayer (two layers), and when all these layers contain a heat ray shielding agent, the heat ray shielding layer 3 Becomes a multilayer (three layers).

  As described above, when the pearl pigment contained in the glittering ink layer 2 is irradiated with light, a photocatalytic action may occur, and the binder resin contained in the glittering ink layer 2 may be deteriorated. On the other hand, in the decorative sheet of the present invention, a heat ray shielding layer 3 containing a heat ray shielding agent is provided on the glittering ink layer 2. For this reason, the heat ray shielding agent absorbs light coming from the heat ray shielding layer 3 side of the decorative sheet, and the binder resin is deteriorated due to the photocatalytic action of the pearl pigment contained in the glittering ink layer 2 located under the heat ray shielding layer 3. Can be suppressed. In particular, the heat ray shielding agent absorbs near infrared light efficiently. For this reason, near-infrared light reaching the glittering ink layer 2 can be reduced. Therefore, the weather resistance of the decorative sheet can be effectively increased. Furthermore, in the decorative sheet of the present invention, since the heat resistance is enhanced by the heat ray shielding layer 3 containing the heat ray shielding agent, it is not necessary to use a large amount of an ultraviolet absorber or the like. Therefore, the bleed-out which arises in a decorating sheet can be suppressed and the temporal stability of a decorating sheet can be improved.

  The heat ray shielding agent is not particularly limited, and can be appropriately selected depending on, for example, functions performed by a protective layer 3a, a primer layer 3b, a transparent resin layer 3d, and the like described later that can be the heat ray shielding layer 3. From the viewpoint of effectively increasing the weather resistance of the decorative sheet, it is preferable to use an inorganic heat ray shielding agent, specifically, antimony-doped tin oxide, tin-doped indium oxide, zinc oxide, tungsten bronze, etc. More preferable examples include antimony-doped tin oxide, tin-doped indium oxide, and zinc oxide. Inorganic heat ray shielding agents are less prone to deterioration and deactivation over time, and therefore weather resistance can be maintained over a long period of time. A heat ray shielding agent may be used individually by 1 type, and may be used in combination of 2 or more types.

Moreover, as a quantity of the heat ray shielding agent in the heat ray shielding layer 3 contained per 1 m ² when the decorative sheet of the present invention is viewed from the stacking direction from the viewpoint of more effectively improving the weather resistance of the decorative sheet. , Preferably 0.1 g / m ² or more, more preferably 0.2 g / m ² or more, and still more preferably 0.3 g / m ² or more. If the amount of the heat ray shielding agent is too large, it may be colored and the design may change. Therefore, from the viewpoint of more effectively improving the weather resistance of the decorative sheet, the decorative sheet of the present invention is viewed from the lamination direction. As an upper limit of the amount of the heat ray shielding agent in the heat ray shielding layer 3 contained per 1 m ^{2 at} the time, for example, 2 g / m ² can be mentioned.

  As described above, in the decorative sheet of the present invention, at least one of the layers such as the protective layer 3a, the primer layer 3b, the pattern layer 3c, and the transparent resin layer 3d provided on the glitter ink layer 2 is a heat ray. The shielding layer 3 is formed. Furthermore, another layer such as an adhesive layer may be provided on the glitter ink layer 2, and the other layer may be the heat ray shielding layer 3. Hereinafter, the protective layer 3a, the primer layer 3b, the pattern layer 3c, and the transparent resin layer 3d that are provided on the glitter ink layer 2 and can be the heat ray shielding layer 3 will be described in detail.

[Protective layer 3a]
The protective layer 3a is located on the outermost surface of the decorative resin molded product when the decorative sheet of the present invention is used to form a decorative resin molded product, and is intended to improve surface properties such as scratch resistance It is a layer formed by. The protective layer 3a can be formed of a resin. Moreover, when the protective layer 3a contains a heat ray shielding agent, the protective layer 3 becomes the heat ray shielding layer 3. For example, in the decorative sheet, when the base layer 1 is excluded and there is only one layer provided on the glitter ink layer 2, the one layer is the protective layer 3a, and the protective layer 3a is a heat ray. The shielding layer 3 is formed. For example, when two layers of the primer layer 3 b and the protective layer 3 a are provided in this order on the glitter ink layer 2, at least one of the primer layer 3 b and the protective layer 3 a becomes the heat ray shielding layer 3. If a heat ray shielding agent is contained in both the primer layer 3b and the protective layer 3a, both layers become the heat ray shielding layer 3.

  When the heat ray shielding layer 3 in the decorative sheet is a single layer only of the protective layer 3a, the content of the heat ray shielding agent in the protective layer 3a is not particularly limited, but it is a viewpoint that effectively enhances the weather resistance of the decorative sheet. Is preferably 10 parts by mass or more, more preferably 15 parts by mass or more with respect to 100 parts by mass of the resin in the protective layer 3a. In addition, when there is too much quantity of a heat ray shielding agent, since it may color and a design may change, as an upper limit of the heat ray shielding agent in the protective layer 3a, it is 20 mass parts with respect to 100 mass parts of resin, for example. Is mentioned.

  Further, in the decorative sheet, when the heat ray shielding layer 3 is a multilayer, and in addition to the protective layer 3a, the primer layer 3b and the like are also the heat ray shielding layer 3, the content of the heat ray shielding agent in the protective layer 3a is: Although not particularly limited, from the viewpoint of effectively increasing the weather resistance of the decorative sheet, the amount is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the resin in the protective layer 3a. Can be mentioned. In addition, as an upper limit of the heat ray shielding agent in the protective layer 3a, 20 mass parts is mentioned with respect to 100 mass parts of resin, for example.

  From the viewpoint of more effectively increasing the weather resistance of the decorative sheet, it is preferable that the protective layer 3a contains at least one of an ultraviolet absorber and a light stabilizer. It does not restrict | limit especially as a ultraviolet absorber, For example, a well-known ultraviolet absorber can be used. The ultraviolet absorber may be either inorganic or organic. As the inorganic ultraviolet absorber, for example, titanium dioxide, cerium oxide, zinc oxide or the like having an average particle diameter of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, a benzotriazole type, a triazine type, a benzophenone type etc. can be used, for example. Examples of the triazole group include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, and 3- [3 of polyethylene glycol. -(Benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester and the like.

  Examples of the triazine series include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- [4 -[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis [ 2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl)] Oki Ci] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like are preferable, and examples of the benzophenone series include 2,4-dihydroxybenzophenone, 2 2, 2 ', 4-trihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and the like.

  Moreover, the polymer of the reactive ultraviolet absorber which has polymerizable groups, such as a (meth) acryloyl group, can also be contained as a ultraviolet absorber. An ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more types.

  Although content in particular of the ultraviolet absorber in the protective layer 3a is not restrict | limited, From a viewpoint of improving the weather resistance of a decorating sheet effectively, Preferably it is 0.00 with respect to 100 mass parts of resin in the protective layer 3a. 5 mass parts or more, More preferably, 1 mass part or more is mentioned. If the amount of the ultraviolet absorber is too large, bleeding out may occur. Therefore, the upper limit of the ultraviolet absorber in the protective layer 3a is preferably 9 parts by mass with respect to 100 parts by mass of the resin. More preferably, 7 mass parts is mentioned.

  The light stabilizer is not particularly limited, and for example, a known light stabilizer can be used. The light stabilizer is preferably a hindered amine light stabilizer, specifically 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate bis (1 , 2,2,6,6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4) -Piperidyl) -1,2,3,4-butanetetracarboxylate and the like. A light stabilizer may be used individually by 1 type and may be used in combination of 2 or more type.

  The content of the light stabilizer in the protective layer 3a is not particularly limited, but is preferably 1 with respect to 100 parts by mass of the resin in the protective layer 3a from the viewpoint of effectively increasing the weather resistance of the decorative sheet. Part by mass or more, more preferably 2 parts by mass or more. In addition, since bleeding out may occur when the amount of the light stabilizer is too large, the upper limit value of the light stabilizer in the protective layer 3a is preferably 9 parts by weight with respect to 100 parts by weight of the resin. Parts, more preferably 7 parts by mass.

  The resin for forming the protective layer 3a is not particularly limited, and examples thereof include an ionizing radiation curable resin and a two-component curable resin from the viewpoint of ensuring surface properties such as scratch resistance. Further, the ionizing radiation curable resin and the two-component curable resin may be used in combination, or may be used in combination with other resins.

  Examples of the two-component curable resin that forms the protective layer 3a include known resins such as urethane resin, (meth) acrylic resin, and epoxy resin.

  The ionizing radiation curable resin suitably used for forming the protective layer 3a is a resin that crosslinks and cures when irradiated with ionizing radiation, and specifically, a polymerizable unsaturated bond or epoxy in the molecule. What mixed suitably at least 1 sort (s) among the prepolymer which has group, an oligomer, a monomer, etc. is mentioned. 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. Therefore, it is suitable for forming the protective layer 3a. used.

  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 can be obtained, for example, by esterifying a polycarbonate polyol with (meth) acrylic acid. 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 polyisocyanate 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. These oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  These ionizing radiation curable resins may be used alone or in combination of two or more.

  Among these ionizing radiation curable resins, polycarbonate (meth) acrylate and acrylic silicone (meth) acrylate are preferably used from the viewpoint of further improving the weather resistance of the decorative sheet.

(Other additives that can be included in the protective layer 3a)
Various additives can be blended in the resin forming the protective layer 3a according to desired physical properties to be provided in the protective layer 3a. Examples of the additive include an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, and a filler. , Solvent, colorant and the like. These additives can be appropriately selected from those commonly used.

(Method for forming protective layer 3a)
When the protective layer 3a is formed of a two-component curable resin, the protective layer 3a can be formed by the same formation method as the primer layer 3b described later.

  Further, when the protective layer 3a is formed of an ionizing radiation curable resin, the protective layer 3a is formed by, for example, preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, and applying the composition. This is performed by crosslinking and curing. In addition, the viscosity of ionizing radiation curable resin composition should just be a viscosity which can form a non-hardened resin layer on an adjacent layer with the application | coating system mentioned later. In the present invention, the prepared coating solution is a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating on the layer adjacent to the protective layer 3a so as to have the thickness described above. Preferably, it is applied 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 and ultraviolet rays to cure the uncured resin layer, thereby forming the protective layer 3a. 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 is higher. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the protective layer 3a, the transmission depth of the electron beam and the protective layer 3a are increased. The acceleration voltage is selected so that the thicknesses of the two are substantially equal. Thereby, irradiation of the extra electron beam to the layer located under the protective layer 3a 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 protective layer 3a 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. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. Can be used. When ultraviolet rays are used as the ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet ray source is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

  By adding various additives to the protective layer 3a, 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, an infrared shielding coating function, etc. You may perform the process which provides this function.

  Although there is no restriction | limiting in particular about the thickness of the protective layer 3a, For example, about 1-1000 micrometers, Preferably it is about 1-50 micrometers, More preferably, about 1-30 micrometers is mentioned. When the thickness in such a range is satisfied, sufficient physical properties as a protective layer such as scratch resistance and weather resistance can be obtained. In addition, if the protective layer 3a is formed of an ionizing radiation curable resin, the ionizing radiation curable resin composition can be uniformly irradiated with ionizing radiation and can be cured uniformly. It becomes economically advantageous. Furthermore, when the thickness of the protective layer 3a after curing satisfies the above range, the three-dimensional formability of the decorative sheet is further improved, so that it has high followability to complicated three-dimensional shapes such as automotive interior applications. Can be obtained. As described above, the decorative sheet of the present invention requires sufficiently high three-dimensional formability because the sufficiently high three-dimensional formability can be obtained even when the thickness of the protective layer 3a is larger than that of the conventional one. It is also useful as a decorative sheet for a member to be used, such as a vehicle exterior part.

[Primer layer 3b]
The primer layer 3b is a layer included as necessary between the glitter ink layer 2 and the protective layer 3a for the purpose of improving the adhesion between the protective layer 3a and the layer located therebelow. . The primer layer 3b can be formed of a resin. Further, when the primer layer 3 b includes a heat ray shielding agent, the primer layer 3 b becomes the heat ray shielding layer 3.

  In the decorative sheet, when the heat ray shielding layer 3 is a multilayer and the protective layer 3a is also the heat ray shielding layer 3 in addition to the primer layer 3b, the content of the heat ray shielding agent in the primer layer 3b is particularly limited. However, from the viewpoint of effectively increasing the weather resistance of the decorative sheet, the amount is preferably 1 part by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass of the resin in the primer layer 3b. In addition, as an upper limit of the heat ray shielding agent in the primer layer 3b, 20 mass parts is mentioned with respect to 100 mass parts of resin, for example.

  Although it does not restrict | limit especially as resin which forms the primer layer 3b, For example, a urethane resin, a (meth) acryl resin, a (meth) acryl-urethane copolymer resin, a polyester resin, a butyral resin etc. are mentioned. Among these resins, a urethane resin, a (meth) acrylic resin, and a (meth) acrylic-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 (meth) 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 Examples include copolymers of esters and other monomers. 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 (meth) acrylic resins may be used alone or in combination of two or more.

  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.

  When the decorative sheet has the primer layer 3b, the primer layer 3b contains at least one of an ultraviolet absorber and a light stabilizer from the viewpoint of more effectively increasing the weather resistance of the decorative sheet. It is preferable. Although it does not restrict | limit especially as an ultraviolet absorber and light stabilizer which may be contained in the primer layer 3b, For example, what was illustrated by said protective layer 3a is mentioned.

  Further, when the primer layer 3b contains an ultraviolet absorber, the content of the ultraviolet absorber in the primer layer 3b is not particularly limited, but from the viewpoint of effectively improving the weather resistance of the decorative sheet, The amount is preferably 1 part by mass or more, more preferably 3 parts by mass or more with respect to 100 parts by mass of the resin. If the amount of the UV absorber is too large, bleeding out may occur. Therefore, the upper limit of the UV absorber of the primer layer 3b is preferably 9 parts by weight with respect to 100 parts by weight of the resin. Preferably 7 mass parts is mentioned. When the primer layer 3b contains a light stabilizer, the content of the light stabilizer in the primer layer 3b is not particularly limited, but from the viewpoint of effectively improving the weather resistance of the decorative sheet, The amount is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the resin. In addition, since bleeding out may occur when the amount of the light stabilizer is too large, the upper limit value of the light stabilizer of the primer layer 3b is preferably 9 parts by weight with respect to 100 parts by weight of the resin. More preferably, 7 mass parts is mentioned.

  Although it does not restrict | limit especially about the thickness of the primer layer 3b, For example, about 0.1-10 micrometers, Preferably about 1-10 micrometers is mentioned. When the primer layer 3b satisfies such a thickness, the weather resistance of the decorative sheet can be further increased, and cracking, breakage, whitening and the like of the protective layer 3a can be effectively suppressed.

  Primer layer 3b is a resin that forms primer layer 3b, 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 3c]
The pattern layer 3c is a layer provided on the glittering ink layer 2 as necessary, for example, for the purpose of imparting decorativeness to the decorative sheet. Moreover, when the pattern layer 3c contains a heat ray shielding agent, the pattern layer 3c becomes the heat ray shielding layer 3.

  When the heat ray shielding layer 3 in the decorative sheet is a single layer composed only of the pattern layer 3c, the content of the heat ray shielding agent in the pattern layer 3c is not particularly limited, but the viewpoint of effectively enhancing the weather resistance of the decorative sheet. Is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the resin in the pattern layer 3c. In addition, when there is too much quantity of a heat ray shielding agent, since it may color and a design may change, as an upper limit of the heat ray shielding agent in the pattern layer 3c, it is 20 mass parts with respect to 100 mass parts of resin, for example. Is mentioned.

  Further, in the decorative sheet, when the heat ray shielding layer 3 is a multilayer, and in addition to the pattern layer 3c, the protective layer 3a, the primer layer 3b, and the like are also the heat ray shielding layer 3, the heat ray shielding agent in the pattern layer 3c Although content in particular is not restrict | limited, From a viewpoint of improving the weather resistance of a decorating sheet effectively, Preferably it is 0.5 mass part or more with respect to 100 mass parts of resin in the pattern layer 3c, More preferably, it is 1 More than mass part is mentioned. In addition, as an upper limit of the heat ray shielding agent in the pattern layer 3c, 20 mass parts is mentioned with respect to 100 mass parts of resin, for example.

  The pattern layer 3c 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 3c, a binder resin, a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like are appropriately mixed. Is used.

  Although it does not restrict | limit especially as binder resin of the ink composition for pattern layers, For example, the thing similar to binder resin illustrated by the glittering ink layer 2 is mentioned. The binder resin of the pattern layer ink composition preferably contains a chlorine-based resin for the same reason as the glitter ink layer 2. Examples of the chlorine-based resin include those similar to the glitter ink layer 2. The binder resin is preferably a mixed resin of a (meth) acrylic resin and a chlorine resin similar to the glitter ink layer 2.

  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 3c is not particularly limited, but for example, a stone pattern, a texture pattern or a cloth-like pattern imitating the surface of a rock such as a wood 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. In addition, the pattern layer 3c is used also in combination with the pattern pattern layer expressing patterns, such as a grain pattern, and the whole surface solid layer. The entire solid layer is usually used as a concealing layer, a colored layer, a colored concealing layer, or the like.

  Although it does not restrict | limit especially as thickness of the pattern layer 3c, For example, about 1-30 micrometers, Preferably about 1-20 micrometers is mentioned.

  The pattern layer 3c is formed, for example, by printing with a pattern layer ink composition so that a desired pattern is obtained. The printing method for forming the pattern layer 3c 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.

[Transparent resin layer 3d]
The transparent resin layer 3d is for the purpose of improving the chemical resistance and scratch resistance of the decorative sheet. For example, when the primer layer 3 is provided between the glitter ink layer 2 and the protective layer 4, the glitter ink layer 2 is provided. And a primer layer 3 as needed. When the transparent resin layer 3d contains a heat ray shielding agent, the transparent resin layer 3d becomes the heat ray shielding layer 3.

  When the heat ray shielding layer 3 in the decorative sheet is a single layer composed only of the transparent resin layer 3d, the content of the heat ray shielding agent in the transparent resin layer 3d is not particularly limited, but the weather resistance of the decorative sheet is effectively improved. From the viewpoint of increasing, the amount is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the resin in the transparent resin layer 3d. If the amount of the heat ray shielding agent is too large, the design may change due to coloring. Therefore, the upper limit value of the heat ray shielding agent in the transparent resin layer 3d is, for example, 20 masses with respect to 100 parts by mass of the resin. Part.

  Further, in the decorative sheet, when the heat ray shielding layer 3 is a multilayer and the protective layer 3a, the primer layer 3b, etc. are also the heat ray shielding layer 3 in addition to the transparent resin layer 3d, the heat ray shielding in the transparent resin layer 3d is performed. The content of the agent is not particularly limited, but from the viewpoint of effectively increasing the weather resistance of the decorative sheet, it is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the resin in the transparent resin layer 3d. Preferably 1 mass part or more is mentioned. In addition, as an upper limit of the heat ray shielding agent in 3 d of transparent resin layers, 20 mass parts is mentioned with respect to 100 mass parts of resin, for example.

  The resin component for forming the transparent resin layer 3d is appropriately selected according to transparency, three-dimensional moldability, shape stability, chemical resistance, etc., but a thermoplastic resin is usually used. The thermoplastic resin is not particularly limited, and examples thereof include acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, ABS resins, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and vinyl chloride resins. Etc. are used. Among these thermoplastic resins, from the viewpoint of chemical resistance, scratch resistance, etc., preferably acrylic resin, polyolefin resin, polycarbonate resin, polyester resin; more preferably acrylic resin, polyester resin; more preferably polyester. Resin.

  When the decorative sheet has the transparent resin layer 3d, from the viewpoint of increasing the weather resistance of the decorative sheet more effectively, the transparent resin layer 3d contains at least one of an ultraviolet absorber and a light stabilizer. It is preferable. Although it does not restrict | limit especially as an ultraviolet absorber and light stabilizer which can be contained in the transparent resin layer 3d, For example, what was illustrated by said protective layer 3a is mentioned.

  In addition, when the transparent resin layer 3d contains an ultraviolet absorber, the content of the ultraviolet absorber in the transparent resin layer 3d is not particularly limited. However, from the viewpoint of effectively improving the weather resistance of the decorative sheet, the transparent resin layer 3d is transparent resin. Preferably it is 1 mass part or more with respect to 100 mass parts of resin in the layer 3d, More preferably, 2 mass parts or more is mentioned. In addition, since bleeding out may occur when there is too much quantity of a ultraviolet absorber, as an upper limit of the ultraviolet absorber in the transparent resin layer 3d, 10 mass parts is mentioned with respect to 100 mass parts of resin. It is done. When the transparent resin layer 3d contains a light stabilizer, the content of the light stabilizer in the transparent resin layer 3d is not particularly limited, but from the viewpoint of effectively improving the weather resistance of the decorative sheet, the transparent resin layer 3d is transparent resin layer 3d. Preferably it is 1 mass part or more with respect to 100 mass parts of resin in the layer 3d, More preferably, 2 mass parts or more is mentioned. If the amount of the light stabilizer is too large, bleeding out may occur. Therefore, the upper limit of the light stabilizer in the transparent resin layer 3d is 10 parts by weight with respect to 100 parts by weight of the resin. Can be mentioned.

  The transparent resin layer 3d is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides as necessary in order to improve the adhesion with other layers that are in contact with each other. May be. These physical or chemical surface treatments are the same as the surface treatments applied to the base material layer 1.

  Although there is no restriction | limiting in particular about the thickness of 3 d of transparent resin layers, For example, about 10-200 micrometers, Preferably about 15-150 micrometers is mentioned.

  The transparent resin layer 3d may be laminated via an adhesive or may be laminated directly without using an adhesive. When laminating via an adhesive, examples of the adhesive used include polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin, polyamide resin, polyolefin resin, polyvinyl acetate resin, cellulose resin, ( (Meth) acrylic resin, polyimide resin, amino resin, rubber, silicon resin and the like. Moreover, when laminating | stacking without using an adhesive agent, it can carry out by methods, such as an extrusion method, a sand lamination method, and a thermal lamination method.

[Glossy metallic layer 4]
The metallic gloss layer 4 is a layer provided as necessary for the purpose of imparting a metallic gloss design to the decorative sheet. The metallic gloss layer 4 can be provided, for example, at a position in contact with the glitter ink layer 2.

  The metallic gloss layer 4 is formed using, for example, an ink composition for a metallic gloss layer, and imparts a metallic gloss design to the decorative sheet. As such an ink composition, a binder resin in which a colorant such as a metal pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used.

  As a metallic pigment contained in the metallic luster layer 4, the same thing as said metallic pigment used for the glittering ink layer 2 as needed can be illustrated. In the conventional decorative sheet, when a metallic gloss layer is provided, the light reflected by the metallic pigment contained in the metallic gloss layer causes deterioration of the binder resin contained in the metallic gloss layer and the glitter ink layer. There is a problem of further promotion. On the other hand, in the decorative sheet of the present invention, the heat ray shielding layer 3 is provided on the glittering ink layer 2, and therefore, when the metallic gloss layer 4 is provided, the glittering property as described above. Even when the ink layer 2 contains a metal pigment, the weather resistance of the decorative sheet can be enhanced.

  Although it does not restrict | limit especially as content of the metal pigment in the metallic luster layer 4, Preferably it is about 10-90 mass parts with respect to 100 mass parts of binder resins in the metallic luster layer 4, More preferably, it is 20-80 masses. About a part.

  Although it does not restrict | limit especially as binder resin of the ink composition for metallic luster layers, For example, the thing similar to binder resin illustrated by the glittering ink layer 2 is mentioned. In addition, the binder resin of the metallic gloss layer ink composition preferably contains a chlorine-based resin for the same reason as the glitter ink layer 2. Examples of the chlorine-based resin include those similar to the glitter ink layer 2. The binder resin is preferably a mixed resin of a (meth) acrylic resin and a chlorine resin similar to the glitter ink layer 2.

  Although it does not restrict | limit especially as thickness of the metallic luster layer 4, For example, about 1-30 micrometers, Preferably about 1-20 micrometers is mentioned.

  The metallic gloss layer 4 is formed by printing on the base material layer 1 etc. using the metallic gloss layer ink composition. Examples of the printing method for forming the metallic gloss layer 4 include the same method as that for the glitter ink layer 2.

  The decorative sheet of the present invention can be laminated on the injection resin layer 7 to decorate a resin molded product, for example, by being subjected to insert molding or injection molding simultaneous decoration described later. Hereinafter, among the decorative sheets of the present invention, a decorative sheet for insert molding used for insert molding and a decorative sheet for simultaneous injection molding used for simultaneous injection molding will be described in detail.

Insert molding decorative sheet In the present invention, the insert molding decorative sheet has at least the glitter ink layer 2 and the heat ray shielding layer 3 in this order on the insert molding substrate layer 1a. That is, the protective layer 3a, the primer layer 3b, the transparent resin layer 3c, and the like are appropriately provided on the glitter ink layer 2 of the insert molding decorative sheet. At least one layer among the positioned layers constitutes the heat ray shielding layer 3.

  As an example of a laminated structure of a decorative sheet for insert molding, a laminated structure in which a base layer for insert molding / a glittering ink layer / a protective layer is laminated in order and the protective layer is a heat ray shielding layer; Laminated ink layer / primer layer / protective layer are laminated in order, and a laminated structure in which at least one of the primer layer and the protective layer is a heat ray shielding layer; insert molding base layer / brilliant ink layer / design layer / protective layer Laminate structure in which at least one of the picture layer and the protective layer is a heat ray shielding layer; a base layer for insert molding / a glittering ink layer / a picture layer / a primer layer / a protective layer are laminated in order, the picture layer and the primer A laminated structure in which at least one of the layers and the protective layer is a heat ray shielding layer; a base layer for insert molding / a metallic gloss layer / a glittering ink layer / a protective layer are laminated in order, and the protective layer is a heat ray shield Laminated structure: insert molding base layer / metal gloss layer / bright ink layer / primer layer / protective layer are laminated in order, and at least one of the protective layer and primer layer is a heat ray shielding layer; insert molding For example, a laminated structure in which a substrate layer for metal / a metallic gloss layer / a glittering ink layer / a pattern layer / a primer layer / a protective layer are sequentially stacked, and at least one of the protective layer, the primer layer, and the pattern layer is a heat ray shielding layer Can be mentioned. FIG. 1 is a schematic view of a decorative sheet in which a base layer for insert molding / a glittering ink layer / a protective layer is sequentially laminated, and the protective layer is a heat ray shielding layer, as one aspect of the laminated structure of the decorative sheet of the present invention. A cross-sectional view is shown. In FIG. 2, as one aspect of the laminated structure of the decorative sheet of the present invention, the base layer for insert molding / the glitter ink layer / the primer layer / the protective layer are laminated in order, and both the primer layer and the protective layer are heated. The schematic sectional drawing of the decorating sheet which is a shielding layer is shown. In FIG. 3, as an aspect of the laminated structure of the decorative sheet of the present invention, a base layer for insert molding / a glittering ink layer / a pattern layer / a primer layer / a protective layer are sequentially laminated, and the protective layer and the primer layer are heat rays. The schematic sectional drawing of the decorating sheet which is a shielding layer is shown. In FIG. 4, as an aspect of the laminated structure of the decorative sheet of the present invention, a base layer for insert molding / a metallic gloss layer / a glittering ink layer / a pattern layer / a primer layer / a protective layer are laminated in order, The schematic sectional drawing of the decorating sheet whose primer layer is a heat ray shielding layer is shown.

[Substrate layer 1a for insert molding]
As shown in FIG. 5, for example, the insert molding base material layer 1 a included in the insert molding decorative sheet is a decorative resin molded product together with the injection resin layer 7, the glitter ink layer 2, and the heat ray shielding layer 3. Integrated. From the viewpoint of improving the three-dimensional formability in insert molding, the insert molding substrate layer 1a is preferably formed of an ABS resin among the resins forming the substrate layer 1. Moreover, the thickness of the base material layer 1a for insert molding is suitably set according to the use etc. of the decorative sheet for insert molding, and is about 50-1000 micrometers normally, Preferably it is about 100-700 micrometers, More preferably, it is about 100-500 micrometers. Is mentioned. If the thickness of the base material layer 1a for insert molding is within the above range, the decorative sheet for insert molding can be provided with more excellent surface properties, three-dimensional formability and design properties, and printing workability ( (Productivity) is also improved, which is advantageous from the viewpoint of cost.

(Method for manufacturing decorative sheet for insert molding)
The decorative sheet for insert molding can be manufactured as follows, for example. First, the ink composition for glitter ink layer that forms the glitter ink layer 2 is applied on one surface of the resin film constituting the insert molding substrate layer 1a, and the insert molding substrate layer is formed. The glitter ink layer 2 is formed on 1a. Application | coating of the ink composition for glittering ink layers can be performed by gravure printing etc., for example. Next, a decorative sheet for insert molding is obtained by laminating layers such as the protective layer 3a, the primer layer 3b, and the transparent resin layer 3c on the glitter ink layer 2 by the above-described methods.

In the present invention, the decorative sheet for simultaneous injection-molding decoration is the above-mentioned base material layer 1 (hereinafter referred to as “release” from the base material layer 1 of the decorative sheet for simultaneous injection-molding decoration). And at least the heat ray shielding layer 3 and the glitter ink layer 2 in this order. Between the release substrate layer and the glitter ink layer 2, the protective layer 3a, the primer layer 3b, the transparent resin layer 3c and the like are appropriately provided in this order from the release substrate layer side. At least one of the layers located on the release base layer and the glitter ink layer 2 constitutes the heat ray shielding layer 3.

  As a preferred example of the laminated structure of the decorative sheet for simultaneous injection molding, a laminated structure in which a glittering ink layer / protective layer / release substrate layer are laminated in order, and the protective layer is a heat ray shielding layer; glittering ink Layer / primer layer / protective layer / release substrate layer are laminated in order, and at least one of the primer layer and the protective layer is a heat ray shielding layer; glitter ink layer / design layer / protective layer / release A base material layer is laminated in order, and a laminated structure in which at least one of the picture layer and the protective layer is a heat ray shielding layer; a glittering ink layer / picture layer / primer layer / protective layer / mold release base material layer is laminated in order, Laminated structure in which at least one of the pattern layer, the primer layer, and the protective layer is a heat ray shielding layer; a metallic gloss layer / brilliant ink layer / protective layer / release substrate layer are laminated in order, and the protective layer is heat ray shielded Layered structure; metallic luster layer / brightness in Layer / primer layer / protective layer / releasing substrate layer are laminated in order, and a laminated structure in which at least one of the protective layer and the primer layer is a heat ray shielding layer; metallic luster layer / brilliant ink layer / design layer / primer layer Examples include a laminated structure in which / protective layer / release substrate layer is laminated in order, and at least one of the protective layer, the primer layer, and the pattern layer is a heat ray shielding layer. Further, as a preferable laminated structure, a laminated structure in which a release layer is provided between the release base material layer and the protective layer can also be mentioned. FIG. 6 is a schematic view of a decorative sheet in which a glittering ink layer / protective layer / release base material layer is sequentially laminated, and the protective layer is a heat ray shielding layer, as one aspect of the laminated structure of the decorative sheet of the present invention. A cross-sectional view is shown. In FIG. 7, as one aspect of the laminated structure of the decorative sheet of the present invention, a metallic gloss layer / bright ink layer / design layer / primer layer / protective layer / release layer / release substrate layer are sequentially laminated. The schematic sectional drawing of the decorating sheet | seat whose protective layer and primer layer are heat ray shielding layers is shown.

[Release Base Material Layer 1b]
The mold release base material layer 1b included in the decorative sheet for simultaneous injection molding decorating is integrated with the injection resin layer 7 by simultaneous injection molding decorating, as described later, and then released from the resin molded product. . That is, in the decorative resin molded product, the release base material layer 1 b is located on the heat ray shielding layer 3. In addition to the three-dimensional moldability in the simultaneous injection molding, from the viewpoint of enhancing the peelability from the decorative resin molded product, the release base material layer 1b is the resin that forms the base material layer 1, It is preferably formed of a polyester resin.

  In the present invention, the polyester resin refers to a polymer containing an ester group obtained by polycondensation from a polyvalent carboxylic acid and a polyhydric alcohol. Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, decanedicarboxylic acid, azelaic acid, dodecadicarboxylic acid, and cyclohexanedicarboxylic acid. Polyhydric alcohols include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentylglycol, 1,4-cyclohexanedimethanol, decanediol, 2-ethyl-butyl-1-propanediol, and bisphenol. A etc. are mentioned. Furthermore, the polyester resin used in the present invention may be a copolymer of three or more types of polycarboxylic acid or polyhydric alcohol, and is a copolymer with a monomer or polymer such as diethylene glycol, triethylene glycol, or polyethylene glycol. There may be.

  Preferred examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). Polyethylene terephthalate (PET) is particularly preferable in terms of heat resistance and dimensional stability. . The polyester resin may be a homopolymer, a copolymer, or a copolymer obtained by copolymerizing a third component. For example, a polyester resin having polyethylene terephthalate, which is generally excellent in heat resistance and dimensional stability as a main component (usually 90 mol% or more, preferably 95 mol% or more), and polybutylene terephthalate, which is generally excellent in moldability, as a main component (usually 90 mol%). Mol% or more, preferably 95 mol% or more). The blending ratio may be appropriately selected depending on the dynamic elastic modulus of the obtained film, and is usually about 70/30 to 95/5, preferably about 75/25 to 85/15. Since the polyester resin blended in this way is excellent in heat resistance, dimensional stability, and moldability, it can be suitably used as the base sheet of the present invention.

  The polyester resin preferably contains fine particles for the purpose of improving workability. Fine particles include inorganic particles such as calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, aluminum oxide, silicon oxide and kaolin, organic particles made of acrylic resin, and internal precipitation particles. And so on. The average particle diameter of the fine particles is not particularly limited, and may be about 0.01 to 5.0 μm, preferably about 0.05 to 3.0 μm. Moreover, it does not restrict | limit especially as content of the microparticles | fine-particles in a polyester-type resin, For example, about 0.01-5.0 mass%, Preferably about 0.1-1.0 mass% is mentioned. Moreover, various stabilizers, lubricants, antioxidants, antistatic agents, antifoaming agents, fluorescent whitening agents, and the like can be blended as necessary.

  The thickness of the release substrate layer 1b is not particularly limited, and is usually about 10 to 150 μm, preferably about 10 to 125 μm, and more preferably 10 to 80 μm.

[Release layer 5]
The release layer 5 is provided in order to easily release the release base material layer 1b from the decorative resin molded product. The release layer 5 is peeled from the decorative resin molded product together with the release base layer 1b. For example, as shown in FIG. 7, the release layer 5 may be a solid release layer that covers the entire surface (a solid surface), or may be provided in a part. In general, a solid release layer is preferable in consideration of peelability.

  The release layer 5 is made of heat such as fluorine resin, acrylic resin, polyester resin, polyolefin resin, polystyrene resin, polyurethane resin, cellulose resin, vinyl chloride-vinyl acetate copolymer resin, and nitrified cotton. Plastic resins, copolymers of monomers forming the thermoplastic resins, those modified with (meth) acrylic acid or urethane, or silicone resins, acrylic silicone resins, melamine resins, acrylic melamine resins, alkyds A thermosetting resin such as a resin or an epoxy resin, or a wax such as a synthetic wax, petroleum wax, animal-derived wax, or plant-derived wax can be formed using a single composition or a mixture of a plurality of them.

  The thickness in particular of the mold release layer 5 is not restrict | limited, For example, about 0.01-5 micrometers, Preferably about 0.05-3 micrometers is mentioned.

[Adhesive layer 6]
In the decorative sheet for simultaneous injection-molding decoration, the adhesive layer 6 is formed on the surface of the glittering ink layer 2 opposite to the heat ray shielding layer 3, so that the decoration for simultaneous injection-molding decoration is performed. The sheet can be transferred to the resin molded product with good adhesiveness. The adhesive layer 6 can be formed of a resin composition such as a heat sensitive adhesive or a pressure adhesive. Examples of the resin contained in the adhesive layer 6 include acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamides. Based resins and the like. The adhesive layer 6 can be formed, for example, by applying and drying a resin composition containing these resins and a solvent on adjacent layers such as the glitter ink layer 2 and the metallic gloss layer 4.

  The thickness of the adhesive layer 6 is not particularly limited, and preferably 0.1 to 0.1 from the viewpoint that the decorative sheet for simultaneous injection molding can be efficiently transferred to a resin molded product. About 6 μm may be mentioned.

(Method for producing a decorative sheet for simultaneous injection molding)
The decorative sheet for simultaneous injection molding can be manufactured, for example, as follows. First, the mold release layer 5 is formed as needed on one surface of the resin film constituting the mold release base material layer 1b. Next, as a layer constituting the heat ray shielding layer 3, layers such as the protective layer 3a, the primer layer 3b, and the transparent resin layer 3c are formed by the above-described methods. Next, the glitter ink layer 2 is formed by applying the ink composition for the glitter ink layer on the layer located below the glitter ink layer 2. Further, the adhesive layer 6 is formed by the above method as necessary. As described above, a decorative sheet for simultaneous injection molding is obtained.

2. Decorative resin molded product The decorated resin molded product of the present invention is formed by integrating the decorative sheet of the present invention and an injection resin. That is, the decorative resin molded article of the present invention has at least an injection resin layer, a glittering ink layer, and a heat ray shielding layer in this order, the glittering ink layer contains a pearl pigment, and the heat ray shielding layer comprises And a heat ray shielding agent.

  The decorated resin molded product of the present invention is produced, for example, by the above-described insert molding method, injection molding simultaneous decorating method, or the like, using the decorated sheet of the present invention.

(Manufacture of decorative resin molded products by insert molding method)
In the insert molding method, first, in the vacuum forming step, the decorative sheet for insert molding of the present invention is previously vacuum formed into a surface shape of a molded product with a vacuum forming die (offline pre-molding), and then an extra portion is removed as necessary. Trimming is performed to obtain a molded sheet for insert molding. This insert molding 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 at the same time as the injection molding, insert molding is performed on the outer surface of the resin molded product. By integrating the decorative sheet for decoration, a decorative resin molded product as shown in FIG. 5 is manufactured.

More specifically, a decorative resin molded product using the decorative sheet for insert molding of the present invention is manufactured by an insert molding method including the following steps.
A vacuum forming step in which the decorative sheet for insert molding of the present invention is previously formed into a three-dimensional shape by a vacuum forming die,
Trimming process of trimming excess part of decorative sheet for insert molding that has been vacuum formed to obtain insert molding sheet, and inserting insert molding sheet into injection mold, closing injection mold, fluid state The integration process of injecting the injection resin into the injection mold and integrating the injection resin and the molding sheet for insert molding.

  In the vacuum forming step in the insert molding method, the decorative sheet for insert molding 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 for insert molding, the thickness of the decorative sheet for insert molding, and the like. If a resin film is used, the temperature can be usually about 100 to 250 ° C, preferably about 130 to 200 ° C. Moreover, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but is usually about 180 to 320 ° C, preferably about 220 to 280 ° C.

(Manufacture of decorative resin molded products by the simultaneous injection molding method)
The manufacturing method of the decorative resin molded product of the present invention by the simultaneous injection molding method includes the following steps (1) to (4).
(1) First, a step of clamping in a state in which the mold release base material layer 1b side of the decorative sheet for simultaneous injection molding of the present invention is directed to the female mold side of the mold,
(2) a step of injecting the injection resin into the mold,
(3) A step of taking out the decorative resin molded product from the mold after the injection resin has cooled, and (4) a step of peeling the release base layer 1b from the decorative resin molded product.

  Moreover, in the said process (1), prior to mold clamping, the process of preforming the decorative sheet for simultaneous injection molding decorating along the inner shape of the mold and closely contacting the inner surface of the mold, You may provide the process of heating the decorating sheet for simultaneous injection-molding decorating with a hot platen in advance. The temperature for heating the decorative sheet for simultaneous injection molding is preferably in the range of not less than the glass transition temperature of the resin forming the release base layer 1b and less than the melting temperature (or melting point). . Usually, it is more preferable to carry out at a temperature near the glass transition temperature. In addition, said glass transition temperature vicinity means the range of about glass transition temperature +/- 5 degreeC, and when using polyester resin suitable as resin which forms the base material layer 1b for mold release, generally 70- It is about 130 ° C.

  In the step (2), the above-described injection resin is melted and injected into the cavity to integrate the injection-molding decorative sheet and the injection resin. When the injection resin is a thermoplastic resin, it is made into a fluid state by heating and melting, and when the injection resin is a thermosetting resin, the uncured liquid composition is injected in a fluid state at room temperature or appropriately heated. Cool and solidify. As a result, the decorative sheet for simultaneous injection-molding decoration is integrated with the injection resin and adhered to form a decorative resin molded product. The heating temperature of the injection resin depends on the type of the injection resin, but is generally about 180 to 320 ° C, preferably about 220 to 280 ° C. Next, after the decorative resin molded product is cooled, the decorative resin molded product is taken out from the mold, and the release base layer 1b and the release layer 5 are peeled off, whereby the heat ray shielding layer 3 and the glitter ink layer 2 are transferred. It becomes a decorative resin molded product.

  In the decorative resin molded product of the present invention, the injection resin layer 7 integrated with the decorative sheet by insert molding, simultaneous injection molding, or the like may be formed by selecting an injection resin according to the application. The injection resin that forms the injection resin layer 7 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.

  Moreover, the said process (4) does not necessarily need to be performed immediately after the said process (1)-(3). That is, the mold release base material layer 1b may be peeled off immediately after the decorative resin molded product is taken out from the mold, or the distribution process of the decorative resin molded product or the actually used decorative resin molded product is used. You may peel the base material layer 1b for mold release immediately before.

  The decorative resin molded product obtained by insert molding and injection molding simultaneous decoration differs in whether or not the base material layer 1 of the decorative sheet is integrated in the decorative resin molded product. This is common in that the heat ray shielding layer 3 and the glitter ink layer 2 are laminated in order from the surface side of the molded product. Therefore, in the decorative resin molded product obtained by any of the insert molding method and the simultaneous injection molding method, the heat ray shielding agent absorbs light coming from the heat ray shielding layer 3 side of the decorative resin molded product, Deterioration of the binder resin due to the photocatalytic action of the pearl pigment contained in the glittering ink layer 2 located under the shielding layer 3 can be suppressed. Therefore, the weather resistance of the decorative resin molded product can be effectively increased. Furthermore, in the decorative resin molded product of the present invention, since the heat resistance is enhanced by the heat ray shielding layer 3 containing the heat ray shielding agent, it is not necessary to use a large amount of an ultraviolet absorber or the like. Therefore, the bleed-out generated in the decorative resin molded product can be suppressed, and the temporal stability of the decorative resin molded product can be improved.

  Since the decorative resin molded product of the present invention is excellent in weather resistance, for example, interior materials or exterior materials of vehicles such as automobiles; construction members such as baseboards and skirts; joinery such as window frames and door frames; It can be used as 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.

<Examples 1-8 and Comparative Examples 1-5>
(Preparation of decorative sheet)
An ABS resin film (thickness: 400 μm) was used as the base material layer. On one surface of the base material layer, an ink composition containing a resin binder made of an acrylic / vinyl chloride / vinyl acetate copolymer and aluminum powder (average particle size 18 μm) is used, and a metallic gloss layer (thickness) is obtained by gravure printing. 1 μm) was formed. Note that the metallic gloss layer was formed only in Example 3 and Comparative Example 2. Next, a glittering ink layer (thickness 1 μm) was formed by gravure printing on the metallic gloss layer using an ink composition containing the same binder resin and pearl pigment (Iriodin 100 manufactured by Merck) as the metallic gloss layer. . In addition, except for Example 3 and Comparative Example 2, a glittering ink layer was formed on one surface of the base material layer. Next, a woodgrain pattern layer (thickness 3 μm) was formed on the glitter ink layer by gravure printing using ink having the resin composition shown in Table 1. Isoindolinone, quinacridone, phthalocyanine, and carbon black were used as yellow, red, blue, and black pigments in the pattern layer, respectively. Next, by using an acrylic resin to which an ultraviolet absorber, a light stabilizer, and a heat ray shielding agent are added at a blending ratio shown in Table 1 on the surface of the pattern layer, the thickness is 3 μm, and gravure printing is performed. A primer layer was formed. In Table 1, the amount (parts by mass) of the metallic pigment in the metallic luster layer is part by mass with respect to 100 parts by mass of the binder resin used for forming the metallic luster layer. Moreover, in Table 1, the quantity (mass part) of the pearl pigment of a glittering ink layer is a mass part with respect to 100 mass parts of binder resin used for formation of a glittering ink layer.

  Next, on the surface of the primer layer, using an uncured electron beam curable resin to which an ultraviolet absorber, a light stabilizer, and a heat ray shielding agent are added at a blending ratio shown in Table 1, the thickness after curing is An uncured protective layer was formed by gravure printing so as to be 10 μm. The composition of the electron beam curable resin forming the protective layer is 64.7 parts by mass of bifunctional polycarbonate acrylate (average molecular weight 10,000), 32.3 parts by mass of bifunctional polycarbonate acrylate (average molecular weight 20000), and tetrafunctional polycarbonate acrylate. (Average molecular weight 6000) 3 parts by mass.

Next, the uncured protective layer was irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to cure the electron beam curable resin to obtain a decorative sheet. In addition, the ultraviolet absorber added to at least one of the primer layer and the protective layer is hydroxyphenyltriazine, the light stabilizer is a hindered amine light stabilizer (HALS), and the heat ray shielding agent is antimony-doped oxidation in Examples 1 to 7. Tin (ATO), zinc oxide in Example 8. In Table 1, the amounts of the ultraviolet absorber, the light stabilizer, and the heat ray shielding agent are parts by mass with respect to 100 parts by mass of the resin contained in each of the primer layer and the protective layer. In addition, about the heat ray shielding agent, it described together also about the quantity (g / m < ² >) of the heat ray shielding agent contained per 1m < ² > when a decoration sheet is seen from a lamination direction. Next, for each decorative sheet obtained in Examples 1 to 8 and Comparative Examples 1 to 5, weather resistance and presence / absence of bleeding out were evaluated by the following methods.

(1) Weather resistance About a decoration sheet, using Atlas weatherometer Ci4000 made from Atlas, the condition (irradiation (B.P.83 degreeC) 3.8 hours, condensation (exposure) of 1000 kJ / m < ² >) B. P. 38 ° C.) Repeated for 1 hour), the weather resistance was tested, and then the appearance of the decorative sheet was evaluated. The evaluation criteria are as follows.

<Color change>
Using a spectrocolorimeter (CM-3700d) manufactured by Konica Minolta, the color difference between the reference color and the color of the sample after the weather resistance test was measured. As the reference color, the color of the sample before the weather resistance test was used. The results are shown in Table 1. The evaluation criteria are as follows.
○: No color change was observed. (Color difference ΔE * <0.5)
Δ: Although a color change was observed, there was no practical problem. (0.5 ≦ ΔE * ≦ 1.0)
X: A remarkable color change was observed. (1.0 <ΔE *)

<Gloss change>
By using microgloss manufactured by BYK Gardner, the gloss value (60 °) of the surface of the sample after the weather resistance test was measured, and the difference from the initial value (gloss value 88) was calculated. The results are shown in Table 1. The evaluation criteria are as follows.
○○: No gloss reduction was observed. (Gross value difference within 9)
○: A slight decrease in gloss was observed. (Gloss value difference 10-19)
Δ: A decrease in gloss was observed, but there was no practical problem. (Gloss value difference 20-29)
X: A decrease in gloss was observed. (Gloss value difference 30-39)
XX: Significant gloss reduction was observed. (Gloss value difference 40 or more)

(2) Generation | occurrence | production of bleed-out After leaving each decorating sheet obtained in Examples 1-8 and Comparative Examples 1-5 at room temperature for 1 week, the surface of the decorating sheet was observed visually. The results are shown in Table 1. The evaluation criteria are as follows.
○: No bleed out was observed.
X: Bleed out was observed.

  As shown in Table 1, the decorative sheets of Examples 1 to 8 containing a heat ray shielding agent in at least one of the protective layer and the primer layer are excellent in weather resistance (inhibition effect on color change and gloss change), and bleed out. It became clear that generation | occurrence | production of was suppressed. On the other hand, it became clear that the decorative sheet of Comparative Examples 1 to 4 in which neither the protective layer nor the primer layer contains a heat ray shielding agent is inferior in weather resistance. Moreover, although neither a protective layer nor a primer layer contains a heat ray shielding agent, the decorative sheet of Comparative Example 5 in which a large amount of an ultraviolet absorber is blended in the protective layer is excellent in weather resistance but is not established as a product. It became clear that bleed out occurred.

<Example 9 and Comparative Example 6>
Gravure printing without using a metallic luster layer and primer layer, using an acrylic / urethane copolymer instead of an electron beam curable resin on the surface of the pattern layer so that the thickness after curing is 3 μm. A decorative sheet was produced in the same manner as in Examples 1 to 7 except that a protective layer was formed by the above method. Table 2 shows the composition of the resin and the like in the picture layer and the protective layer. Next, the weather resistance of each decorative sheet obtained in Example 9 and Comparative Example 6 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

  As shown in Table 2, according to Example 9 containing a heat ray shielding agent in the protective layer, it does not have a metallic luster layer and a primer layer, and further compared with Examples 1-8 and Comparative Examples 1-5. Although the protective layer is thin, it has become clear that a decorative sheet having a practically satisfactory weather resistance can be obtained. On the other hand, it was revealed that the decorative sheet of Comparative Example 6 in which the protective layer did not contain a heat ray shielding agent was inferior in weather resistance.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 1a ... Base material layer 1b for insert molding ... Base material layer 2 for mold release ... Bright ink layer 3 ... Heat ray shielding layer 3a ... Protective layer 3b ... Primer layer 3c ... Pattern layer 3d ... Transparent resin layer 4 ... Glossy metallic layer 5 ... Release layer 6 ... Adhesive layer 7 ... Injection resin layer

Claims (20)

At least a decorative sheet used for molding a decorative resin molded product having an injection resin layer, a glitter ink layer, and a heat ray shielding layer in this order,
On the base material layer and the base material layer, at least the glitter ink layer and the heat ray shielding layer,
The glitter ink layer includes a binder resin and a pearl pigment,
The pearl pigment content in the glitter ink layer is 50 to 90 parts by mass with respect to 100 parts by mass of the binder resin.
The decorating sheet in which the said heat ray shielding layer contains an inorganic type heat ray shielding agent. It is a decorative sheet used for insert molding,
The decorative sheet according to claim 1, comprising at least the glitter ink layer and the heat ray shielding layer in this order on the base material layer. It is a decorative sheet used for simultaneous injection molding,
The decorative sheet according to claim 1, comprising at least the heat ray shielding layer and the glitter ink layer in this order on the base material layer.   The decorative sheet according to any one of claims 1 to 3, wherein the heat ray shielding agent is at least one selected from the group consisting of antimony-doped tin oxide, tin-doped indium oxide, zinc oxide, and tungsten bronze. The amount of the heat ray-shielding agent of the heat ray shielding layer included in 1 m ² per when viewed the decorative sheet from the stacking direction, is 0.1 g / m ² or more, in any one of claims 1 to 4 The decorative sheet as described. The decorative sheet according to any one of claims 1 to 5 , further comprising a metallic luster layer containing a metal pigment. The decorative sheet according to any one of claims 1 to 6 , wherein the glitter ink layer further contains a metal pigment. The decorative sheet according to any one of claims 1 to 7 , wherein the glitter ink layer contains a chlorine-based resin. The decorative sheet according to claim 8 , wherein the glitter ink layer further comprises a (meth) acrylic resin. The mass ratio of the (meth) acrylic resin and chlorine type resin in brilliant ink layer ((meth) acrylic resin / chlorine resin) is in the range of 3 / 7-8 / 2, according to claim 9 Decorative sheet. The chlorinated resin is selected from the group consisting of polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, polypropylene chloride, and chlorinated polypropylene. The decorative sheet according to any one of claims 8 to 10 , which is at least one kind.   The decorative sheet according to claim 2, further comprising a protective layer on the glitter ink layer, wherein the protective layer is the heat ray shielding layer.   The decorative sheet according to claim 3, further comprising a protective layer between the base material layer and the glitter ink layer, wherein the protective layer is the heat ray shielding layer.   The decorative sheet according to claim 2, further comprising a primer layer and a protective layer in this order on the glitter ink layer, wherein at least one of the primer layer and the protective layer is the heat ray shielding layer.   Between the base material layer and the glitter ink layer, a protective layer and a primer layer are sequentially provided from the base material layer side, and at least one of the protective layer and the primer layer is the heat ray shielding layer. The decorative sheet according to claim 3. The decorative sheet according to claim 14 or 15 , wherein at least one of the primer layer and the protective layer contains at least one of an ultraviolet absorber and a light stabilizer. The decorative sheet according to any one of claims 12 to 16 , wherein the protective layer is formed of a resin composition containing an ionizing radiation curable resin or a two-component curable resin. It has at least an injection resin layer, a glittering ink layer, and a heat ray shielding layer in this order,
The glitter ink layer includes a binder resin and a pearl pigment,
The pearl pigment content in the glitter ink layer is 50 to 90 parts by mass with respect to 100 parts by mass of the binder resin.
The decorative resin molded product, wherein the heat ray shielding layer contains an inorganic heat ray shielding agent. The decorative resin molded product according to claim 18 , comprising a base material layer between the injection resin layer and the glitter ink layer. The decorative resin molded product according to claim 18 , comprising a base material layer on the heat ray shielding layer.