JP2017177539A - Decorative sheet and decorative resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet usable for a purpose of three-dimensional molding, excellent in designability and having brightness.SOLUTION: A decorative sheet at least includes: a brilliant layer containing a brilliant glass flake and a binder resin; and a coloring layer containing a coloring agent and a binder resin in this order on one side on a transparent thermoplastic resin film. The binder resin of the brilliant layer is substantially composed of a thermoplastic acrylic resin. The binder resin of the coloring agent is substantially composed of a thermoplastic vinyl chloride-acetic acid vinyl copolymer and a thermoplastic acrylic resin.SELECTED DRAWING: None

Description

  The present invention relates to a decorative sheet and a decorative resin molded product using the decorative sheet.

  2. Description of the Related Art Conventionally, there is known a technique for applying a high-quality design to a car interior / exterior product, an electrical appliance, or the like using a paint containing a light luminance pigment and baking. However, such a technique has a problem that the process is complicated and the environmental load due to the solvent is large.

  As a decorating means replacing painting, an insert molding method using a decorating sheet and an injection molding simultaneous decorating method are widely used. In particular, a decorative sheet having a layer using glass flakes coated with a metal or metal oxide has been proposed for applications that require a high-class feeling.

  For example, in Patent Document 1, glass flakes coated with metallic silver are kneaded with an acrylic resin to form a sheet, and a decorative sheet provided with the sheet as a surface layer is subjected to vacuum forming and injection molding, thereby providing a sense of brightness. It is described that the resin molded product which has was obtained. However, in the configuration of Patent Document 1, it is necessary to prepare a dedicated sheet for each design, and production efficiency and design freedom are low. Therefore, it is desirable to use glass flakes for a decorative layer provided by printing or the like, as in a general decorative sheet.

  On the other hand, for example, Patent Document 2 discloses a transfer foil including a glitter layer formed by coating a composition containing glass flakes coated with a metal or metal oxide and a transparent resin. Here, as the transparent resin, an amino-based cured resin such as urea resin or melamine resin is suitable. However, it is assumed that the transfer foil described in Patent Document 2 is mainly used as a hot stamp foil, and is formed into a three-dimensional shape by vacuum molding or injection molding like the insert molding method or the simultaneous injection molding method. It is not intended to be used.

  In addition, as in Patent Documents 1 and 2, in the decorative sheet, a decorative layer may be provided on the back surface of the glittering layer to improve decorativeness and ensure concealment. However, the glass flakes are large in size and have a large variation in shape compared to common pigments. For this reason, when a colored layer is further provided on the glittering layer containing glass flakes by printing or the like, it is difficult to uniformly laminate the colored layer on the glittering layer having large irregularities, and there is a problem that the decorativeness is impaired. .

JP 2004-284019 A JP 2007-175842 A

  Under such circumstances, the main object of the present invention is to provide a decorative sheet that can be used for three-dimensional molding applications, and has excellent design properties and glitter. Another object of the present invention is to provide a decorative resin molded product using the decorative sheet and a method for producing the same.

  The present inventors have intensively studied to solve the above problems. As a result, at least one surface of the transparent thermoplastic resin film is provided with a glittering layer containing a glittering glass lake and a binder resin, and a colored layer containing a colorant and a binder resin in this order. The decorative sheet is substantially composed of a thermoplastic acrylic resin, and the binder sheet of the colored layer is substantially composed of a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin. It has been found that it can be used for original molding applications, has excellent design properties, and has glitter.

  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 one surface of the transparent thermoplastic resin film is provided with a glittering layer containing a glittering glass lake and a binder resin, and a colored layer containing a colorant and a binder resin in this order,
The binder resin of the glitter layer is substantially composed of a thermoplastic acrylic resin,
The binder resin of the colored layer is substantially composed of a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin.
Decorative sheet.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the transparent thermoplastic resin film is composed of a thermoplastic acrylic resin.
Item 3. Item 3. The decorative sheet according to item 1 or 2, wherein the transparent thermoplastic resin film has a thickness of 50 µm or more and 200 µm or less.
Item 4. The mass ratio of the thermoplastic vinyl chloride-vinyl acetate copolymer and the thermoplastic acrylic resin in the binder resin of the colored layer is in the range of 3: 7 to 7: 3, according to any one of Items 1 to 3. Decorative sheet.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the glitter layer and the colored layer each have a thickness of 0.1 μm or more and 10 μm or less.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, wherein at least one surface of the transparent thermoplastic resin film includes the glitter layer, the colored layer, and an adhesive layer in this order.
Item 7. Item 6. The additive according to any one of Items 1 to 5, wherein at least one surface of the transparent thermoplastic resin film is provided with the glitter layer, the colored layer, the support sheet, and the adhesive layer in this order. Decorative sheet.
Item 8. At least a molding resin layer, a coloring layer containing a colorant and a binder resin, a glittering layer containing a glittering glass lake and a binder resin, and a transparent thermoplastic resin film are provided in this order.
The binder resin of the glitter layer is substantially composed of a thermoplastic acrylic resin,
The binder resin of the colored layer is substantially composed of a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin.
Decorative resin molded product.
Item 9. The process of obtaining the molded sheet by vacuum forming the decorative sheet according to any one of Items 1 to 7 with a vacuum mold,
The molded sheet is inserted into an injection mold, the injection mold is clamped, and the resin in a fluid state is injected into the mold from the colored layer side, solidified, and simultaneously with the injection molding, on the outer surface of the resin molded product Integrating the molded sheet;
A method for producing a decorated resin molded product.

  ADVANTAGE OF THE INVENTION According to this invention, it can be used for a three-dimensional shaping | molding use, Furthermore, it is excellent in the designability and can provide the decorating sheet provided with glitter. Furthermore, according to this invention, the decorative resin molded product using the said decorating sheet and its manufacturing method can also be provided.

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 decorative resin molded product manufactured using the decorating sheet of this invention. It is a schematic sectional drawing of an example of the decorative resin molded product manufactured using the decorating sheet of this invention.

1. Decorative sheet The decorative sheet of the present invention comprises at least one surface of a transparent thermoplastic resin film, a glittering layer containing a glittering glass lake and a binder resin, and a colored layer containing a colorant and a binder resin. The binder resin of the glitter layer is substantially made of a thermoplastic acrylic resin, and the binder resin of the colored layer is substantially made of a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin. It is characterized by comprising. By providing such a configuration, the decorative sheet of the present invention can be used for three-dimensional molding applications, and has excellent design properties and glitter. Specifically, in the decorative sheet of the present invention, since the glittering layer is visible through the transparent thermoplastic resin film located on the surface, even if the layer located on the surface does not contain glittering glass flakes, Brightness can be exhibited. In addition, the decorative sheet of the present invention has three-dimensional formability because the transparent thermoplastic resin film, the glittering layer, and the colored layer contain a thermoplastic resin. Further, in the decorative sheet of the present invention, the binder resin of the glitter layer is substantially made of a thermoplastic acrylic resin, and the binder resin of the colored layer is substantially made of a thermoplastic vinyl chloride-vinyl acetate copolymer and Since it consists of a thermoplastic acrylic resin, a colored layer is printed uniformly on the surface of a glittering layer, and it is excellent in the designability expressed by the combination of a glittering layer and a colored layer. Hereinafter, the decorative sheet of the present invention will be described in detail.

Laminated structure of decorative sheet The decorative sheet of the present invention has, for example, at least a transparent thermoplastic resin film 1, a glittering layer 2, and a colored layer 3 in this order, as shown in FIGS. It has a laminated structure. Moreover, for example, as shown in FIG. 2 or FIG. 3, in the decorative sheet of the present invention, for the purpose of improving the adhesion between the decorative sheet of the present invention and the molded resin layer 6, as necessary. The adhesive layer 4 may be provided on the surface opposite to the transparent thermoplastic resin film 1. Moreover, as shown in FIG. 3, from the viewpoint of increasing the rigidity of the decorative sheet of the present invention, a support sheet 5 may be provided on the colored layer 3 side of the decorative sheet. One or more other layers may be laminated on the decorative sheet of the present invention depending on the function to be imparted to the decorative sheet or the decorative resin molded product.

  As a laminate structure of the decorative sheet of the present invention, a laminate structure in which a transparent thermoplastic resin film / brightness layer / colored layer is laminated; a laminate in which a transparent thermoplastic resin film / brightness layer / colored layer / adhesive layer is laminated Structure: A laminated structure in which a transparent thermoplastic resin film / brightness layer / colored layer / support sheet / adhesive layer are laminated may be mentioned. FIG. 1 shows a schematic cross-sectional view of an example of a decorative sheet in which a transparent thermoplastic resin film / brightness layer / colored layer is laminated in this order as an embodiment of the laminated structure of the decorative sheet of the present invention. FIG. 2 is a schematic cross-sectional view of an example of a decorative sheet in which a transparent thermoplastic resin film / brightness layer / colored layer / adhesive layer are laminated in this order as an embodiment of the laminated structure of the decorative sheet of the present invention. Show. FIG. 3 is a schematic view of an example of a decorative sheet in which a transparent thermoplastic resin film / brightness layer / colored layer / support sheet / adhesive layer are laminated in this order as an embodiment of the laminated structure of the decorative sheet of the present invention. A cross-sectional view is shown.

Composition and configuration of each layer forming the decorative sheet

[Transparent thermoplastic resin film 1]
The transparent thermoplastic resin film 1 is a layer provided for the purpose of imparting three-dimensional formability, scratch resistance, etc. to the decorative sheet while making the glittering layer 2 visible through the transparent thermoplastic resin film 1. .

  The material constituting the transparent thermoplastic resin film 1 is not particularly limited, but from the viewpoint of suitably three-dimensionally molding a decorative sheet by an insert molding method or an injection molding simultaneous decorating method, preferably an acrylic resin, Vinyl chloride resin, ABS resin (acrylonitrile-styrene-butadiene copolymer), styrene resin, polycarbonate resin, polyester resin (for example, polyethylene terephthalate, moldable polyester resin, etc.), polyolefin resin (polyethylene, polypropylene, polymethylpentene, Polybutene, ethylene-propylene copolymer, propylene-butene copolymer, olefin-based thermoplastic elastomer, etc.). Among these, a thermoplastic acrylic resin is particularly preferable from the viewpoint of excellent transparency and moldability. By using a thermoplastic acrylic resin with high transparency and gloss on the surface, the decorative resin molded product using the decorative sheet of the present invention has a synergistic effect with the glitter exhibited by the glitter layer 2 described below. A high-class design with a feeling of painting and brightness can be achieved.

  Examples of the thermoplastic acrylic resin include polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-styrene copolymer, and the like. . A thermoplastic acrylic resin may be used individually by 1 type, and may be used in combination of 2 or more types. In the present invention, (meth) acrylate means acrylate or methacrylate.

  The transparent thermoplastic resin film 1 may be a single layer or may be composed of a plurality of layers. Moreover, the transparent thermoplastic resin film 1 may be colored to such an extent that the glitter layer 2 can be visually recognized. Furthermore, the transparent thermoplastic resin film 1 may contain various additives such as a stabilizer, a plasticizer, an ultraviolet absorber, and a hindered amine light stabilizer as necessary.

  Although it does not restrict | limit especially as thickness of the transparent thermoplastic resin film 1, While ensuring the outstanding three-dimensional moldability of the decorating sheet | seat by the insert molding method or the injection molding simultaneous decorating method, etc., it has high brightness and design property. From the viewpoint of performance, it is preferably 50 μm or more and 200 μm or less, more preferably 75 μm or more and 150 μm or less. If thickness is 50 micrometers or more, while being able to ensure the flaw resistance etc. which are calculated | required by the surface of a decorating sheet, the design feeling like the coating with the depth can be obtained. In addition, the decorative sheet has sufficient rigidity, the decorative sheet is difficult to bend, and when the glitter layer 2 is formed by printing or the like, the orientation of the glass flakes is good, and the decorative sheet is likely to exhibit glitter. . On the other hand, when the thickness is 200 μm or less, it is easy to visually recognize the brightness of the glitter layer 2, and the productivity when the glitter layer is formed by printing or the like is improved. In addition, the said thickness is the total thickness of a some layer, when the transparent thermoplastic resin film 1 is comprised by the some layer.

  Necessary for the purpose of surface modification such as adjustment of wettability and improvement of adhesion with other layers in contact with the transparent thermoplastic resin film 1 on the front surface, back surface, or both front and back surfaces of the transparent thermoplastic resin film 1 Accordingly, corona discharge treatment, plasma treatment, or the like may be performed.

[Brightness layer 2]
The glitter layer 2 is a layer provided for imparting a glitter design to the decorative sheet of the present invention. The glitter layer 2 includes glitter glass flakes and a binder resin in order to express a glitter design (for example, metallic tone), and the binder resin is substantially made of a thermoplastic acrylic resin. In the present invention, “the binder resin substantially consists of a thermoplastic acrylic resin” means that the content of the thermoplastic acrylic resin in the binder resin is, for example, about 80% by mass or more.

  The glittering layer 2 usually includes glittering glass flakes, thermoplastic acrylic resin, and a solvent, and if necessary, a glittering composition in which extender pigments, stabilizers, plasticizers, catalysts, curing agents, and the like are appropriately mixed. Can be formed by printing on the transparent thermoplastic resin film 1.

  The glittering glass flakes contained in the glittering layer 2 are not particularly limited as long as they exhibit a glittering design, but preferably include glass flakes coated with at least one of a metal and a metal oxide. Although it does not restrict | limit especially as a metal which coat | covers glass flakes, For example, metal alloys, such as gold | metal | money, silver, platinum, palladium, nickel, copper, aluminum, chromium, brass, and tin, hastelloy, silver tin alloy, etc. Is mentioned. Among these, silver is preferable from the viewpoint of exhibiting high glitter. Further, as the metal oxide, titanium oxide and the like are preferably used from the viewpoint of exhibiting high glitter. Further, the glass serving as the base material of the glass flake is not particularly limited, but preferably silicate glass, silicate acrylic glass, soda lime glass, lead glass and the like can be mentioned. The glittering glass flake is obtained by coating the surface of a glass substrate with at least one of a metal and a metal oxide by a method such as electroless plating or sputtering. Such glittering glass flakes can also be obtained commercially. The glittering glass flakes may be used alone or in combination of two or more.

  The particle size of the glittering glass flake is not particularly limited, and may be appropriately set according to the thickness of the glittering layer 2 and the colored layer 3. Specific examples of the particle diameter of the glittering glass flake include 100 μm or less, more preferably 1 μm or more and 90 μm or less.

  The content of the glass flake in the glitter layer 2 is not particularly limited, but is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 10 parts by mass with respect to 100 parts by mass of the binder resin in the glitter layer 2. Part or more and 30 parts by weight or less.

  Examples of the thermoplastic acrylic resin used as the binder resin for the glitter layer 2 include polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and methyl (meth). Examples thereof include acrylate-styrene copolymers. A thermoplastic acrylic resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  The binder resin of the glitter layer 2 is substantially made of a thermoplastic acrylic resin, but may contain other thermoplastic resins as long as the effects of the present invention are not impaired. Examples of other thermoplastic resins include chlorinated resins, polyurethanes, polyesters, polyamides, butyral resins, polystyrenes, nitrocellulose resins, and cellulose acetate resins, and preferably chlorinated resins. These other thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the thermoplastic acrylic resin contained in the binder resin of the glitter layer 2 is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 90% by mass or more, more preferably 95% by mass or more. 100% by mass is particularly preferable.

  The solvent contained in the glitter composition is not particularly limited as long as it uniformly disperses components such as glitter glass flakes and binder resin in the glitter composition and is suitable for printing, but preferably methyl ethyl ketone, Examples include ethyl acetate and toluene. A solvent may be used individually by 1 type and may be used in combination of 2 or more types.

  The thickness of the glitter layer 2 is not particularly limited, but from the viewpoint of three-dimensional formability, glitter, and design, it is preferably 0.1 μm or more and 10 μm or less, more preferably about 1 μm or more and 5 μm or less. . The thickness of the glitter layer 2 is a position where the cross section of the decorative sheet is observed with an optical microscope, the glitter glass flakes are not present, and the surface of the glitter layer 2 is not raised by the glitter glass flakes. It is the value measured by.

  The glitter layer 2 is formed, for example, by printing using a glitter composition. The printing method for forming the glitter 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.

[Colored layer 3]
The colored layer 3 is a layer provided for the purpose of imparting design properties to the decorative resin molded product by being formed together with the glitter layer 2. In the present invention, the colored layer 3 contains a colorant and a binder resin, and the binder resin substantially consists of a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin. In the present invention, the colored layer 3 is provided adjacent to the above-described glittering layer 2 using an acrylic resin as a binder resin, and the colored layer 3 can be printed on the surface of the glittering layer 2 without unevenness. An excellent design can be exhibited by the combination of the layer 2 and the colored layer 3. In the present invention, “the binder resin substantially consists of a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin” means that the thermoplastic vinyl chloride-vinyl acetate copolymer and the heat in the binder resin. It means that the total content of the plastic acrylic resin is, for example, about 80% by mass or more.

  The colored layer 3 can be formed by printing the ink for forming the colored layer on the surface of the glittering layer 2 by a conventionally known printing method such as gravure printing, silk screen printing, or offset printing.

  The ink for forming the colored layer is composed of a colorant such as a pigment or a dye, a binder resin containing a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin, and various additives and solvents appropriately added to these.

  In the binder resin of the colored layer 3, the mass ratio of the thermoplastic vinyl chloride-vinyl acetate copolymer and the thermoplastic acrylic resin is not particularly limited, but the colored layer 3 is printed evenly on the surface of the glitter layer 2. From the viewpoint of exhibiting an excellent design, a range of 3: 7 to 7: 3 is preferable, and a range of 40:60 to 65:35 is more preferable.

  The binder resin of the colored layer 3 is substantially composed of a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin, but may contain other thermoplastic resins as long as the effects of the present invention are not impaired. . Examples of other thermoplastic resins include polyester resins, cellulosic resins, chlorinated polypropylene, urethane resins, and polyamide resins. These other thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The total content of the thermoplastic vinyl chloride-vinyl acetate copolymer and the thermoplastic acrylic resin contained in the binder resin of the colored layer 3 is not particularly limited as long as the effects of the present invention are not impaired. From the viewpoint of suitably suppressing unevenness and exhibiting an excellent design, it is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 100% by mass.

  The colorant is not particularly limited. For example, inorganic pigments such as carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, and cobalt blue; quinacridone red And organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue.

  The solvent contained in the ink for forming the colored layer is not particularly limited as long as it uniformly disperses components such as a colorant and a binder resin and is suitable for printing, but preferably methyl ethyl ketone, ethyl acetate, toluene, and the like. Can be mentioned. A solvent may be used individually by 1 type and may be used in combination of 2 or more types.

  Although it does not restrict | limit especially as thickness of the colored layer 3, From a viewpoint of three-dimensional moldability, glitter, and design property, Preferably it is 0.1 to 10 micrometer, More preferably, about 0.6 to 7 micrometer is mentioned. It is done. The thickness of the colored layer 3 is a value measured at a position where the surface of the colored layer 3 is not raised by a colorant (for example, pigment) or the like by observing a cross section of the decorative sheet with an optical microscope.

[Adhesive layer 4]
The adhesive layer 4 is a layer provided as necessary for the purpose of improving the adhesion between the decorative sheet and the molded resin layer 6. The adhesive layer 4 is usually provided on the surface (that is, the back surface) of the decorative sheet opposite to the transparent thermoplastic resin film 1.

  The resin that forms the adhesive layer 4 is not particularly limited as long as it can improve the adhesion and adhesion between the decorative sheet and the molded resin layer 6. For example, a thermoplastic resin or a thermosetting resin can be used. Resin is used. Examples of the thermoplastic resin include acrylic resin, acrylic-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber-based resin. . A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the thermosetting resin include a urethane resin and an epoxy resin. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  Although the adhesive layer 4 is not necessarily a necessary layer, it is assumed that the decorative sheet of the present invention is applied to a decorative method by sticking onto a resin molded body prepared in advance, such as a vacuum pressure bonding method described later. Is preferably provided on the surface of the decorative sheet that contacts the resin molded body. When using for the vacuum press-bonding method, it is preferable to form the adhesive layer 4 using a conventional resin that exhibits adhesiveness by pressurization or heating among the various resins described above.

  The thickness of the adhesive layer 4 is not particularly limited and may be appropriately set according to the position where the adhesive layer 4 is provided and the adjacent layer. For example, the thickness is about 0.1 μm to 30 μm, preferably 0.5 μm to 20 μm. More preferably, it is about 1 μm or more and 8 μm or less.

[Support sheet 5]
The support sheet 5 is a layer provided as necessary in order to provide a decorative sheet suitable for vacuum forming or the like by an insert molding method or the like by imparting rigidity to the decorative sheet and maintaining its shape. The support sheet 5 is provided on the colored layer 3 side of the decorative sheet. For example, the support sheet 5 is provided on the surface of the decorative sheet opposite to the transparent thermoplastic resin film 1 (that is, the back surface) or the adhesive layer 4 is provided. In some cases, it is provided between the colored layer 3 and the adhesive layer 4.

  The support sheet 5 is preferably formed of a thermoplastic resin from the viewpoint of making the decorative sheet suitable for the insert molding method, the simultaneous injection molding method, and the like. The thermoplastic resin is not particularly limited, but acrylonitrile-butadiene-styrene resin (hereinafter also referred to as “ABS resin”), acrylic resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride resin Polyethylene terephthalate (PET) resin, acrylonitrile-butadiene-styrene resin; acrylonitrile-styrene-acrylic ester resin and the like. The support sheet 5 is preferably formed of the same resin as the molded resin layer 6 described later. For example, when the molded resin layer 6 is formed of ABS resin, the support sheet 5 is also formed of ABS resin. In the case where the molded resin layer 6 is made of polypropylene, the support sheet 5 is also preferably made of polypropylene. The resin forming the support sheet 5 may be one type or two or more types.

  The thickness of the support sheet 5 is not particularly limited, but is preferably about 50 μm or more and 1000 μm or less, more preferably 100 μm from the viewpoint of making the decorative sheet suitable for the insert molding method or the simultaneous injection molding method. For example, about 700 μm or less.

  The support sheet 5 may be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides as necessary in order to improve the adhesion with the adjacent layer. . Examples of the oxidation method performed as the surface treatment of the support sheet 5 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method. Moreover, as the uneven | corrugated method performed as surface treatment of the support body sheet 5, the sandblasting method, the solvent processing method, etc. are mentioned, for example. These surface treatments are appropriately selected depending on the type of the resin constituting the support sheet 5, and from the viewpoint of effects and operability, a corona discharge treatment method is preferable.

  The support sheet 5 may be colored with a colorant or the like, painted for adjusting the color, or formed with a pattern for imparting design.

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 a molded resin. That is, as shown in FIG. 4 or FIG. 5, the decorative resin molded product of the present invention includes at least a molded resin layer 6, a colored layer 3 containing a colorant and a binder resin, a glittering glass lake and a binder resin. And the transparent thermoplastic resin film 1 in this order. The binder resin of the glitter layer 2 is substantially made of a thermoplastic acrylic resin, and the binder resin of the colored layer 3 is substantially It is characterized by comprising a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin. As described above, the decorative resin molded product may be further provided with the adhesive layer 4 and the support sheet 5.

  The decorative resin molded product of the present invention is produced, for example, by various injection molding methods such as insert molding, simultaneous injection molding, blow molding, and gas injection molding using the decorative sheet of the present invention. The Among these injection molding methods, an insert molding method and an injection molding simultaneous decorating method are preferable. In addition, the decorative resin molded product of the present invention is a decorative method of sticking the decorative sheet of the present invention on a three-dimensional resin molded body (molded resin layer 6) prepared in advance, such as a vacuum pressure bonding method. Can also be produced.

  In the insert molding method, first, in the vacuum forming step, the decorative sheet of the present invention is vacuum formed (off-line pre-molding) into a molded product surface shape in advance by a vacuum forming die, and then an excess portion is trimmed as necessary. A molded sheet is obtained. This molded sheet is inserted into an injection mold, the injection mold is clamped, a resin in a fluid state is injected into the mold from the colored layer 3 side, solidified, and simultaneously with the injection molding, on the outer surface of the resin molded product A decorative resin molded product is manufactured by integrating the decorative sheet.

More specifically, the decorative resin molded product of the present invention is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance by a vacuum forming die,
Trimming process to trim the excess part of the vacuum-decorated decorative sheet to obtain the molded sheet, and insert the molded sheet into the injection mold, close the injection mold, and inject the fluidized resin from the colored layer 3 side An integration process in which the resin and the molded sheet are integrated by injection into the mold.

  In the vacuum forming step in the insert molding method, the decorative sheet may be heated and molded. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, for example, when an ABS resin film is used as the base material layer. For example, the temperature is 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.

  In addition, in the simultaneous injection molding decoration method, the decorative sheet of the present invention is placed in a female mold that also serves as a vacuum forming mold provided with a suction hole for injection molding, and preliminary molding (in-line preliminary molding) is performed with this female mold. After performing, the injection mold is clamped, and the resin in a fluid state is injected and filled into the mold from the colored layer 3 side, solidified, and decorated on the outer surface of the resin molding simultaneously with the injection molding. A decorative resin molded product is manufactured by integrating the sheets.

More specifically, the decorative resin molded product of the present invention is manufactured by the simultaneous injection molding method including the following steps.
After the decorative sheet of the present invention is installed so that the surface of the base material layer of the decorative sheet faces the molding surface of the movable mold having a molding surface of a predetermined shape, the decorative sheet is heated, A pre-molding step of pre-molding the decorative sheet by softening and vacuum-sucking from the movable mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable mold,
After clamping the movable mold and the fixed mold having the decorative sheet closely adhered along the molding surface, the fluidized resin is injected from the colored layer 3 side into the cavity formed by both molds. Filling and solidifying to form a resin molded body, integrating the resin molded body and the decorative sheet by stacking and integrating, and moving the movable mold away from the fixed mold, the entire decorative sheet is laminated The extraction process of taking out the molded resin product.

  In the preforming step of the simultaneous injection molding method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, etc. If a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can usually be about 70 to 130 ° C. In the injection molding process, the temperature of the resin in the fluidized state is not particularly limited, but is usually about 180 to 320 ° C, preferably about 220 to 280 ° C.

  In the vacuum bonding method, first, the decorative sheet and the resin molded body of the first pressure chamber located on the upper side and the second vacuum chamber located on the lower side in the vacuum pressure bonding machine, the decorative sheet is the first. The vacuum chamber side is placed in a vacuum pressure bonding machine so that the resin molded body is on the second vacuum chamber side and the colored layer 3 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state. . The resin molding is installed on a lifting platform that is provided on the second vacuum chamber side and can be moved up and down. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using an elevator, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. Adhere to the surface. Finally, the two vacuum chambers are opened to the atmospheric pressure, and the decorative resin molded product of the present invention can be obtained by trimming the excess portion of the decorative sheet as necessary.

  In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve the formability before the step of pressing the molded body against the decorative sheet. The vacuum pressure bonding method provided with the said process may be especially called a vacuum thermocompression bonding method. Although the heating temperature in the said process should just be suitably selected with the kind of resin which comprises a decorating sheet, the thickness of a decorating sheet, etc., if it is a case where a polyester resin film or an acrylic resin film is used as a base material layer Usually, it can be about 60-200 degreeC.

  In the decorative resin molded product of the present invention, the molded resin layer 6 may be formed by selecting a resin according to the application. The resin forming the molded resin layer 6 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.

  The decorative resin molded product of the present invention includes, for example, interior materials or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for buildings such as walls, floors, and ceilings; television receivers and air conditioners. It can be used as a housing for home appliances such as a machine;

  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.

<Example 1>
Using an ink containing a thermoplastic acrylic resin (100 parts by mass) and silver-coated glass flakes (average diameter 25 μm, 12 parts by mass) on one side of a thermoplastic transparent acrylic film (thickness 125 μm), it is brilliant by gravure printing. A layer (thickness 1 μm at a position without glass flakes) was formed on the entire surface. Next, on the glitter layer, thermoplastic vinyl chloride-vinyl acetate copolymer and thermoplastic acrylic resin (each 50 parts by mass, total 100 parts by mass) and white pigment (titanium oxide, average diameter 0.4 μm, 30 parts by mass) ) Was used, and a colored layer (thickness of 1 μm at a position without a pigment) was formed on the entire surface by gravure printing. Furthermore, an acrylic adhesive layer (1 μm) was formed to obtain a decorative sheet.

<Comparative Example 1>
In the glittering layer of Example 1, instead of the thermoplastic acrylic resin (100 parts by mass), a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin (each 50 parts by mass, total 100 parts by mass) A decorative sheet was obtained in the same manner as in Example 1 except that was used.

<Comparative example 2>
In the colored layer of Example 1, a thermoplastic acrylic resin (100 parts by mass) was used instead of the thermoplastic vinyl chloride-vinyl acetate copolymer and the thermoplastic acrylic resin (each 50 parts by mass, a total of 100 parts by mass). Except that, a decorative sheet was obtained in the same manner as in Example 1.

<Comparative Example 3>
In the glittering layer of Example 1, instead of the thermoplastic acrylic resin (100 parts by mass), a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin (each 50 parts by mass, total 100 parts by mass) And in the colored layer of Example 1, instead of the thermoplastic vinyl chloride-vinyl acetate copolymer and the thermoplastic acrylic resin (50 parts by mass, 100 parts by mass in total), a thermoplastic acrylic resin ( A decorative sheet was obtained in the same manner as in Example 1 except that (100 parts by mass) was used.

(Evaluation of printability and designability)
The surface of each decorative sheet obtained above was visually observed, and the printability of the colored layer and the designability of the decorative sheet were evaluated according to the following criteria. The results are shown in Table 1.
A: The unevenness of the ink which forms a colored layer is not recognized, but the design property is very favorable.
B: Although the unevenness of the ink which forms a colored layer is recognized a little, the design property is favorable as a whole.
C: Unevenness of the ink forming the colored layer is recognized, and the design is poor.
D: Remarkable unevenness is recognized in the ink forming the colored layer, and the design is remarkably bad.

(Three-dimensional formability evaluation)
Each decorative sheet obtained above was heated to 160 ° C. with an infrared heater and softened. Next, vacuum forming was performed using a vacuum forming die (maximum draw ratio: 100%) to form the internal shape of the die. After the molded decorative sheet was cooled, the decorative sheet was released from the vacuum forming mold. The obtained decorative sheet was visually observed and the moldability was evaluated according to the following criteria. The results are shown in Table 1.
A: No cracking or whitening of the coating film is observed, and the three-dimensional formability is excellent.
B: Although a fine coating crack or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion, there is no problem in practical use.
C: Slight coating cracking or whitening occurs in a part of the three-dimensional shape portion or the maximum stretched portion, which is slightly problematic in practical use.
D: Coating failure and whitening are observed in the surface protective layer without following the shape of the mold, and there are practical problems.
E: The decorative sheet was too hard to be vacuum formed.

(Illumination evaluation)
It confirmed visually and evaluated the glitter of the decorating sheet according to the following references | standards. The results are shown in Table 1.
A: The glitter design is expressed.
B: The glitter design is slightly expressed.
C: The glitter design is not expressed.

  As shown in Table 1, the decorative sheets of Example 1 and Comparative Examples 1 to 5 were all excellent in three-dimensional formability. In addition, the decorative sheet of Example 1 was provided with a uniform colored layer, and was excellent in design and glitter. Moreover, the decorative sheet of Example 1 was excellent in design and glitter even after molding. On the other hand, in the decorative sheets of Comparative Examples 1 to 5, the printed state of the colored layer was poor, and even before molding, the oblique lines and streaks of the plate were generated in the colored layer, and ink unevenness was recognized.

DESCRIPTION OF SYMBOLS 1 ... Transparent thermoplastic resin film 2 ... Glossy layer 3 ... Colored layer 4 ... Adhesive layer 5 ... Support sheet 6 ... Molding resin layer

Claims (9)

At least one surface of the transparent thermoplastic resin film is provided with a glittering layer containing a glittering glass lake and a binder resin, and a colored layer containing a colorant and a binder resin in this order,
The binder resin of the glitter layer is substantially composed of a thermoplastic acrylic resin,
The binder resin of the colored layer is substantially composed of a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin.
Decorative sheet.   The decorative sheet according to claim 1, wherein the transparent thermoplastic resin film is made of a thermoplastic acrylic resin.   The decorative sheet according to claim 1 or 2, wherein the transparent thermoplastic resin film has a thickness of 50 µm or more and 200 µm or less.   The mass ratio of the thermoplastic vinyl chloride-vinyl acetate copolymer and the thermoplastic acrylic resin in the binder resin of the colored layer is in the range of 3: 7 to 7: 3. Decorative sheet.   The decorative sheet according to any one of claims 1 to 4, wherein each of the glitter layer and the colored layer has a thickness of 0.1 µm or more and 10 µm or less.   The decorative sheet according to any one of claims 1 to 5, comprising at least one of the glitter layer, the colored layer, and the adhesive layer in this order on one surface of the transparent thermoplastic resin film.   At least one surface of the transparent thermoplastic resin film is provided with the glitter layer, the colored layer, a support sheet, and an adhesive layer in this order, according to any one of claims 1 to 5. Decorative sheet. At least a molding resin layer, a coloring layer containing a colorant and a binder resin, a glittering layer containing a glittering glass lake and a binder resin, and a transparent thermoplastic resin film are provided in this order.
The binder resin of the glitter layer is substantially composed of a thermoplastic acrylic resin,
The binder resin of the colored layer is substantially composed of a thermoplastic vinyl chloride-vinyl acetate copolymer and a thermoplastic acrylic resin.
Decorative resin molded product. A process of obtaining a molded sheet by vacuum forming the decorative sheet according to any one of claims 1 to 7 with a vacuum forming mold;
The molded sheet is inserted into an injection mold, the injection mold is clamped, and the resin in a fluid state is injected into the mold from the colored layer side, solidified, and simultaneously with the injection molding, on the outer surface of the resin molded product Integrating the molded sheet;
A method for producing a decorated resin molded product.