JP2000153587A - Decorating sheet and decorated molding using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize excellent solvent resistance by forming a surface protective layer made of a crosslinking curable type acrylic resin on a surface side of a base material sheet containing an acrylic resin, a polystyrene resin or a mixture of the both as a main component. SOLUTION: A surface protective layer 2 is formed on a surface of a base material sheet 1 to become a front side. A decorative layer 3 and further an adhesive layer 4 as needed are sequentially laminated in this order on a surface of the sheet 1 to become a rear side to the decorative sheet S. Then, the sheet 1 is made of a thermoplastic resin containing an acrylic resin, a polystyrene resin or a mixture of the both as a main component. The layer 2 is constituted of a crosslinking curable type acrylic resin. Then, the layer 2 is laminated on a molding so as to become a front side. Thus, even in the case of using the sheet 1 made of the polystyrene resin, excellent solvent resistance can be realized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a painting sheet used for simultaneous painting by injection molding such as injection molding or the like, or for painting by molding on the surface of an existing resin molded product by vacuum molding or the like. Related to painted moldings. In particular, the present invention relates to a paint sheet and a paint molded product having improved surface properties such as solvent resistance.

[0002]

2. Description of the Related Art Conventionally, painted molded products obtained by painting (decorating) the surface of a resin molded product have been used for various purposes. For example, in the simultaneous injection molding painting method disclosed in Japanese Patent Publication No. 50-19132 and the like, a painting sheet is laminated and integrated on the surface of a resin molded product at the same time as the molding of the resin molded product, so that the painting is performed on the surface. A molded article is obtained. As a method of laminating a painting sheet on a resin molded product or the like which has already been molded and painting it to make a painted molded product, Japanese Patent Publication No.
In the so-called vacuum forming and laminating method disclosed in JP-A-6-45768 and JP-B-60-58014, a painting sheet is placed on a resin molded product, and painting is performed by a pressure difference caused by vacuum suction from the molded product. By forming the sheets and laminating and integrating them, a painted molded product can be obtained. Further, as a base sheet of such a painting sheet, a transparent resin sheet made of a polystyrene-based resin or particularly an acrylic resin has been used because of its excellent moldability and transparency. By forming the decorative layer on the back surface of the base sheet, the base sheet on the front side can be used as a protective layer for the decorative layer, and also, because of its transparency, an excellent paint feeling can be obtained. is there.

[0003]

However, for example, an acrylic resin sheet made of polymethyl methacrylate (PMMA) or a styrene resin sheet made of polystyrene or the like has excellent transparency, but on the other hand,
Solvent resistance is poor, and when an organic solvent comes into contact with the surface, there is a problem that the surface is whitened or dissolved and easily deteriorates depending on the type.

[0004] Therefore, an object of the present invention is to provide a paint sheet for laminating even if a base sheet made of an acrylic resin or a polystyrene resin having excellent moldability and transparency is used. It is to be excellent. Also,
An object of the present invention is to provide a painted molded article obtained by using such a painted sheet having excellent solvent resistance.

[0005]

Therefore, in order to solve the above-mentioned problems, a painting sheet according to the present invention is a painting sheet for laminating on the surface of a molded product, comprising an acrylic resin,
A surface protection layer made of a cross-linking-curable acrylic resin was formed on the front surface of a base sheet mainly composed of a polystyrene resin or a mixture of both. As a result, surface properties such as solvent resistance are improved.

[0006] In addition, in the painting molded article of the present invention, the above-mentioned painting sheet has its surface protective layer facing the front side.
It was configured to be laminated on the surface of the molded product. as a result,
Surface properties such as solvent resistance are improved.

[0007]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view illustrating the painting sheet of the present invention in one embodiment, FIG. 2 is a cross-sectional view illustrating the painting molded article of the present invention in one embodiment, FIG.
FIG. 1 is a conceptual view illustrating an example of a simultaneous painting method for injection molding as an example of a method of manufacturing a painted article, and FIG. 4 is a cross-sectional view illustrating a conventional painting sheet as an example.

Painting sheet The painting sheet of the present invention is formed by crosslinking a surface of a base sheet 1 mainly composed of an acrylic resin or a polystyrene resin, as shown in the painting sheet S shown in FIG. This is a painting sheet having a configuration in which a surface protective layer 2 made of a curable acrylic resin is formed. Usually, as shown in the figure, a decorative layer 3 is further provided on the surface on the back side of the base sheet 1. Accordingly, a painting sheet having a configuration in which the adhesive layers 4 are laminated in this order is obtained.

[Base Sheet] The base sheet 1 is a resin sheet made of a thermoplastic resin whose main component is an acrylic resin, a polystyrene resin, or a mixture of both. By using such a resin sheet as the base sheet, excellent transparency and moldability can be imparted. As the acrylic resin or the polystyrene resin, a resin conventionally known as a resin sheet may be used. For example, as the acrylic resin, polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-
Butyl (meth) acrylate copolymer, methyl (meth)
An acrylic resin such as an acrylate-styrene copolymer (provided that (meth) acrylate means acrylate or methacrylate). Examples of the styrene-based resin include polystyrene and acrylonitrile-styrene copolymer (AS resin). These resins are
A sheet of a single layer or a laminate of two or more layers as a single substance or as a mixture of two or more kinds (including any combination of different acrylic resins, different polystyrene resins, and acrylic resin and polystyrene resin) Used as The base sheet may be colored and transparent in addition to colorless and transparent. In addition, if the base material sheet is mainly composed of an acrylic resin or a styrene resin, other resins may be contained in the range of subcomponents as needed for adjusting physical properties as needed. In the base sheet, if necessary, benzotriazole-based, benzophenone-based, ultraviolet absorbers such as fine cerium oxide-based, light stabilizers such as hindered amine radical scavengers, plasticizers, stabilizers, Various additives such as a coloring agent may be added for adjusting physical properties. The thickness of the substrate sheet is not particularly limited, but is generally 20 to 5
It is about 00 μm.

[Surface Protective Layer] The surface protective layer 2 is made of a cross-linking-curable acrylic resin. The surface protective layer is a layer for improving surface physical properties such as solvent resistance. In addition, since the surface protective layer is a layer made of a crosslinked cured material in a painted product, the surface physical properties such as scratch resistance can be improved with respect to a base sheet made of a thermoplastic resin sheet. . Usually, the surface protective layer is a transparent layer. As the crosslink-curable acrylic resin, for example, a two-pack curable resin that crosslinks and cures an acrylic polyol with isocyanate, a two-pack curable resin that crosslinks and cures with a silane coupling agent, or the like is used. By using an acrylic resin as a cross-linking cured resin, in addition to surface properties such as solvent resistance, weather resistance, or an acrylic resin or a styrene resin, especially a base material mainly composed of an acrylic resin It can be excellent in adhesion to a sheet and the like.

The acrylic polyol is not particularly limited, and may be selected and used from conventionally known ones according to the use and required physical properties. The acrylic polyol is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, -n-propyl (meth) acrylate,
Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, octyl (meth) acrylate, and alkyl (meth) acrylate such as ethylhexyl (meth) acrylate;
Acrylic monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate Is a polyol having a plurality of hydroxyl groups. If necessary, a styrene monomer may be further copolymerized in addition to the above. In addition, (meth) acrylic acid means acrylic acid or methacrylic acid.

As the above isocyanate, for example,
Aromatic isocyanate such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or fat such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate A group (or alicyclic) isocyanate or an adduct or a polymer of these various isocyanates may be used. For example,
Adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and the like.

As the silane coupling agent, a known silane coupling agent having an amino group, a vinyl group, an epoxy group, a mercapto group, a chloro group and the like in addition to the alkoxy group may be used. For example, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxy Propyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane,
γ-acryloxypropylmethyldiethoxysilane, γ
-Acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like. In the case of a silane coupling agent, the amount added as a crosslinking agent to the acrylic polyol is about 5 to 15 parts by weight based on 100 parts by weight of the polyol.

The surface protective layer may be composed of only a cross-linkable curable acrylic resin, but may optionally contain various additives.

For example, lubricants such as polyethylene wax and paraffin wax, lubricating agents consisting of particles such as silica, spherical α-alumina, and flaky α-alumina, and ultraviolet absorption such as benzotriazole, benzophenone, and fine cerium oxide. Various additives such as a light stabilizer such as an agent and a hindered amine radical scavenger, a plasticizer, a stabilizer, and a colorant may be added to adjust physical properties.

The method for forming the surface protective layer is not particularly limited, but may be any known method such as a printing method such as gravure printing or silk screen printing, or a coating method such as gravure coating or roll coating. good. The thickness of the surface protective layer may be appropriately set according to the required physical properties, applications, and the like, and is usually about 1 to 10 μm.

[Decoration Layer] The decoration layer 3 is a layer in which a pattern or the like is formed by a conventionally known printing method or material such as gravure printing, silk screen printing, offset printing or the like. The pattern is suitable for the application, for example, wood pattern, stone pattern, cloth pattern, tile pattern, brick pattern, leather pattern,
Use characters, geometric patterns, solid colors, etc. In addition, all solid patterns may be formed by coating with a gravure coat or the like. The ink (or coating liquid) for forming the decorative layer, like a general ink (or coating liquid), is composed of a vehicle such as a binder, a coloring agent such as a pigment or a dye, and various additives appropriately added thereto. As the resin used for the binder, for example, a simple substance such as an acrylic resin, a vinyl chloride-vinyl acetate copolymer, a polyester resin, a polyurethane resin or the like, or a mixture containing these resins is used. Examples of the coloring agent include inorganic pigments such as titanium white, carbon black, red iron oxide, graphite, and ultramarine blue; organic pigments such as aniline black, quinacridone, isoindolinone, and phthalocyanine blue; and glittering properties such as titanium dioxide-coated mica foil powder. A pigment or other dye is used. Further, a metal thin film layer or the like may be used as the decoration layer.
Aluminum, brass, gold, silver,
It is formed by a vacuum evaporation method, a sputtering method, or the like using copper, chromium, or the like. In addition, the metal thin film layer is an entire surface or a partial (picture-like or the like) layer. The decorative layer 3 is often formed on the back surface (molded side) of the base sheet 1 as shown in FIG. 1, but is formed on the front side (opposite the molded body) of the base sheet 1. You can also.

In the present invention, since the main component of the base sheet is an acrylic resin or a polystyrene resin, the resin of the binder is an acrylic resin and a vinyl chloride resin.
A mixture with a vinyl acetate copolymer is preferred. The acrylic resin improves the adhesion to the base sheet, and the vinyl chloride-vinyl acetate copolymer improves the suitability for printing (or coating) and the suitability for molding.

Here, the acrylic resin is appropriately selected from those listed for the surface protective layer, as well as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. , 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and other alkyl (meth) acrylates; 2-hydroxyethyl (meth) acrylate; 2-hydroxybutyl (meth) acrylate;
An acrylic polyol obtained by copolymerizing a (meth) acrylate having a hydroxyl group in a molecule such as -hydroxy-3-phenoxypropyl (meth) acrylate can also be used. Further, as the vinyl chloride-vinyl acetate copolymer, the vinyl acetate content is usually 5 to 20.
Those having a weight percentage of about 350 and an average degree of polymerization of about 350 to 900 are used. If necessary, a carboxylic acid such as maleic acid or fumaric acid may be further copolymerized with the vinyl chloride-vinyl acetate copolymer. The mixing ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer is about 1/9 to 9/1 (weight ratio) of the acrylic resin / vinyl chloride-vinyl acetate copolymer.

[Other Decorations] The painting sheet of the present invention usually has a structure in which the above-mentioned decoration layer is formed, but may be a sheet which has been subjected to decoration processing other than the decoration layer. For example, coloring by adding a coloring agent to the base sheet itself. Specifically, it is a painting sheet or the like in which only the surface protective layer is formed on the surface to be the front side of the base sheet colored by adding a coloring agent without a decorative layer. In this case, the coloring of the base sheet may be transparent or opaque. The coloring agent is various inorganic pigments, organic pigments, brilliant pigments, dyes or the like as described in the decorative layer. In the simplest example, a configuration in which only a surface protective layer is formed on an uncolored base sheet may be used. This painting sheet is used, for example, for the purpose of imparting a feeling of painting, or improving the solvent resistance of the molded article itself to be adhered. The surface protection layer is usually transparent, but when the decoration is not decoration by a pattern such as a decoration layer, the surface protection layer may be opaque (for example, the surface protection layer and the base sheet are made to have the same color, and the concealing properties are both provided. Etc.). In addition, as a decoration process in the decorating sheet, there is shaping of a concavo-convex pattern on the base sheet by embossing or the like. The concavo-convex pattern is usually formed as a grain pattern, a matte pattern, or the like on the surface on the front side of the base sheet.
Of course, the surface protection layer is formed on this uneven pattern.

[Adhesive Layer] If the adhesion between the decorative sheet and the molded product is insufficient, a corona discharge treatment is applied to the back surface of the decorative sheet in contact with the molded product to improve the adhesiveness. The back surface may be subjected to an easy-adhesion treatment such as various primer coatings, or this adhesive layer may be provided by a known printing or coating method such as gravure printing or roll coating. Known resins such as a thermoplastic resin and a thermosetting resin are used for the adhesive layer. For example, in the case of a thermoplastic resin, a styrene resin such as polystyrene and poly-α-methylstyrene or a styrene copolymer, an acrylic resin such as poly (methyl) acrylate, ethyl poly (meth) acrylate, and butyl poly (meth) acrylate are used. Resin, chlorinated polyolefin resin such as chlorinated polypropylene, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, vinyl polymer such as polyvinyl butyral, polyisoprene rubber, polyisobutyl rubber, styrene butadiene rubber, butadiene One or a mixture of two or more of a rubber-based resin such as acrylonitrile rubber and a thermoplastic resin such as a polyamide resin is used. As the thermosetting resin, a urethane resin, an epoxy resin, or the like is used. The method of forming the adhesive layer is not particularly limited, but is usually formed by a known printing or coating means such as gravure printing or roll coating as an ink or coating liquid composed of a resin liquid obtained by diluting the above resin with a diluting solvent. I do.
The thickness of the adhesive layer is not particularly limited, but is usually 1 to
It is about 100 μm.

[Other layers] For example, in order to improve the interlayer adhesion between the base sheet and the surface protective layer, the base sheet and the decorative layer, the decorative layer and the adhesive layer, a primer is provided between the layers. Layers may be provided as needed. The resin of the primer layer is not particularly limited, and may be appropriately selected from known ones. For example, a urethane resin may be used. As the urethane resin, a thermoplastic urethane resin or a two-component curable urethane resin may be used. Further, the primer layer may be formed by a known printing method (or coating method) such as gravure printing (or roll coating) using an ink (or coating liquid) containing such a resin.

The painted molded article of the present invention is the same as the painted molded article P illustrated in FIG. 2 except that the above-described painted sheet S of the present invention has the surface protective layer 2 on the front side. Thus, the molded article 5 is painted on the surface of the molded article 5 by being laminated. By the way, the painted molded product P in FIG.
The painting sheet S including the surface protective layer 2, the base sheet 1, the decorative layer 3, and the adhesive layer 4 is laminated on the molded product 5 from the front side. Although the adhesive layer 4 is illustrated as a component of the painting sheet S, it may be supplied after being applied to the molded product 5 side (for example, when manufacturing by a vacuum forming lamination method). The painting sheet S used for the painting molded article P in FIG. 2 corresponds to the painting sheet S in FIG. Since the surface protective layer is made of a cross-linking-curable acrylic resin, the molded article has excellent surface properties such as solvent resistance. Note that, of course, in the painted molded article, the cross-linkable acrylic resin of the surface protective layer is a cured product. In addition, since an acrylic resin or a styrene resin having excellent transparency is used for the base sheet, an excellent painting feeling can be obtained.

Note that the painted molded article is usually a three-dimensional object having a non-planar surface such as an uneven surface due to the lamination of the painting sheets. However, the painting molded article of the present invention does not exclude a three-dimensional object whose painting surface is flat but the other surface is non-planar and a plate-like object whose painting surface is flat.

Although the painted molded article of the present invention can be easily obtained by using the above-described painted sheet of the present invention, if the structure is the same, the painted sheet of the present invention can be used. It does not exclude products manufactured without.
For example, it is a painted molded product in which each layer on a resin molded product is formed by painting or hand drawing. Alternatively, after laminating a painting sheet on which only the above-mentioned surface protective layer is not formed on a molded product,
It is a painted molded article or the like in which the surface protective layer is formed by painting or the like.
However, it is of course preferable to use the above-described painting sheet of the present invention because of easy production. Further, as a method for producing a painted molded article by painting a molded article with such a painting sheet, a so-called simultaneous injection molding painting method is suitable. However, the method for obtaining the painted molded article of the present invention is not limited to this injection molding simultaneous painting method. For example,
It can also be obtained by another painting method as appropriate according to the molded article (the shape of the painting surface by the painting sheet in the adherend), the available manufacturing equipment, and the like. For example,
No. 45768 (overlay method), Japanese Patent Publication No. 60-5
A so-called vacuum forming and laminating method described in JP-A-8014 (vacuum pressing method) and the like, a lapping method described in JP-B-61-5895, and the like may be used. Of course, it is preferable to adopt the simultaneous injection molding painting method in that molding and painting can be performed simultaneously in one step, and the production efficiency is good.

[Molded Article] The molded article 5 is a resin molded article which is formed simultaneously with the molding of the painted article when the painted article is obtained by the simultaneous painting method of injection molding. When a painted product is obtained by a molding lamination method or the like, it is a molded product that has already formed before the production of the painted product. In the case of the latter, a resin molded product may be used, but a molded product of a material other than the resin may be used. For example, for example, MDF
It is a molded product obtained by molding a wood-based material such as (medium-density fiberboard), a metal-based material such as iron, or a non-metallic inorganic-based material such as ceramics by various known methods such as cutting and pressing. In these, the material of the molded product is not particularly limited and may be a known material, and may be selected according to the method of laminating the painting sheet, application, required physical properties, cost, and the like.

For example, as a resin to be a resin molded product used in the simultaneous painting method for injection molding, if it is a thermoplastic resin, for example, ABS (acrylonitrile-butadiene-styrene copolymer) resin, styrene resin, acrylic resin Resin, vinyl chloride resin, polycarbonate resin, or polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-
Polyolefin resins such as propylene-butene copolymers and olefin thermoplastic elastomers. Also,
If it is a curable resin, it is a two-part curable resin, for example, an uncured resin liquid such as a urethane resin, an unsaturated polyester resin, or an epoxy resin. In the simultaneous painting method for injection molding, the thermoplastic resin is heated and melted, injected into the cavity in a fluidized state, and cooled and solidified. In addition, the curable resin (the uncured product) is injected at room temperature or by appropriately heating and flowing, and is crosslinked and polymerized to be solidified.

The simultaneous injection molding picture Tsukekata method Next, the preferred one way of obtaining decorating molded article of the present invention, so-called simultaneous injection molding painting method, previously described herein.

In the simultaneous painting method of injection molding, Japanese Patent Publication No. 50
As described in JP-19132, JP-B-43-27488, etc., after the painting sheet is arranged between the male and female molds for injection molding, a resin in a fluid state is injected and filled into the mold. This is a method in which a painting sheet is laminated on the surface of a molded article and painted at the same time.

In the simultaneous injection molding painting method, conventionally known various forms can be adopted. For example, the form in which the pre-forming of the painting sheet is performed or not may be performed. Further, the pre-heating of the painting sheet may or may not be performed. Note that the painting sheet is usually preheated during the preforming. Of course, if the drawing sheet has a large aperture,
Preforming is preferably performed. On the other hand, when the drawing sheet has a small aperture, the painting sheet can be formed only by the resin pressure of the resin in the flowing state to be injected. At this time, if the drawing is small, the painting sheet may be formed only by the resin pressure of the resin in a flowing state to be filled in the mold at the same time as the resin injection without the preliminary molding. Further, even when the painting sheet is formed by the resin pressure, the painting sheet may utilize the heat of the injection resin without preheating. In addition, in the preforming of the painting sheet, usually, the injection molding die is also used as a vacuum molding die, but before supplying the painting sheet between the dies, the painting sheet is formed with another vacuum molding die outside the mold. Preforming such as vacuum forming may be used. In addition, the vacuum forming includes vacuum pressure forming.

The injection molding simultaneous painting method will be described with reference to a conceptual diagram of FIG. In addition, the form described here is a form in which the painting sheet is heated and softened between the molds, pre-molded by vacuum molding with an injection mold, and then resin is injected by clamping before the mold is clamped. . This form is a more preferable form when the drawing sheet has a large aperture among the various combinations of the preforming and preheating of the painting sheet described above.

First, as shown in FIG. 3A, as an injection mold, a mold Ma having a runner (runner) and a gate (gate) communicating with the injection nozzle, and a suction hole 4 in the cavity surface.
A pair of molds Mb having the number 1 and also serving as a sheet preform is used. These molds are made of metal such as iron or ceramics. Both molds Ma and Mb in the mold open state
The painting sheet S is supplied in between and the painting sheet S is supplied to the mold Mb.
Is fixed by pressing or the like with a frame-shaped sheet clamp 42. At this time, the surface protection layer side, which is the front side surface of the painting sheet, faces the cavity surface side of the mold Mb on the left side of the drawing, and the back side surface where the adhesive layer and the like are appropriately provided is the injection resin side on the right side of the drawing. Of course you do. Next, the painting sheet is appropriately heated and softened by a heater (not shown) inserted between the two molds. The heating is, for example, non-contact radiation heating, but may be conduction heating by contact. Then, it is sucked through the suction hole and vacuum formed, and the painting sheet is preformed along the cavity surface of the mold Mb. Note that the vacuum forming may be vacuum press forming using both compressed air and compressed air. Next, the heater is retracted from between the two dies, the two dies are clamped as shown in FIG. 3B, and a cavity formed by the two dies is filled with a resin in a flowing state such as a heated and molten state. After the resin is solidified by cooling or the like, the mold is opened and the molded product is taken out. If there is an unnecessary portion of the painting sheet, trimming is appropriately performed. Then, as shown in FIG. 2, a painted molded article P having a configuration in which the painted sheet S is laminated on the molded article 5 and painted is obtained.

At the stage immediately after the simultaneous painting by injection molding,
When the cross-linking-curable acrylic resin of the surface protective layer is not yet cross-linked and cured, the painted molding is appropriately heated by an oven or the like to complete the curing and obtain final surface physical properties. Like

[0034]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples.

[Example 1] A painting sheet S having a structure as shown in Fig. 1 was used as a base sheet 1 made of a transparent acrylic resin sheet having a thickness of 125 µm. After the decorative layer 3 (including the entire solid layer) and the adhesive layer 4 are formed in this order, the other surface is composed of 100 parts by weight of an acrylic polyol and 20 parts by weight of a silane coupling agent as a crosslinking agent. A coating liquid composed of a liquid-curable cross-linkable acrylic resin was applied by gravure coating to form a surface protective layer 2, and a painting sheet S was produced. In the decorative layer, the binder resin is one of an acrylic resin and a vinyl chloride-vinyl acetate copolymer.
The mixture was in a weight ratio of 1: 1. As the colorant, a red ink was added to which a red ink was added. For the adhesive layer, an adhesive composed of a vinyl chloride-vinyl acetate copolymer was used.

The above-mentioned painting sheet is laminated on the surface of the molded article made of resin simultaneously with the molding of the molded article by the simultaneous painting method of injection molding as shown in the conceptual diagram of FIG.
As a result, a painted molded product P of the present invention having a configuration in which the painted sheet S was laminated on the molded product 5 was obtained. In addition, in the simultaneous injection molding painting method, the painting sheet was formed by using an injection molding die as a vacuum molding die, supplying between the dies, softening by heating, and preforming by vacuum molding. In addition, the injection mold
A mold having a suction hole for preforming a sheet on a female mold side was used as a mold from which a molded product to be a box-shaped panel was obtained.
In addition, an ABS resin was used as the injection resin.

Example 2 A decorating sheet was produced in the same manner as in Example 1 except that the styrene resin sheet was used instead of the acrylic resin sheet as the base sheet. Then, in the same manner as in Example 1, using this painting sheet, painting was performed simultaneously with injection molding to obtain a painted molded product.

Comparative Example 1 A painting sheet 10 having the structure shown in FIG. 4 was produced in the same manner as in Example 1 except that the formation of the surface protective layer was omitted. That is, it is a sheet in which the decorative layer 3 and the adhesive layer 4 are formed in this order on one surface of the base sheet 1. Then, in the same manner as in Example 1, using this painting sheet, painting was performed simultaneously with injection molding to obtain a painted molded product.

Comparative Example 2 A painting sheet 10 having the structure shown in FIG. 4 was produced in the same manner as in Example 2 except that the formation of the surface protective layer was omitted. A painting sheet was prepared. Then, in the same manner as in Example 1, using this painting sheet, painting was performed simultaneously with injection molding to obtain a painted molded product.

[Evaluation of Performance] As the surface physical properties of the painted molded product, the solvent resistance was comparatively evaluated for each Example and each Comparative Example. The solvent resistance was measured by a drop test in which methyl ethyl ketone as an organic solvent was dropped on the surface (painted surface) of a painted product and visually evaluated for abnormal appearance after drying. As a result, in Examples 1 and 2, no whitening was observed on the surface, and the solvent resistance was good. However, in Comparative Examples 1 and 2 without the surface protective layer, whitening was observed 3 minutes after the addition of the solvent,
The solvent resistance became poor. In addition, the painted molded products of Examples 1 and 2 became highly-designed painted products due to the excellent paint feeling overflowing with transparency.

[0041]

According to the painting sheet of the present invention, even if a base sheet made of an acrylic resin or a polystyrene resin having excellent moldability and transparency is used, the painting sheet having excellent solvent resistance can be obtained. Become. According to the painted molded article of the present invention, the painted surface is a molded article having excellent solvent resistance. In addition, the acrylic resin or styrene resin of the base sheet makes it possible to form a highly decorative painted product with a highly transparent coating feeling.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a painting sheet of the present invention in one form.

FIG. 2 is a cross-sectional view illustrating the painted product of the present invention in one form.

FIG. 3 is a conceptual diagram illustrating an example of a simultaneous painting method for injection molding as an example of a method for manufacturing a painted article.

FIG. 4 is a sectional view showing an example of a conventional painting sheet.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base sheet 2 Surface protection layer 3 Decorative layer 4 Adhesive layer 5 Molded article 10 Conventional painting sheet 41 Suction hole 42 Sheet clamp Ma Injection molding die (male) Mb Injection molding die (female) P Painting Product S Painting sheet

Continued on the front page F-term (reference) 4F100 AH06 AK12A AK15 AK22 AK25A AK25B AK54 BA02 BA16 CA13 CB00 EH36 EJ05B EJ08B EJ24 EJ91 HB00 HB01 HB31 JB07 JB12B JN01 4F202 AA13 A11 AA12 A12 AA12 AA12 A28 AD20 AG03 JA07 JB13 JB22 JF05 JQ81

Claims (2)

[Claims] 1. A painting sheet for laminating on the surface of a molded product, wherein a cross-linking hardening type is provided on a surface of a base sheet mainly composed of an acrylic resin, a polystyrene resin, or a mixture of both. A painting sheet on which a surface protective layer made of an acrylic resin is formed. 2. A painted molded article, wherein the painted sheet according to claim 1 is laminated on the surface of the molded article such that the surface protective layer is on the front side.