JPH0725910B2 - Transparent resin molding having a colored layer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention has a weather resistance having a colored layer and a hard coat layer for improving the low abrasion resistance, which is the greatest drawback of plastic materials. The present invention relates to a transparent resin molded product having various physical properties such as properties.

[Prior Art] In recent years, a molded body made of a transparent plastic material has advantages such as light weight, easy workability and excellent impact resistance in place of transparent glass. Widely used as a material. However, these plastic materials do not have sufficient strength against friction and are easily scratched, so a hard coat treatment with a hard coat agent is applied, but the hard coat surface is poor in hydrophilicity and is chemically stable. Normal paint is hard to attach,
Also, the adhesiveness is poor. On the other hand, these plastic materials naturally need to be provided with a colored layer in order to perform various types of display. For example, there is one that uses a resin plate such as a polycarbonate plate or an acrylic plate in place of the windshield of an automobile. Generally, when attaching the windshield of an automobile to a window frame, a weather strip made of rubber is fitted around it. In order to broaden the field of view, the peripheral edge of the glass may be directly adhered to the window frame, and in order to hide the adhered part from the outside, only the peripheral edge may be painted black. Therefore, even when a transparent plastic material is used instead of the wind glass, it is necessary to apply such coating. Plastic materials are generally difficult for paints to adhere to, and in particular, hard coat agents for improving the abrasion resistance of plastic surfaces are generally silicone-based agents, which have little adhesion to various paints. Therefore, it has been difficult to use a hard-coated plastic material for such an application. As a means for solving such a problem, it is possible to remove the hard coat layer by sandblasting the periphery of a polycarbonate plate having a silicone-based hard coat layer, and then form a black coating film on the removed portion. A proposal has been made (Japanese Utility Model Laid-Open No. 61-78628), but this method requires one extra step and is inefficient. Further, a method has been proposed in which the surface of a silicone-based hard coat layer is roughened, and then plasma treatment is performed to increase the activity of the surface, and then a coating film is formed (JP-A-62-121735). The method also requires extra steps such as surface roughening and plasma treatment, and the apparatus is expensive and not industrial.

[Means for Solving Problems] The present inventors have arrived at the present invention as a result of earnest studies in view of the conventional problems. That is, the present invention is based on a transparent resin molding, vinyl-acrylic resin-based, vinyl-based
A transparent resin having a colored layer characterized in that at least one colored layer selected from a methacrylic resin type and a modified polyester resin type, a polymethylmethacrylate type primer layer, and a silicone type hard coat layer are sequentially formed. It is a molded body.

Examples of the transparent resin molded article that is the object of the present invention include resins having excellent impact resistance and high transparency such as polycarbonate and acrylic resin.

In the present invention, since the hard coat treatment is performed after the formation of the colored layer, the colored layer can be formed on the flat resin plate, and highly accurate printing can be performed by screen printing. On the other hand, when the colored layer is formed after the hard coat treatment, the hard coat layer is too hard to be curved after the hard coat layer is formed. In forming the colored layer, since a curved surface is formed, screen printing cannot be performed, and a means such as spraying is used, but it is not easy to form a colored layer having excellent adhesion through the hard coat layer. , The hard coat layer of the colored layer forming portion must be peeled off beforehand, or the colored layer forming portion must be masked in advance before the hard coat treatment, and the adhesion to the curved hard coat surface is excellent. Even if the colored layer can be formed, masking is required at that time, and highly accurate coloring is difficult, and the working environment is deteriorated, which is not preferable.

In the present invention, the colored layer is sandwiched between the transparent resin body and the primer layer, and it is, of course, necessary that the colored layer and the primer layer are well compatible with each other. It is necessary that the substance does not elute due to the influence of the solvent in the drug.

From these viewpoints, the present inventors have earnestly studied various paints and inks, and as a result, vinyl / acrylic resin-based, vinyl / methacrylic resin-based or modified polyester resin-based inks satisfy these required performances. I found it. Examples of such an ink include a screen process ink SS8 manufactured by Toyo Ink Mfg. Co., Ltd. as a vinyl / acrylic resin system, an Eight special manufactured by Nagase Screen Printing Laboratory Co., Ltd. as a vinyl / methacrylic resin system, and a modified polyester resin system. Examples include Seiko Advance's PAC II. As the primer agent used in the present invention, it is preferable to use a polymethylmethacrylate-based one, which is usually diluted with a solvent such as ethyl cellosolve, for example, Toshiba Silicone Co., Ltd.
Made by PH91 or PH93. In the present invention, a silicone-based hard coat layer is formed as a top coat on this primer layer.
In particular, those mixed with colloidal silica are preferable, and examples include Tosgard 510 manufactured by Toshiba Silicone Co., Ltd.

The colored layer ink used in the present invention is usually dried at room temperature, but is preferably dried at about 100 ° C. in order to prevent denaturation by the primer applied thereon.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1 Various black inks were screen-printed on a 50 mm × 200 mm × 3 mm polycarbonate plate (Teijin Kasei Panlite) using a 250 mesh Tetoron screen. After drying at 100 ° C for 30 minutes, a colored layer test was conducted to evaluate the adhesion of the colored layer. Only those with a result of 100/100 were washed with a trichlorotrifluoroethane-ethanol azeotrope solvent (CG Triflon E manufactured by Central Glass Co., Ltd.), and then used as a primer PH91 (PMMA system manufactured by Toshiba Silicone Co., Ltd.). ) Was applied by dipping for 1 minute at room temperature. Visually observe the change in the black ink layer due to washing and primer treatment, and for only those with no abnormalities, dry at 25 ° C for 30 minutes, then use Silicone hard coat agent Tosugad 510 manufactured by Toshiba Silicone Co., Ltd.
Was applied by dipping for 1 minute at room temperature. 120
Various performance tests were performed by drying the test pieces at 1 ° C. for 1 hour. The results are shown in Table 1. The thickness of each coating layer was about 8 μm for the colored layer, about 1 μm for the primer layer, and about 5 μm for the hard coat layer.

The performance test method is as follows.

Scratch resistance: According to JASOM312-'85 5.9 method A. Rubbing using steel wool (# 000) at a surface pressure of 66 g / cm ² and a speed of 600 cm / min Is JIS Class No. 1 of JIS D0202-9-1 Appearance Criteria Table 15 Gobang Eye test: JIS K5400-6-15 And JIS D0202-8-1
According to 2, JISK5400-6-15 Table 11 rating score 10 and whether it is 100/100 in the adhesive tape test Boiling water resistance: According to JISK5400-7-3 (2 hours) Liquid resistance: with a dropper 0.3 to 0.5 cc is dropped, and it is left at room temperature for 4 hours and then left at 90 ° C ± 2 ° C for 4 hours, and whether it is Class 1 of JIS D0202-9.1 appearance judgment standard table 15 (gasoline and light oil are at room temperature. Leave for 8 hours) Repeated heat and cold test: According to JASOM312-85-5.1-4- (4),
High temperature depends on method B. The cooling / heating cycle is as follows.

110 ℃ × 3Hr → Room temperature × 0.5Hr → −40 ℃ × 2Hr → Room temperature × 0.5Hr
→ 70 ° C, 90% RH × 3Hr → Room temperature × 0.5Hr → −40 ° C × 14Hr → Room temperature × 0.5Hr (2 cycles or more) JISD0202-9.1 Appearance Criteria Whether or not it is Grade 15 in Table 15 Accelerated weather resistance: JISD0205-1976 7.7 Solvent resistance according to the sunshine carbon weather meter in Table 13: Conforms to JIS K5400 7.7. The ink used is as follows.

Ink: Toyo Ink Mfg. Co., Ltd. SS8-Conk 911 ink (vinyl chloride vinyl acryl resin type) Ink: Seiko Advance Co., Ltd. PAC II name plate (modified polyester type) Ink: Nagase screen printing research Eight special (vinyl chloride vinyl acetate / methacrylic resin type) Ink: MPX (modified vinyl chloride type) made by Nagase Screen Printing Laboratory, Inc. Ink: Lecrack # 72 (acrylic resin type) made by Fujikura Kasei Co., Ltd. Ink: Japan High Urethane No. 5000P (acrylic polyol type) manufactured by Yushi Co., Ltd. The liquids used for the liquid resistance test are as follows.

Sulfuric acid: 10% concentration Engine oil: Shell 10W-30 Sodium carbonate solution: 5% concentration Detergent: Kao Family Fresh Artificial sweat: Disodium phosphate (anhydrous) 3.17g, sodium chloride 8g, acetic acid 8g dissolved in distilled water 1 ethanol : Special grade washer fluid: AUTO CHEMICAL stock solution Gasoline: − Light oil: − Example 2 An acrylic resin plate (Paragrass R, manufactured by Kyowa Gas Chemical Co., Ltd.) was used as a transparent resin body, a primer PH93 (PMMA type) manufactured by Toshiba Silicone Co., Ltd. was used as a primer, and a product manufactured by Toshiba Silicone Co., Ltd. was used as a hard coating agent. A performance test was conducted in the same manner as in Example 1 except that Tosgard 520 (silicone type) was used. The results are shown in Table 2. However, the ink had poor adhesion and was not tested for performance.

EFFECTS OF THE INVENTION According to the present invention, a colored layer having excellent adhesiveness in screen printing by selecting a specific resin component among general-purpose inks for a resin having high impact resistance such as a polycarbonate resin plate and an acrylic resin plate. Can be formed easily and with high precision, and the molded product obtained by sequentially forming the primer layer and the hard coat layer has excellent abrasion resistance and extremely high adhesion between these layers, and has excellent weather resistance, for example, in automobiles. It can be fully used as a substitute for the wind glass of.

Claims (1)

[Claims] 1. A transparent resin molding, and at least one coloring layer selected from vinyl / acrylic resin, vinyl / methacrylic resin, and modified polyester resin, a polymethylmethacrylate primer layer, and a silicone resin. A transparent resin molded product having a colored layer, wherein a hard coat layer is sequentially formed.