JPH0247543B2 - - Google Patents

Description

[Detailed description of the invention]

Technical Field of the Invention The present invention relates to a method for producing a molded product for chemical plating, which is made of a thermoplastic resin that can be used as a printed circuit product with excellent adhesion to metal and solder heat resistance using a special connecting agent. This invention relates to a method for obtaining a molded product for chemical plating. Technical Background of the Invention Conventionally, ABS resin has been used as a material that can be easily plated on the surface of thermoplastic resin molded products. However, in general, the surface of each molding is mirror-like and cannot be easily plated. Therefore, there are methods in which the molded product is swollen in a solvent and then chemically plated, or an adhesion improver is applied to the surface of the molded product by dipping, roll coating, or brushing, dried, and then chemical plating is applied. There is a way to do it. When molded products are plated by these methods, the plating is mostly done to give the surface a metallic appearance or for decorative purposes. Problems with the Known Techniques Therefore, most of the platings described above are not required to have the level of adhesion required for printed circuit boards and have low heat resistance. Although ABS resin had excellent adhesion, it had significantly poor heat resistance, making it unsuitable for use in printed circuits. These conventional printed circuit products obtained by chemically plating thermoplastic resin molded products have the drawback of low reliability in terms of adhesion strength and solder heat resistance. Purpose of the Invention The present invention has been made in view of the above points, and
As a result of extensive research into adhesives for plating formed on the surface of thermoplastic resin molded products, we have developed a molded product made of a special adhesive and polyphenylene sulfide resin, polyphenylene oxide resin, or polybutylene terephthalate resin using a chemical method. It has been found that when plated and used as a printed circuit product, a chemically plated molded product with good adhesion strength and solder heat resistance and sufficient reliability can be produced. SUMMARY OF THE INVENTION The present invention provides a thermoplastic resin molded product that is composed of butadiene nitrile rubber, xylene resin, epoxy resin, sulfur, and dicyandiamide on the surface of a thermoplastic resin molded article, and that the butadiene nitrile rubber is the sum of butadiene nitrile rubber, xylene resin, and epoxy resin. The composition contains 30 to 60% by weight based on the amount
A thermosetting resin adhesive containing 100 parts by weight and 5 to 20 parts by weight of finely powdered silicon oxide is applied to a thickness of 15 to 20 parts by weight.
This is a method for producing a molded product for chemical plating, characterized in that by uniformly coating the adhesive layer to a thickness of 70 μm and curing it by heating, activation treatment can be applied to the adhesive layer as a printed circuit product. The present invention will be explained in detail below. The molded article molded using the thermoplastic resin of the present invention is molded from any one of polyphenylene sulfide resin, polyphenylene oxide resin, and polybutylene terephthalate resin. They may be reinforced with glass fibers, carbon fibers, or unreinforced. Commercially available products include Ryton (manufactured by Philips Oil Co., Ltd.), Daigomp (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Noryl, and Barox (manufactured by General Electric Company). The molded product may be a three-dimensional molded product or a plate-like product, and the shape is not particularly important. The special adhesive used in this invention is
The first component is butadiene nitrile rubber, which is a copolymerization of acrylonitrile and butadiene or a third component such as acrylic acid.
Commercial products of such butadiene nitrile rubber include, for example, Nipole 1042 (trade name manufactured by Nippon Zeon Co., Ltd.) and Hiker 1072 (trade name manufactured by Gutsudoritsu Co., Ltd.).
and so on. The amount of butadiene nitrile rubber to be used is 30 to 60% by weight based on the resin content (total amount of the first to third adhesive components), taking into account the adhesion, heat resistance, and electrical properties of the plating metal layer. You can choose as appropriate. The xylene resin, which is the second component of the adhesive, is a phenol-modified resin obtained by reacting xylene and formaldehyde in the presence of a catalyst, and is commercially available as Nicanol (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.). Considering the adhesion and electrical insulation properties of the plating metal layer when heated, it is preferable to use the resin in an amount of 60 to 10% by weight based on the resin content. Examples of the epoxy resin, which is the third component, include bisphenol type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, etc. Considering the adhesion and heat resistance of the plating metal layer, the amount of resin used is It is preferable to use 10 to 30% by weight. Further, by adding dicyandiamide and sulfur as a crosslinking agent, improvement in heat resistance is observed. As the adhesive component of the present invention, the composition consisting of the above-mentioned butadiene nitrile rubber, xylene resin, epoxy resin, sulfur and dicyandiamide is sufficient to achieve the purpose, but if finely powdered silicon oxide is further added to this, this composition can be used. It has been found that when the molded product is used as a printed circuit product with a metal layer coated by chemical plating, the solder heat resistance is significantly improved. The mixing ratio of silicon oxide is preferably in the range of 5 to 20 parts by weight per 100 parts by weight of the resin. If it is less than 5 parts by weight, no effect can be obtained, while if it exceeds 20 parts by weight, it becomes difficult to form an adhesive suitable for chemical plating, and various properties are adversely affected. The above adhesive components are dissolved in an appropriate organic solvent to form a solution, applied to the surface of the molded product by dipping, roll coating, curtain coating, brush coating, etc. and drying, followed by a specified chemical plating method. It can be used for printed circuit products with metal layers. Next, the present invention will be specifically explained with reference to Examples. Parts below mean parts by weight. Example 1 80 parts of butadiene nitrile rubber, epoxy resin
Add 60 parts of xylene resin, 2.4 parts of dicyandiamide, 1 part of sulfur, and 0.09 parts of curing accelerator to a solution in which 60 parts of methyl ethyl ketone are swollen and dissolved in 500 parts of methyl ethyl ketone and 200 parts of toluene.
1 part, and 20 parts of finely powdered unoxidized silicon were added thereto and thoroughly stirred and mixed to prepare an adhesive solution. Next, the thickness was molded using polyphenylene sulfide resin.
The coating thickness is different on both sides of the 2.0m/m molded product.
The adhesive was applied to a thickness of 40 to 50 μm and dried to form an adhesive film. Further, it was heated and dried at 150°C for 1 hour to obtain a molded product for chemical plating. This molded product was immersed in a chromium sulfuric acid solution (consisting of 75 g of chromic anhydride, 300 ml of concentrated sulfuric acid, and 700 ml of water) at 50°C for 7 minutes, and after making it hydrophilic, it was sequentially subjected to an activation treatment and a chemical plating treatment. A 0.5 μm copper plating layer was provided, and electroplating was further applied to build up to approximately 35 μm. Regarding the molded product with the above-mentioned copper plating layer,
Peel strength and solder heat resistance tests and electrical tests were conducted in accordance with JIS C-6481 copper clad laminate test method for printed circuits. The results are shown in Table 1 along with the compositions of the molded product and adhesive described above. Example 2 Example 1 was applied so that the thickness of the coating film was 30 to 40 μm on both sides of a 2.0 m/m thick molded product molded using polybutylene terephthalate resin.
The adhesive solution prepared above was applied and dried to form an adhesive film. Further, this film was dried by heating at 140° C. for 1 hour to obtain a molded article for chemical plating. Example 1
A molded product with a copper plating layer obtained by performing copper plating treatment in the same manner as above was tested in accordance with JIS C-6481 Test Method for Copper Clad Laminates for Printed Circuits. The results of this journal experiment are shown in Table 1. Examples 3 to 6 Adhesive solutions were prepared in which the amount of finely powdered silicon oxide added was changed from the adhesive composition in Example 1,
Adhesive films were formed on both sides of the molded product in the same manner as in Example 1, and the molded product was further heated and dried at 150° C. for 1 hour to obtain a molded product for chemical plating. Regarding the types of resins used for the molded products, those shown in Table 1 were used. Example 1
Table 1 shows the test results of molded products obtained by copper plating in the same manner as above. Comparative Example 1 Nitrile Rubber 100 was used instead of the adhesive of the present invention.
An adhesive consisting of 150 parts of phenol resin was prepared, and an adhesive film was formed on a polyphenylene sulfide resin molded article in the same manner as in Example 1. Next, the molded articles obtained by heating and drying at 150 DEG C. for 1 hour and chemically plating in the same manner as in Examples 3 to 6 were subjected to the same tests, and the results are shown in Table 1.

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Claims (1)

[Claims] 1. Butadiene nitrile rubber, xylene resin, epoxy resin,
100 parts by weight of a composition consisting of sulfur and dicyandiamide and containing 30 to 60% by weight of the butadiene nitrile rubber based on the total amount of the butadiene nitrile rubber, xylene resin and epoxy resin, and 5 to 20 parts by weight of finely powdered silicon oxide. By uniformly applying a thermosetting resin adhesive with a thickness of 15 to 70 μm and curing it by heating, it is possible to apply activation treatment to the adhesive layer as a printed circuit product. Characteristic method for manufacturing molded products for chemical plating.