JPH0116255B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a copper-clad laminate, and particularly to a method for manufacturing a copper laminate that has both antibacterial properties, properties as an electrically insulating material, and properties as a printed wiring board. Copper-clad laminates made of epoxy resin, silicone resin, polyimide resin, polyurethane resin, polyester resin, etc. used for printed wiring are susceptible to the growth of fungi (mold, bacteria, etc.) when exposed to high temperature and high humidity. . When bacteria grow on such copper-clad laminates, it causes major damage such as an extreme drop in electrical insulation, erosion of circuits, and changes in appearance. Recently, as circuits have become more precise, there has been a demand for highly reliable copper-clad laminates that do not allow even the slightest erosion of the circuits. For this reason, it would be desirable if the copper-clad laminates themselves could be made resistant to bacteria, but copper-clad laminates are manufactured through a high-temperature drying process or a molding process, and they also require an etching process or an etching process. The plating process involves intense exposure to chemicals.
Therefore, it was not easy to find a manufacturing method that could simultaneously satisfy the requirements of germ resistance, electrical insulation, and printed wiring processability. A commonly used method for manufacturing copper-clad laminates will be explained step by step. Depending on the purpose of use, thermosetting resins such as epoxy resins, polyimide resins, and silicone resins are dissolved in a solvent to create prepreg varnishes. A solvent is further added to this varnish to obtain a suitable viscosity for impregnation, and this is impregnated into a base material such as glass cloth or paper and dried to form a prepreg. Depending on the purpose of use, apply an adhesive resin liquid such as phenol resin, epoxy resin, vinyl butyral resin, etc. to one side of the copper foil, heat and dry it in an oven at 120 to 150°C for 5 to 20 minutes, and then apply the adhesive resin liquid to one side of the copper foil. The volatile content of the adhesive is adjusted to about 2 to 8% by weight to obtain an adhesive-coated copper foil. Layer several sheets of prepreg, then layer copper foil with adhesive, with the adhesive side facing the prepreg.
Sandwiched between press plates heated to 150-180℃,
A copper-clad laminate is obtained by heating and pressing under a pressure of 10 to 150 Kg/cm ² for 60 to 180 minutes. The present invention was developed as a result of various studies on manufacturing methods that provide copper-clad laminates with bacteria resistance, properties as an electrical insulating material, and properties as a printed wiring board.
The method described below was invented. That is, the present invention provides N-(trichloromethylthio)-4-cyclohexene-1,2-dicarbonimide, N-(fluorodichloromethylthio)
two or more compounds selected from the group consisting of phthalimide, 10,10'-oxybisphenoxaarsine, and 2-(4-thiazolyl)benzimidazole, or N-(trichloromethylthio)-4-cyclohexene-1, 2-dicarbonimide, or N
- (Fluorodichloromethylthio)phthalimide is added and mixed at a ratio of 0.02 to 2.0% by weight based on the resin solid content in the adhesive, and an adhesive is interposed between the copper foil and the laminate and bonded under heat and pressure. This is a method for producing a copper-clad laminate having antibacterial properties. The antibacterial agent used in the present invention has the following structural formula. (1) N-(trichloromethylthio)-4-cyclohexene-1,2-dicarbonimide [N-
(trichloromethylthio)-4-cyclohexene-
1,2-dicarboximide] (2) N-(fluorodichloromethylthio)phthalimide
phthalimide〕 (3) 10,10'-oxybisphenoxarsine [10,10-oxybisphenoxarsine] (4) 2-(4-thiazolyl)benzimidazole These antibacterial agents are antibacterial agents that do not lose their properties during the manufacturing and processing steps of the copper-clad laminate described above. The antibacterial agent is used by being added to the adhesive. By incorporating it into the adhesive, the invasion of bacteria into the circuit can be best prevented and the amount of antibacterial agent used can be minimized. Moreover, the growth of bacteria can be prevented even on the laminate surface of a single-sided copper-clad laminate. The amount of one or more antibacterial compounds to be added has been studied, and it is recommended that they be added at a rate of 0.02 to 2.0% by weight based on the resin solid content in the adhesive. If the amount added is less than the lower limit, sufficient bacterial resistance cannot be obtained. Furthermore, if the amount added exceeds the upper limit, it will begin to have an adverse effect on solder heat resistance, chemical resistance, peel strength, and electrical properties, which will not only be a practical hindrance, but also cause a decrease in bacterial resistance. . When adding and mixing the antibacterial agent to the adhesive, it is preferable to dissolve it in a solvent such as methyl ethyl ketone and then add it.
To bond the copper foil and the laminate, as described above, the copper foil with adhesive may be used and bonded at the same time as the prepreg is formed, or the copper foil may be stacked on a synthetic resin sheet and heated and pressed for bonding. It's okay. By adhering copper foil to a film, a flexible copper-clad board can be obtained. According to the present invention, a copper-clad laminate having antibacterial properties can be easily obtained by simply adding a step of adding and mixing an antibacterial agent to a copper foil adhesive. The obtained copper-clad laminate satisfies not only bacterial resistance but also electrical properties and properties for printed wiring, and is effective in preventing corrosion of circuits by bacteria in a very small amount. Examples will be shown below, but the present invention is not limited to these examples. Parts and % mean parts by weight and % by weight, respectively. Example 1 Adhesive: 45 parts of liquid phenolic resin using an alkali catalyst, epoxy resin (Araldite ECN
-1280 (trade name, Ciba Corporation) and 50 parts of polyvinyl butyral were dissolved in a 1:1 mixed solvent of ethyl alcohol and methyl ethyl ketone to prepare an adhesive having a concentration of 20%. Addition of antibacterial agent: As an antibacterial agent, Vinazine [10,
10'-Oxybisphenoxaarsine, trade name]
and TBZ [2-(4-thiazolyl)benzimidazole, trade name] were each dissolved in methyl ethyl ketone to make a 2% solution, and 0.25 parts each of a 2% solution of binazine and TBZ were added to 100 parts of the adhesive, and the mixture was heated at room temperature. The mixture was stirred and mixed until the mixture was sufficiently homogeneous. Adhesive-coated copper foil: An antibacterial agent-containing adhesive was applied to one side of a 35 μ thick copper foil, air-dried, and then dried at 120°C for 10 minutes to obtain an adhesive-coated copper foil. Copper clad adhesive: Copper foil with adhesive is superimposed on epoxy resin cellulose paper impregnated prepreg, heated at 150℃,
A copper-clad laminate (1.6 mm thick) was obtained by molding under heating and pressing conditions of 120 Kg/cm ² and 90 minutes. Examples 2 to 7 Paper-based epoxy resin copper-clad laminates and glass cloth-based epoxy resin copper-clad laminates were obtained in the same manner as in Example 1, except for the addition of adhesives and antibacterial agents. Adhesive: An adhesive was prepared in the same manner as in Example 1, except that the composition was as shown in Table 1. Addition of antibacterial agents: Dissolve each of the antibacterial agents shown in Table 2 in methyl ethyl ketone to make a 2% solution.
A 2% solution in the amount shown in the table was added to 100 parts of the adhesive, and the mixture was stirred and mixed uniformly.

【table】

[Table] Comparative Examples 1 to 3 Paper-based epoxy resin copper-clad laminates were prepared in the same manner as in Example 1, using an adhesive having the composition shown in Table 3 and without adding an antibacterial agent. Obtained.

[Table] Bacterial resistance, soldering heat resistance, adhesion, electrical properties, chemical resistance, etc. of Examples and Comparative Examples were measured.
Comparisons are shown in the table. The Example showed excellent results.

[Table] *Glass cloth base epoxy

Claims (1)

[Claims] 1 N-(trichloromethylthio)-4-cyclohexene-1,2-dicarbonimide, N-(fluorodichloromethylthio)phthalimide, 10,
10′-oxybisphenoxaarsine and 2-(4
- two or more compounds selected from the group consisting of -thiazolyl)benzimidazole, or N-(trichloromethylthio)-4-cyclohexene-1,2
- An adhesive in which dicarbonimide or N-(fluorodichloromethylthio)phthalimide is added and mixed in a proportion of 0.02 to 2.0% by weight based on the resin solid content in the adhesive is interposed between the copper foil and the laminate. A method for producing a copper-clad laminate having antibacterial properties, the method comprising: heating and press-bonding the copper-clad laminate.