JPH0119834B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a one-component epoxy resin ink composition, and its purpose is to have excellent electrical insulation, moisture resistance, heat resistance, chemical resistance, adhesion, and hardness, and to prevent discoloration of silver and copper. The object of the present invention is to provide a one-component epoxy resin ink composition having anti-migration properties, fast curing at medium to high temperatures of 130 to 200°C, and a long pot life. A so-called thick film is formed by screen printing a desired circuit using silver-based conductors, resistors, capacitors, etc. using glass frit as a binder on an inorganic insulating substrate made of an inorganic material such as ceramic or glass as a base material, and then firing at a high temperature. Hybrid integrated circuits, chip capacitors, resistors, etc., as well as paper-phenol,
A desired circuit is formed by screen printing using silver-based conductors and resistors using phenol resin, epoxy resin, etc. as a binder on a laminated insulating substrate made of organic materials such as paper-epoxy or glass-epoxy as a base material. Printed circuit boards made by baking at medium to high temperatures, and printed circuits in which a desired circuit is formed by etching the copper foil of a copper-clad laminate, which is made by laminating copper foil onto a laminate made of the same organic material as a base material. Conductor circuits etc. formed on the board are
Since it is usually exposed flat on its surface, it is easily affected by the environmental atmosphere. That is, this is an accident caused by corrosion of the conductor circuit portion due to adhesion of conductor-corrosive impurities or moisture contained in the atmosphere to the conductor. In order to prevent accidents caused by such factors and further improve the reliability of the circuit, a method is generally used to form a permanent protective coating called a mask on the circuit by screen printing, etc. In this case, protective coatings are required to have various properties such as electrical insulation, moisture resistance, chemical resistance, adhesion, and hardness. Furthermore, in the thick-film hybrid integrated circuit boards and printed circuit boards, the formed circuits are often minute and complicated, and when plating with nickel, gold, copper, solder, etc., short circuits may occur due to the plating. In order to prevent accidents due to this cause, a protective paint called resist ink is applied by screen printing to areas other than those that require plating, and after curing to form a coating film, apply only to the necessary areas. A method of plating is known,
In this case, the protective coating is required to have functions as an ink, such as viscosity suitable for screen printing, threadability, and thixotropic properties. In addition, as electric and electronic equipment becomes smaller, lighter, and more reliable, printed circuit boards, etc. are required to be smaller, more dense, and more reliable. It is generated by applying a voltage below. Discoloration and migration of silver and copper conductor circuits are becoming a problem. As measures to prevent discoloration and migration of silver and copper conductors, efforts are being made to develop conductor materials, circuit board materials, circuits, and structures.However, regarding protective paints, triazine resin, Except for bismaleimide triazine resin alone or in combination with other resins, almost no useful products have been found. Traditionally, protective coatings with the above-mentioned properties and functions include baking-type glass-based coatings, heat-curing epoxy resin-based, phenolic resin-based, melamine-based, epoxy-melamine-based, silicone-based resins, and ultraviolet-curable resins. Paints of this type are known, but
Except for the glass type, all of them are insufficient in preventing discoloration and migration of silver and copper conductors. Regarding the triazine resin system and the bismaleimide triazine resin system, there are problems in curing conditions (temperature, time), pot life, etc., and it cannot be said that they are in a satisfactory state. In view of these circumstances, the inventors of the present invention have conducted extensive research to develop a protective coating (resist ink) that is one-component, has a long pot life, prevents discoloration and migration of silver and copper conductors, and is We have now discovered an epoxy resin ink composition that has various properties and functions. That is, 100 parts by weight of epoxy resin and filler.
20 to 100 parts by weight and 2-vinyl-4 as a hardening agent.
The desired purpose was achieved by uniformly dispersing and blending 5 to 20 parts by weight of 6-diamino-S-triazine as an essential component. The one-component epoxy resin ink composition according to the present invention can be used as a protective coating (resist ink) for thick film hybrid integrated circuit boards, printed circuit boards, etc., and as an insulating layer for multiple wiring. Epoxy resins suitable for carrying out the present invention include polyglycidyl ethers of polyhydric phenols, such as bisphenol A diglycidyl ether and bisphenol F diglycidyl ether, as well as other epoxidized phenols, novolac resins, epoxidized cresol novolac resins, etc. may be used together. Examples of the filler include barium sulfate, calcium carbonate talc, mica, silica, aluminum hydroxide, etc., and one type or a combination of two or more of these can be used, and the filler is not limited to these. 2-vinyl-4,6-diamino-S-triazine as a curing agent is produced by a method of reacting biguanide with acrylic acid chloride [JACS80988
(1958)], a method for reacting dicyandiamide with β-dimethylamino-propionitrile (French Patent No. 1563255) and 1,2-di{4′,6′-
Method of heating diamino-S-triazinyl-(2)′}-dichlorobutane under reduced pressure (Japanese Patent Publication No. 35068/1983)
The appropriate amount to be added is 5 to 20 parts by weight, preferably 7 to 15 parts by weight, per 100 parts by weight of the epoxy resin. If the amount of 2-vinyl-4,6-diamino-S-triazine is outside the above range and is too small, there will be no effect of preventing discoloration or migration of silver or copper, and the curing speed will be slow, making it impractical. Moreover, if there is too much, the available time will be shortened, which is not preferable. In carrying out the present invention, dicyandiamide or 2,4-diamino-6{2'-methylimidazolyl is used as a co-curing agent in the range of 1 to 5 parts by weight.
(1)'}ethyl-S-triazine/isocyanuric acid adduct or 2,4-diamino-6{2'-methylimidazolyl-(1)'}ethyl-S-triazine can be used in combination; in this case, Curing speed can be adjusted and adhesion can be improved without compromising pot life. In addition, in the composition of the present invention, a coloring pigment may be added for coloring if necessary, and a thixotropy imparting agent for imparting suitability for screen printing,
It is also possible to add antifoaming agents, surface fluidity modifiers, and organic solvents for viscosity adjustment. The curing temperature of the epoxy resin ink composition in the present invention is preferably in the range of 130 to 200°C. The present invention will be specifically explained below using practical examples and comparative examples. The compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were uniformly dispersed and kneaded using a three-roll mill to a grain size of 10μ or less, and numerical units are expressed in parts by weight unless otherwise specified. It is something. Example 1 Epoxy resin "Epicote #828" (manufactured by Yuka Ciel Epoxy) 70 Epoxy resin "Epicote #152" (manufactured by Yuka Ciel Epoxy) 30 2-vinyl-4,6-diamino-S-triazine
10 Talc 10 Barium sulfate 30 Dispersant "Disparon NS-30" (manufactured by Kusumoto Kasei) 2 "Disparon #230" ( ) 0.3 Cellosolve Acetate 3 Example 2 Epoxy resin "YD-128" (manufactured by Toto Kasei) 70 "EOCN-102S" (manufactured by Nippon Kayaku) 30 2-vinyl-4,6-diamino-S-triazine
7 Mica 10 Barium sulfate 30 Elozin #300(5) 2 Dispersant “Disparon #230” (manufactured by Kusumoto Kasei) 0.3 〃 “Disparon #1930 ( ) 0.3 Cellosolve acetate 5 Example 3 Epoxy resin “YD-128” (Toto) (manufactured by Kasei) 70 Epoxy resin “EOCN-102S” (manufactured by Nippon Kayaku) 30 2-vinyl-4,6-diamino-S-triazine
7 2,4-diamino-6{2'-methylimidazolyl-(1)'}ethyl-S-triazine isocyanuric acid adduct 3 Mica 10 Barium sulfate 30 Erosil #300 2 Dispersant "Disparon #230" (Kusumoto Kasei Co., Ltd.) ) 0.3 "Disparon #1930" ( ) 0.3 Cellosolve acetate 5 Comparative example 1 Epoxy resin "YD-128" (manufactured by Toto Kasei) 70 "EOCN-102S" (manufactured by Nippon Kayaku) 30 2,4-diamino -6 {2'-Methylimidazolyl-(1)'} Ethyl-S-triazine isocyanuric acid adduct 7 Mica 10 Barium sulfate 30 Erosil #300 2 Dispersant "Disparon #230" (manufactured by Kusumoto Kasei) 0.3 "Disparon"#1930” ( ) 0.3 Cellosolve Acetate 5 Comparative Example 2 Epoxy resin “YD-128” (manufactured by Toto Kasei) 70 “EOCN-102S” (manufactured by Nippon Kayaku) 30 2,4-diamino-6{2′- Methylimidazolyl-(1)'}ethyl-S-triazine 5 Mica 10 Barium sulfate 30 Erosyl #300 2 Dispersant "Disparon #230" (manufactured by Kusumoto Kasei) 0.3 "Disparon #1900" ( ) 0.3 Cellosolve acetate 5 Above Tables 1 and 2 show the results of performance tests conducted on the compositions obtained by the formulations of Examples and Comparative Examples.

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Claims (1)

[Claims] 1 Characteristic: 100 parts by weight of epoxy resin, 20 to 100 parts by weight of filler, and 5 to 20 parts by weight of 2-vinyl-4,6-diamino-S-triazine as a hardening agent are uniformly dispersed as essential components. A one-component epoxy resin ink composition.