JPS60123572A - One-pack epoxy resin ink composition - Google Patents

Abstract

PURPOSE:To obtain titled composition with high electrical insulation and moisture resistance, capable of preventing metals such as silver and copper from discoloration or migration, long in the pot life, by incorporating epoxy resin and filler with, as curing agent, vinyl-diamino-triazine through dispersion. CONSTITUTION:The objective composition comprising (A) 100pts.wt. of an epoxy resin such as from bisphenol A diglycidyl ether, (B) 20-100pts.wt. of filler such as barium sulfate and (C) as curing agent, 5-20(pref. 7-15)pts.wt. of 2-vinyl- 4,6-diamino-s-triazine with these components homogeneously dispersed. Incorporation, as cocuring agent, of dicyandiamide etc. in said composition would enable curing rate to be regulated or adhesivity to be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a one-component epoxy resin ink composition, and its purpose is to improve electrical insulation, moisture resistance,
It has excellent heat resistance, chemical resistance, lubricity and hardness, and also has the ability to prevent discoloration and migration of coins and copper, and is also 1!1
It is an object of the present invention to provide a one-component evoki resin ink composition having quick curing properties at medium to high temperatures of 0 to 200'C and a long pot life.

A so-called thick film is formed by screen printing a desired circuit using silver thread 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-
A desired circuit is formed by screen printing using a silver thread conductor and a resistor using a binder such as a phenol resin or ceboxy resin on a laminated insulating substrate made of an organic material such as phenol, paper-epoxy, or glass-epoxy as a base material. Printed circuit boards formed by baking at medium to high temperatures, and copper-clad laminates in which copper foil is laminated to a laminate based on the same organic feather. Conductor circuits formed on a circuit board are usually exposed directly opposite the bottom surface, so
Easily affected by environmental atmosphere. In other words, this is an accident caused by corrosion of the conductor circuit portion due to adhesion of conductor-corrosive impurities and moisture contained in the atmosphere.

In order to prevent accidents caused by such factors and further improve circuit reliability, various performances such as electrical insulation, moisture resistance, chemical resistance, adhesion, and hardness are required for the protective coating film used in screen printing, etc. has been done.

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 due to plating may occur. In order to prevent accidents due to this cause, a protective paint called resist ink is applied by screen printing etc. to areas other than the required areas for plating, and after curing and forming a coating film, it is applied to the necessary areas. There is a known method of plating only
In this case, the retention paint is required to have ink functions such as viscosity, stringiness, and thixotropic properties suitable for screen printing and the like.

In addition, as electrical and electronic equipment becomes smaller, lighter, and more reliable, printed circuit boards are becoming more compact, denser, and more reliable. It is generated by applying a voltage under certain conditions. Discoloration and migration of silver and copper conductor circuits have become problems.

As a measure to prevent discoloration and migration of pots and copper conductors, we have developed new conductor materials, developed circuit board materials,
Although the development of circuits and +1 "structures" etc. has been carried out,
Regarding paints, there are almost no useful ones except triazine resins and bismaleimide triazine resins used alone or in combination with other resins.

Traditionally, protective coatings with the above-mentioned characteristics and functions include baking-type glass-based, heat-curing epoxy resin-based, phenolic resin-based, melamine resin-based, epoxy-melamine resin-based, silicone resin-based, and ultraviolet curing. Type resin-based paints are known, but with the exception of glass-based paints, all of them are insufficient in preventing discoloration and migration of silver and cap conductors.

Regarding the triazine resin system and the bismaleimide triazine resin system, there are also 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 intensive research to develop a coating material that has a long OJ usage time, prevents discoloration and migration of silver and copper conductors, and furthermore provides a protective coating (
We have now discovered an epoxy resin ink composition that has the same properties and functions as a resist ink.

That is, 40 parts of epoxy (100 parts by weight of fat, 20 to too many parts of filler, and 2-vinyl-4,
The desired objective was achieved by uniformly blending 5 to 20 parts of 6-diami-8-triazine as an essential component in fractions.

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 multi-blade single wiring.

Epoxy resins suitable for carrying out the present invention are polyglycidyl ethers of polyhydric phenols, such as bisphenol A diglycidyl ether and bisphenol F diglycidyl ether, and may be used in combination with other epoxidized phenols, novolak resins, epoxidized cresol novolac resins, etc. It's okay.

Fillers include barium sulfate, calcium carbonate talc,
Mica, silica, aluminum IV hydride, etc. can be used alone or in combination of two or more of these, and are not limited to these.

2-vinyl-4,6-diamitsu-triazine as a curing agent can be produced by reacting biguanide with acrylic acid chloride (JAcs80, 98B (+958)), or by reacting dicyandiamide with β-dimethylamino-norovionitrile. (French Patent No. 1,563,25
No. 5) and 1,2-di(4' + 6'-diamino-s
-Triazinyl-(21) -7 It can be produced by heating cloptane under reduced pressure (Japanese Patent Publication No. 4/1973, No. 35068), and the appropriate amount of addition is 5 to 5 parts by weight per 100 parts by weight of epoxy resin. 20i parts by weight, preferably 7 to 15 parts by weight.

If the blending amount of 2-vinyl-4,6-cyamitsu S-) riazine is outside the above range and is too small, there will be no effect of preventing discoloration or migration of silver or helmet, 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 addition, in carrying out the present invention, as a co-curing agent, 1 to
Dicyandiamide or 2,4-diamino-6(gumethylimidazolyl(1)') ether-8 within the range of 5 folds
-) riazine/incyanuric acid adduct or 2,4-diamino-6(gumethylimidazolyl-(1/ethyl-)
8-) It is possible to use riazine in combination, and h) it is possible to improve the W alignment and adhesion during curing without impairing the 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, an antifoaming agent, and a surface flow agent for imparting suitability for screen printing may be added. b
Regulator, viscosity 1. ! It is also possible to add an organic solvent for conditioning.

The curing temperature of the epoxy resin ink composition in the present invention is preferably in the range of 160 to 200''C.

The present invention will be specifically explained below using practical examples and comparative examples.

The compositions of Example 1 and Comparative Examples 1 and 2 were uniformly dispersed using a three-roll mill to a grain size of 10μ or less.
It is a kneaded product, and numerical units are expressed in parts by weight unless otherwise specified.

Example 1 Epoxy resin "Epicoat ≠ 828" (manufactured by Yuka Ciel Epoxy) 70 Epoxy resin "Epicoat ++52J (= ) self 0 2-vinyl-4,6-diabanor S-triazine talc 10 Barium sulfate 30 Dispersant 1 Day Paron NS-ro LJ (4i'a Ki Kasei!
! ! -! ! )〃 [Daysparon+;230J( =
)0,3 Cellosolve acetate 5 Example 2 Epoxy resin [yD. -128J (manufactured by Tobu Kasei) 0 [rcocN-+02. s J (manufactured by Nippon Kayaku) 0 2-vinyl-4.6-cyamitsu s- triazine mica -0 Barium sulfate 30 Elozin 00 (5) 2 Dispersant [Dice Baron = +230J (manufactured by Kusumoto Kasei) 0,
5 〃 [Disparon + 9 + O (/l) 0, 3 Cellosolve acetate 5 Example epoxy resin 1-yp-128J (manufactured by Tobu Kasei) 0 (Epoxy resin [woaN-1 028 J-chome Honkayaku) 0 2 -vinyl-4,6-raremitsu-S-triazine 2,4
-diamino-6(7-methyl f-midazolyl=(1)'
) Ethyl-s-triazine incyanur
3 Mica -0 Barium sulfate Ro0 Erosil 100 2 Dispersant "Disparonji 2, oJ ((r\i Honkasei)
0, 6 "Disparon+.1930" (/l) 0, 5 Cellosolve Acetate 5 Comparative Example 1 Epoxy Resin 1-y: o-128J (Tobu Kasei! I'.
! ! )0 # [woaN-102SJ (Nippon Kayaku) 0 2,4-diamino-6(2'-methylimidazolyl-(
1)') Ethyl-8-triazine/incyanuric acid adduct 7 Mica 10 Barium sulfate 30 Erosil Life 300 2 Dispersant [Disparonkai 250J (Kyokusui Kasei) 0, RO "Disparon ≠ 193oJ (= ) 0.6 Ceronlube acetate 5 Comparative example 2 Epoxy resin "yD-+28J (manufactured by Toto Kasei) 0 [cocN-102SJ (manufactured by Nippon Kayaku) 30 2.4-diamino-6 [coumethylimidazolyl-uf]
) Ethyl-s-triazine 5 Mica 10 Barium sulfate 30 Erosil Φ300 2 minute machining "Disparonkai 250J (Kyokusui Kasei) 0""Disbaronna 1900J (ll 10.5 Ceronlube acetate 5 Above examples and ratios 1 The results of a performance test conducted on the composition obtained by blending !2ff1l are shown in Part 1 and Table 2.

Place about 0.3 f and spread it thinly with a spatula for complete assembly, and the time until no thread is drawn between the spatula and the mixture.

(2) Time until the viscosity reaches twice the initial value as measured by a B-type rotational viscometer.

Table 2 Performance test of cured product (20p thick coating 11α formed by screen printing and cured by heating at 150°C for 15 minutes) (Continued) Note (8) The test piece was heated to 60°C. , humidity 9596, and applied voltage DC 100V.

(4) Etching the copper foil of the NEMA standard When a test piece obtained by screen printing and heat curing was left under the above conditions for 500 hours.

(5) Apply silver powder-phenolic resin paste on a laminate of N M A standard After screen-printing a comb-shaped η4 circuit of Isyts and baking it at a temperature of 150'C for 30 minutes, each formulation I was screen-printed on the circuit, and the test pieces were heat-cured with A and N. When left under the conditions of (3) above for 96 hours.

(6) Screen-print a silver/palladium powder-glass paste on a ceramic substrate into a comb-shaped electrode circuit with a conductor width of 1 inch and a conductor spacing of 0.5/i, and then bake at a temperature of 700°C for 2 hours. , when a test piece obtained by screen printing each side's formulation on the circuit and heat curing it was left for 500 hours under the above dispute (8).

(γ) J engineering 80-210! According to +, the jl and IJ composites on each side were screen printed on an aluminum plate to form a retention film, and then measured.

(8) The test piece prepared by the method of (4) above was
After being immersed in the molten solder bath of 'c for 50 seconds, the appearance of the coating film was observed for blistering, peeling, etc., and a cross-cut peeling test was conducted in accordance with JISD-0202.

(Test piece prepared by the method described in 'aUil (4)?, 10
After 48 hours of immersion in a 10% sulfuric acid solution and a 10% 6% caustic soda solution, the vM test was carried out to determine the change in coating.

4. The test piece prepared by the method described in (4) above was tested according to JISD-0
Negative according to 202>'! i (one ship in 6 history was determined by 4 rivers).

patent applicant Shikoku Kasei Kou Co., Ltd.

Claims (1)

[Claims] Epoch resin 100% hard part, filler 20~100% hardened part and 2-vinyl-4,6-diami2-8- as curing agent.
) A one-component epoxy resin ink composition characterized by uniformly blending 5 to 20 parts by weight of riazine as an essential component.