JPS59170116A - Liquid epoxy resin composition - Google Patents

Abstract

PURPOSE:To provide a liquid epoxy resin composition composed of a liquid epoxy resin, a specific hardener, a flame retardant and an inorganic filler, having excellent moisture resistance and long pot life, and suitable for electronic parts and electronic apparatuses. CONSTITUTION:The objective composition is prepared by compounding (A) a liquid epoxy resin (e.g. phenol novolak epoxy resin, etc.), (B) a reaction product of (i) preferably 100pts.wt. of an aromatic diamine (e.g. diaminodiphenylmethane) with (ii) preferably 1-100pts.wt. of a quaternary phosphonium salt (e.g. tetrabutyl phosphonium acetate), (C) a flame retardant (e.g. hexabromobenzene) and (D) an inorganic filler (e.g. quartz glass). The preferable amounts of the components (B), (C) and (D) are 0.1-30pts.wt., 3-150pts.wt. and 20- 450pts.wt. per 100pts.wt. of the component (A), respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid epoxy resin composition that has extremely excellent moisture resistance and has an extremely long pot life, and is suitable for use in electronic parts and devices.

Epoxy resins have excellent electrical properties, mechanical properties, etc., and are therefore widely used for sealing, impregnation, etc. of electronic components and devices such as semiconductor devices.

However, conventional epoxy resin compositions, especially liquid types, have insufficient moisture resistance, so electronic components sealed with them may lose their insulation properties and increase leakage current as they are used. A major drawback is that the wiring can corrode and break.

As a result of intensive research in order to eliminate the above-mentioned drawbacks, the inventors of the present invention have found that especially 1. The present inventors have discovered that the use of a reaction product of an aromatic diamine and a quaternary phosphonium salt significantly improves moisture resistance and significantly lengthens pot life, leading to the completion of the present invention.

That is, the present invention includes +11 liquid epoxy resin, (2) a curing agent which is a reaction product of an aromatic diamine and a quaternary phosphonium salt, (3) a flame retardant, and (4) an inorganic filler as essential components. It relates to a liquid epoxy resin composition characterized by containing as follows.

The liquid epoxy resin in the present invention is not particularly limited and any known one can be used, such as phenol novolak epoxy resin, cresol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, glycidyl Ether type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, epoxy resin derived by epoxidation of olefin bonds, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, halogenated Epoxy resin, polybutadiene modified epoxy resin, acrylonitrile-butadiene copolymer rubber modified epoxy all, acrolein, epoxy resin derived from phenol and shrimp chlorohydrin, benzaldehyde, epoxy resin derived from phenol and shrimp chlorohydrin, etc. 2 epoxy groups in 1 molecule
At least one of these is used.

In the present invention, aromatic diamine and quaternary
The reaction product with a class phosphonium salt is used. The reaction product is a curing agent newly developed by the present inventor, and its use significantly improves moisture resistance and significantly lengthens pot life.

The reaction product is produced by using usually about 1 to 100 parts by weight of a quaternary phosphonium salt to 100 parts by weight of the aromatic diamine and reacting it at a temperature of about 100 to 150°C for about 10 minutes to 5 hours. , prepared. This reaction is preferably carried out under a nitrogen atmosphere, but may also be carried out in the atmosphere. If the amount of the quaternary phosphonium salt used is less than 1 part by weight, the pot life cannot be extended, and if it exceeds 100 parts by weight, the cost will increase, which is not preferable.

Examples of aromatic diamines that can be used above include m-phenylenediamine, 4,4'-methylenedianiline,
Benzidine, 4,4'-thiodianiline, dianisidine, 2,4-)luenediamine, diaminoditolylsulfone, 4-methoxy-6-methyl-m-phenylenediamine, diaminodiphenyl ether, diaminodiphenylsulfone, 4,4'-bis( 0-) Luizine), 0-
Phenylenediamine, methylenebis(0-chloroaniline), bis(8,4-diaminophenyl)sulfone, 2
Examples include 6-diamitpyridine, 4-chloro-〇-phenylenediamine, m-aminobenzylamine, diaminodiphenylmethane, and xylenediamine. Similarly, examples of quaternary phosphonium salts include methyltrioctylphosphonium dimethylphosphate (MTOP-DMP), tetrabutylphosphonium acetate (T'r5 F A ), and methyltributylphosphonium dimethylphosphate. Phate (MTBP-DMP), benzyltriphenylphosphonium chloride (BTPPC), tetrabutylphosphonium chloride (TBPC'), methyltriphenylphosphonium dimethylphosphate (
MTPP-DMP), triphenylethylphosphonium iodide (TPEPI), and the like.

The amount of the reaction product of aromatic diamine and quaternary phosphonium salt used is 0 to 100 parts by weight of epoxy resin.
．． It is 1 to 80 parts by weight. If the amount is less than 0.1 parts by weight, the moisture resistance will not be improved, and if it exceeds 80 parts by weight, the pot life will be shortened.

In the present invention, a curing accelerator may be used in combination in order to adjust the curing speed or to ensure sufficient curing. Examples of curing accelerators include benzyldimethylamine, triethanolamine, dimethylaminomethylphenol,
Tris(dimethylaminomethyl)phenol, triethyltetramine, 3.9-bis(8-aminopropyl)-
8.8-tertiary amines such as 2,4゜8.10-tetraoxaspiro(5,5)undecane, 1,8-diaza-bicyclo(5,4,0)undecene-7 or its phenol or organic acid derivative; 1.2.8-benzotriazole,
Triazoles such as 5-methyltriazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecyl Imidazole, ■-vinyl-2-methylimidazole, 2-phenyl-4゜5-dihydroxymethylimidazole, 2-phenyl-4-methylimidazole, 2-isopropylimidazole, 1
-2-methylimidazole, 2,4-diamino-6-[2'-methylimidazolehy(ge-ethyl]-sym-)riazine or its incyanuric acid adduct, 2,4-diamino-6-[ imidazoles such as 2'-undecylimidazolyl-(1)'-ethyl]-sym-triazine or its incyanuric acid adduct, aluminum, titanium, zinc, zircon, nickel, iron, lead,
Examples include acetylacetonates of metals such as cerium, manganese, magnesium, cobalt, copper, chromium, vanadium, uranium, thorium, strontium, sodium, potassium, and beryllium, or derivatives thereof;
At least one of these is used. When using these curing accelerators together, the amount used is epoxy resin 100
Appropriately, the amount is about 10 parts by weight or less. 10
Exceeding parts by weight will result in poor storage stability (short pot life)
Become.

As the flame retardant used in the present invention, a wide variety of known flame retardants can be used, such as hexabromobenzene, antimony dioxide, tetrabromobisphenol A1 hexabromobiphenyl, decachlorobiphenyl, red phosphorus, etc. One type is used. The amount of flame retardant used is 3 to 15 parts by weight per 100 parts by weight of epoxy resin.
0 parts by weight is suitable. If the amount is less than 8 parts by weight, no flame retardant effect can be expected.

In addition, in the present invention, the moisture resistance is improved, the expansion coefficient is reduced,
A wide range of known inorganic fillers can be used to improve thermal conductivity, such as quartz glass,
Crystalline silica, fused silica, glass fiber, talc, alumina, hydrated alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, zirconium silicate,
Examples include clay and mica, and at least one of these is used. These inorganic fillers are preferably used in powder form. The appropriate amount of the inorganic filler to be used is 20 to 450 parts by weight per 100 parts by weight of the epoxy resin. If it is less than 20 parts by weight, no reduction in the expansion coefficient can be expected.

Moreover, if it exceeds 450 parts by weight, the melt viscosity becomes extremely high, making it difficult to use.

Furthermore, in the present invention, in addition to the above-mentioned components, additives commonly used in this type of composition, such as colorants such as carbon black, red iron, and phthalocyanine green,
Moisture resistance and adhesion improvers such as silane coupling agents and titanium-based camping agents, thixotropic agents (thickeners) such as finely powdered silica and finely powdered calcium carbonate, antifoaming agents such as silicone oil, etc. It may be added in combination.

The liquid epoxy resin composition of the present invention is prepared using the above-mentioned components according to a conventional method. In addition, its use is not particularly limited and can be applied to a wide range of areas, but it is particularly suitable for sealing electronic parts and electronic equipment, and the molding method for this type of composition is For example, casting, potting, encapsulation, injection molding, compression molding, hot press molding, sealing, pressure and heat molding, hot roll molding, transfer molding, far infrared curing adhesive, etc. Furthermore, it can be used for impregnation by dissolving it in a suitable solvent such as methyl ethyl ketone, styrene monomer, butyl carbinol, etc.

The liquid epoxy resin composition of the present invention has extremely excellent moisture resistance l+ (I) and has an extremely long pot life due to the use of the specific curing agent. Advantages include automation, complete degassing, no loss due to runners, culls, etc., and no defects due to deformation of lead wires of electronic parts, etc.

The liquid epoxy resin composition of the present invention can be applied to a wide range of electronic components and devices without any particular limitations, such as integrated circuits (ICs), large-scale integrated circuits (LSIs, VLSIs), Hybrid IC (
HIC), transistors, thyristors, diodes,
Examples include optical semiconductor devices (LEDs), capacitors, coils, transformers, resistors, insulators, sockets, cases, connectors, baristas, etc. In addition to electronic applications, it can also be applied to optical fiber adhesion, various other mechanical parts, various containers, etc.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Examples 1-2 and Comparative Examples 1-2 100 parts by weight of diaminodiphenylmethane and 50 g parts of tetrabutylphosphonium acetate were reacted at 120°C for 1 hour in a nitrogen atmosphere, and then cooled to produce a pale yellow reaction product. Obtained.

Using the above reaction product or diaminodiphenylmethane or phenol novolac resin as a curing agent, liquid epoxy resin compositions of the present invention and comparisons having the compositions shown in Table 1 below (however, only Comparative Example 2 is in solid form) were prepared. did.

Table 1 All numerical values in the table indicate parts by weight.

Note 1) Yuka Shell Epoxy Co., Ltd. 'N r x Hi:
1-)828J.

2) rEOCN-1 manufactured by Nippon Kayaku Co., Ltd. 3) rMP-L20j manufactured by Gunei Chemical Industry Co., Ltd.

4) 1-KBM-403j manufactured by Shin-Etsu Chemical Co., Ltd.

Next, each component was stirred as a whole at 80° C. in a vacuum state using a planetary mixer, then taken out, and an integrated circuit component on a ceramic substrate was cast using a dispenser.
It was cured at 100° C. for 1 hour and then at 150° C. for 3 hours to obtain a resin-sealed semiconductor device.

However, only in the case of Comparative Example 2, the resin-sealed semiconductor device was obtained by transfer molding at 170° C. under a pressure of 80 Ky/cm 2 for 2 minutes and curing at 150° C. for 5 hours.

Next, the gelation time, pot life, and yield of each of the compositions obtained above, as well as the moisture resistance of each resin-sealed semiconductor device, deformation of lead wires, and generation of bubbles were investigated. The test method is shown below.

■Gelation time ・Place 1y of sample on a hot plate at 150℃,
Stir with a metal rod. The time (seconds) until stirring became impossible due to gelation was measured, and this was taken as the gelation time.

○Pot life: When stored in a sealed container at a temperature of 23℃ and a humidity of 60% or less, the time until the gelation time at 150℃ becomes 1/2 of the initial value ( (days) was defined as the pot life.

Q yield was determined by the following formula.

Total amount of composition used Moisture resistance: Evaluated by pressure Kutzker test (PCT). That is, 30 resin-sealed semiconductor devices were heated at 20v11000 under high-pressure steam at 120°C.
Disconnection due to corrosion of aluminum wiring was investigated when time was applied.

○Deformation of lead wire...30 names of each resin-sealed semiconductor device
The deformation of the lead wire was examined using X-rays.

- Generation of bubbles: The generation of bubbles was examined for each of the 30 resin-sealed semiconductor devices by external appearance and X-rays.

The results of each test are shown in Table 2 below.

Table 2 (that's all)

Claims (1)

[Claims] ■ Contains (1) liquid epoxy resin, (2) curing agent which is a reaction product of aromatic diamine and quaternary phosphonium salt, (3) flame retardant, and (4) inorganic filler as essential components. A liquid epoxy resin composition characterized by: