JPS62141018A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition excellent in moisture resistance, cracking resistance, etc., by mixing an epoxy resin with a curing agent, a cure accelerator, an unsaturated double bond-containing synthetic rubber and a silica filler treated with a thiol group-containing silane coupling agent. CONSTITUTION:The purpose epoxy resin composition is prepared by mixing an epoxy resin (e.g., bisphenol A epoxy resin or novolak epoxy resin) with a curing agent (e.g., phthalic anhydride or maleic anhydride), a cure accelerator (e.g., trimethylamine or octylphosphine), a synthetic rubber having unsaturated double bonds in the skeleton (e.g., butadiene rubber) and a reaction product of a silica filler with 0.1wt% or above, based on the silica filler, thiol group- containing silane coupling agent (e.g., formula I or formula II). The obtained low-stress epoxy resin composition can be suitably used for sealing semiconductors.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a low-stress epixy resin composition that has excellent crack resistance and moisture resistance when subjected to thermal shock, and is characterized by its structure having no structure. It contains a synthetic rubber having saturated double bonds, a reaction product of a silica filler, and a thiol group-containing silane coupling agent.

[Prior art]

Conventionally, various low-stress epixy resin compositions using synthetic rubber have been studied, but both when adding synthetic rubber and when using synthetic rubber modified epixy resin, moldability (especially curability) has been improved. There were problems with mold releasability), etc. For example, when a carboxyl group-containing diene rubber IJ polymer is added [JP-A-58-176958
No.] not only had a problem with moldability due to the dissolution of the rubber, but also had extremely poor moisture resistance because it contained a hydrophilic carboxyl group. Further, even when a carboxyl group-containing diene-based rubbery polymer is pre-reacted with an epoxy resin, it tends to be thermally decomposed and has the same drawback as addition.

Various low stress resin compositions that do not use synthetic rubber are also being studied. For example, a method using a silicone-modified resin or adding all silicone [JP-A-56-12]
No. 9246, JP-A-58-47014, etc.], but
It not only has the same drawbacks as rubber-modified epixy resins, but also has the problem of being expensive, that is, lacking in versatility.

Epoxy resin compositions have superior moisture resistance compared to phenolic resin compositions and polyester resin compositions. For example, it is used in circuit boards, semiconductor sealing materials, and the like. Currently, low stress is strongly required in these applications, especially in connection with sealing materials. This is to internationalize the final product, allowing it to be used at any time and place.

In other words, because it is used in many different ways and by many people,
They are required to be resistant to rough handling and rapid temperature changes.

[Purpose of the invention]

The present invention improves these drawbacks of low stress epixy resin compositions made of synthetic rubber, which conventionally had problems with moldability and could not be applied at the market level, and is suitable for application at the industrial level, that is, practical products. As a result of research aimed at developing
By using a synthetic rubber with an unsaturated double bond in its skeleton and a reaction product of a silica filler and a thiol group-containing silane coupling agent, it has the desired moldability, moisture resistance, and resistance to thermal shock. It has been discovered that a low stress epoxy resin composition having excellent crack resistance and the like can be obtained.

[Structure of the invention]

The present invention comprises (a) an epixy resin, (b) a curing agent, (c) a curing accelerator, (d) a synthetic rubber having an unsaturated double bond in its skeleton, (e) a silica filler and a silica filler, 1ii%
This is an epoxy resin composition characterized by containing a reactant of the above thiol group-containing silane cassilling agent.

The epoxy resins used in the present invention include bisphenol A epoxy resins, novolac type epixy resins, alicyclic epixy resins, etc. These epoxy resins can be used alone or in combination of two or more types. May be used.

As the curing agent, polybasic carboxylic acid anhydrides may be used alone or in combination of two or more. Examples of these include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cono-phosphoric anhydride, maleic anhydride, and the like. Alternatively, a phenol novolac resin may be used as a curing agent. The amount of curing agent added to the epixy resin is desirably 0.5 to 1.2 equivalents per 1 epixy equivalent; otherwise, serious defects may occur in moldability.

As a curing accelerator, ■ tertiary amine or its conductor-visitor trimethylamine, triethylamine, 2.3.4.6
．． 7.8.9, l' O-octahydro-pyramide (
1,2-a) Azepine, etc., or these 'vJ4 ammonium salts ■ M-type phosphine compounds (a>1st, u 2.443 phosphine, octylphosphine, diphenylphosphine, butylphenylphosphine, tricyclohexylphosphine, triphenylphosphine, etc.) , (b) Betaine type attached line 'v!lJ' of compounds having all π bonds with organic tertiary phosphine: maleic anhydride-triphenylphosphine adduct, thioisocyanate-triphenylphosphine adduct, diazodiphenylmethane-triphenylphosphine Adducts, etc. (c) Yes + several phosphonium salts “(ρ3PCH2 shell”) ■Ct○, (1213PEt)
■16', (a3PEt, l■Br○etc■organoaluminium compound (a) kt(OR)3 (R:H, alkyl group, aryl group, aryl group-containing hydrocarbon group): aluminum isozoroboxide, aluminum n-butoxide, aluminum tert-butoxide, aluminum sec -
7'Tele-1・, aluminum benzoate, etc. (b)
Beta-diketone complexes of aluminum (aluminum chelate): aluminum acetylacetonate, aluminum trifluoroacetylacetonate, aluminum acetylacetonate, etc., ■ titanium compounds butyl titanate, titanium white, etc., ■ acids such as para-toluenesulfonic acid, etc. be able to.

Synthetic rubbers with unsaturated double bonds in the skeleton include butadiene rubber, imprene rubber, acrylonitrile rubber, copolymers thereof, and rubbers with vinyl groups, hydroxyl groups, or
Refers to modified products that have functional groups such as carboxyl groups, amino groups, and ezoxy groups introduced.

The thiol group-containing silane coupling agent refers to a silane coupling agent having a thiol group and a silanol group or a Si-0-R (R is an alkyl group) group in the molecule. For example, H5C3H6S i (OCH3)3, H
8C3H6Si(OCH3)2a (3 etc. are included in this.

The reaction between the silica filler and the thiol group-containing silane coupling agent can be easily carried out by heating. By completely dispersing the thiol group-containing silane coupling agent in the silica filler and heating it to 100° C. or higher, the silane reaction is almost completed. It is preferable to use the thiol group-containing silane coupling agent in an amount of 0.1 t or more of the silica filler, and if it is less than 0.1 wt %, the moldability and moisture resistance deteriorate.

By using synthetic rubber, a reactant of a silica filler, and a thiol group-containing silane coupling agent, it is possible to achieve both low stress and high moisture resistance. By reacting the thiol group-containing silane coupling agent with the silica filler, a chemical bond between synthetic rubber, silane coupling agent, and silica is easily formed in the resin composition, which prevents the synthetic rubber from eluting. do not have.

Further, due to the formation of this bond, no gap is created at the silica/synthetic rubber interface, and moisture resistance does not deteriorate. When a silane coupling agent other than a thiol type is used, the bond between the synthetic rubber and the silane coupling agent is not formed well, and the synthetic rubber is eluted and the moldability deteriorates. Further, there is a problem that a gap is formed at the silica/synthetic rubber interface, resulting in deterioration of moisture resistance.

The reaction product of the silica filler and the thiol group-containing silane coupling agent can be used as all or part of the base material.

〔Effect of the invention〕

According to the method of the present invention, it is possible to obtain a low-resistance carboxy resin composition that has excellent moldability, moisture resistance, and crack resistance when subjected to thermal shock. especially,
It is expected that plastic groove cages will be used more and more in the future for semiconductor encapsulation applications, and as a result, there is a demand for lower stress in plastics, so the present invention plays an extremely important role in industry.

〔Example〕

The following is an explanation using a study example of a molding material for semiconductor encapsulation. All parts used in the examples are parts by weight. The examples according to the present invention are superior to the comparative examples according to the prior art in terms of moldability, moisture resistance, and crack resistance, and have high added value that can be used industrially.

Example 1 0.5 parts of thiol group-containing silane coupling agent (A-189 manufactured by Nippon Unicar) was added to 100 parts of fused silica (Tatsumori!).
After mixing with a mixer, the mixture was stirred for 5 minutes while heating to 100° C. to obtain a reaction product of fused silica and a thiol group-containing silane coupling agent. To 70 parts of this reaction product, 0.4 part of a surface treatment agent (Nippon Unicar A-186) was added and mixed using a mixer. Furthermore, 20 parts of epixy resin (Asahi Chino <: ECN-1273), 10 parts of phenol novolac (Gunei Chemical MP-120), and a curing accelerator (KII Kasei PP-360/Shikoku Kasei 2MZ = %)
0.2 part, pigment (Mitsubishi Kasei) 0.5 part, mold release agent (Hoechst JAN 2: HEX) OP/Hoechst 5=J) o, 4
and 3 parts of synthetic comb (R-45EPI manufactured by Idemitsu Petrochemical) were added and mixed, and then kneaded in a co-kneader to obtain an epixy resin composition.

Example 2 To 30 parts of the reaction product of fused silica and thiol group-containing silane coupling agent used in Example 1, 40 parts of fused silica (manufactured by lti Mori) was added, and 0 and 4 parts of a surface treatment agent were added and mixed in a mixer. Mixed. Additionally, 20 parts of epoxy resin, 10 parts of phenol novolac, 0.2 parts of curing accelerator, and 0.0 parts of pigment.
5 parts, mold release agent 04 parts, synthetic rubber (CHEMIGUM P
83 (manufactured by Good Year) were added and mixed, and then kneaded in a co-kneader to obtain an epixy resin composition. (For raw materials not specifically described, the same raw materials as in Example 1 were used.) Comparative Example 1 0.05 part of a thiol group-containing silane coupling agent was added to 100 parts of fused silica, mixed with a mixer, and then heated at 100°C.
Stirring was carried out for 5 minutes while heating to obtain a reaction product of fused silica and a thiol group-containing silane coupling agent. Using this reaction product, an epixy resin composition was obtained in the same manner as in Example 1.

(All raw materials were the same as in Example 1) Comparative Example 2 0.4 parts of a surface treatment agent was added to 70 parts of fused silica, and the mixture was mixed with a mixer. Furthermore, 20 parts of epoxy resin, 10 parts of phenol novolak, 0.2 parts of curing accelerator, 05 parts of pigment,
0.4 parts of a mold release agent (all the same raw materials as in Example 1) and 3 parts of synthetic rubber (CTBN 1300 X 8 manufactured by Ube Industries) were added and mixed, and then kneaded in a co-kneader to obtain an epoxy resin composition.

Comparative Example 3 0.4 parts of a surface treatment agent was added to 70 parts of fused silica and mixed with a mixer. Additionally, 20 parts of epoxy resin, 10 parts of phenol novolac, 0.2 parts of curing accelerator, and 140.5 parts of epoxy resin.
1 part, and 0.4 parts of a mold release agent (all the same raw materials as in Example 1) were added and mixed, and then kneaded in a co-kneader to obtain an epixy resin composition.

As a result of measuring the moldability, crack resistance, moisture resistance, and bending strength of these molding materials, it was found that the examples were superior to the comparative examples as shown in the attached table.

Compared to the examples, if synthetic rubber is not used, the crack resistance is inferior, and even if synthetic rubber is used, the amount of reaction of the thiol group-containing silane coupling agent to silica is small, or if the thiol group-containing silane coupling agent is not used. had serious problems with moldability and moisture resistance.

*L 16 pin DIP 'c Determine the degree of tension on the lead bin when forming )D *2TC'r 14 rtrm
30 minutes). Thermal shock from room temperature (5 minutes) to 150°C (30 minutes) was applied for 200 cycles and determined by the number of cracks generated/number of a. 165
℃ (2 minutes) -150℃ (2 minutes) thermal shock is applied for 200 cycles and judged by the number of cracks generated/total number *4 Moisture resistance, 16 pin sealed with aluminum simulated element
DIP was stored at 135℃ and 100% condition for 1000 hours and judged by defective rate/total number due to aluminum corrosion.

Claims (1)

[Claims] (a) Epoxy resin, (b) Curing agent, (c) Curing accelerator, (d) Synthetic rubber having an unsaturated double bond in the skeleton, (e
) An epoxy resin composition comprising a silica filler and a reaction product of a thiol group-containing silane coupling agent in an amount of 0.1% by weight or more of the silica filler.