JPS62138523A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition having excellent crack resistance under thermal shock and moisture-resistance and low stress, by compounding an epoxy resin, etc., with a reaction product of a specific synthetic rubber and a silane coupling agent containing thiol group. CONSTITUTION:The objective composition can be produced by compounding (A) an epoxy resin with (B) a curing agent (e.g. phthalic anhydride), (C) a silica filler, (D) a cure accelerator (e.g. organic phosphine compound) and (E) a compound produced by reacting (i) a synthetic rubber (e.g. butadiene rubber) having unsaturated double bond in the skeleton with (ii) a silane coupling agent containing thiol group. The amount of the component E in the composition is 0.1-5(wt)% and that of the coupling agent is >=0.1% of the synthetic rubber.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a low stress epoxy resin composition that has excellent crack resistance when subjected to thermal shock and moisture resistance.1)
Its feature is that it contains a reaction product of a synthetic rubber having an unsaturated double bond in its skeleton and a thiol group-containing silane coupling agent.

[Prior art]

Various low-stress epoxy resin compositions using synthetic rubber have been studied in the past, but both when adding synthetic rubber and when using synthetic rubber-modified epoxy resin, moldability (especially curability, parity) , mold releasability), etc. For example, when a carboxyl group-containing diene-based rubbery polymer is added [JP-A-58-176958]
In this case, not only did the rubber elute and formability was problematic, but it also contained a hydrophilic carboxyl group, resulting in significantly poor moisture resistance. Further, even when a carboxyl group-containing diene rubbery remer is pre-reacted with an epoxy resin, it tends to be thermally decomposed and suffers from the same drawbacks as addition.

Various low stress resin compositions that do not use synthetic rubber are also being studied. For example, a method using silicone-modified resin or adding silicone [JP-A-56-12]
No. 9246, JP-A-58-47014, etc.], but
It not only has the same drawbacks as rubber-modified epoxy 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 ester 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.

That is, since it is used in many different cities and by many different people, it is required to be resistant to rough handling and sudden temperature changes.

[Purpose of the invention]

The present invention is a low-resistance crab made of synthetic rubber, which conventionally had problems with moldability and could not be applied at the market level. As a result of research aimed at improving these drawbacks of silane resins and compositions and developing practical products for application at the industrial level, we found that synthetic rubbers with unsaturated double bonds in their skeletons and silanes containing thiol groups were developed. By adding a reaction product of a coupling agent to an epoxy resin composition, a low-stress epiquino resin composition with excellent moldability, moisture resistance, and crank resistance when subjected to thermal shock can be obtained. This is what I found out.

[(invention)]

The present invention deals with the reaction of (a) niboxy resin (b) curing agent (c) silica filler (d) curing accelerator (e) synthetic rubber having an unsaturated double bond in the skeleton and a thiol group-containing silane curing agent. This is an epoxy resin composition characterized in that it contains 0.1 to 5 % of a compound.

The epoxy resins used in the present invention include bisphenol A epoxy resins, novolak type epoxy resins, alicyclic edoxy resins, and the like. One or more may be used in combination.

Polybasic carboxylic acid anhydride as a hardening agent? Use alone or in combination of two or more. Examples of these include phthalic anhydride, hegisahydrophthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. Alternatively, a phenol novolac resin may be used as a curing agent. The amount of curing agent to be added to the epoxy resin is preferably 0.5 to 1.2 equivalents per 1 epoxy equivalent; anything else may cause serious defects in moldability.

As a curing accelerator, ■ tertiary amine or its derivatives trimethylamine, triethylamine, 2.3.4.6
．． 7.8.9.10-octahydro-pyramide (1,
2-a) Azepine, etc. or quaternary ammonium salts thereof ■Organophosphine compounds (a) Primary, secondary, m3 phosphine Octylphosphine, diphenylphosphine, butylphenylphosphine, tricyclohexylphosphine, triphenylphosphine, etc. (b ) Bemain-type adducts of compounds having organic tertiary phosphine/ and π bonds: maleic anhydride-triphenylphosphine adduct, thioisocyanate-triphenylphosphine adduct, diazodiphenylmethane-triphenylphosphine adduct, etc. (c) Organic Phosphonium salt: Ce3
PCH2n)■C7C).

[J3PEt:I■xc”), (p3PEt)■Br○
etc■Organoaluminum compound (a) kl (OR)3 (R', H, alkyl group,
Aryl group, aryl group-containing hydrocarbon group] Nialuminum impropoxide, aluminum n-phytoxide,
aluminum tert-butoxide, aluminum 5e
c-butyrate, aluminum benzoate, etc. (b)
Beta-diketone complexes of aluminum (aluminum chelate): Aluminum acetylacetonate, aluminum driblioroacetylacetonate, aluminum pentafluoroacetylacetonate, etc.; ■Titanium compounds butyl titanate, titanium white, etc.; ■Acids such as nomuradolenesulfonic 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 epoxy 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, H5C3H6Si (OCH3)3, H8
This includes C3lI6Si(OCH3)2CH3 and the like.

The reaction between the synthetic rubber and the thiol group-containing silane coupling agent can be easily carried out by heating.

The reaction is almost completed by dispersing the thiol group-containing silane cassilling agent in the synthetic rubber and heating it to 100° C. or higher in an air atmosphere. It is preferable to use a thiol group-containing silane coupling agent in a proportion of 0.1% by weight or more based on the synthetic rubber. Can be seen.

By using a reaction product of synthetic rubber and a thiol group-containing silane coupling agent, the stress of the composition itself can be reduced.

By reacting synthetic rubber with a thiol group-containing silane coupling agent, the synthetic rubber can easily form a chemical bond between synthetic rubber, silane coupling agent, and silica in the resin composition, so it cannot be eluted. do not have. Also, due to the formation of this bond, no gaps are created at the silica-synthetic rubber interface.
No deterioration of moisture resistance occurs. 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, resulting in gaps at the silica/synthetic rubber interface that cause the synthetic rubber to elute and deteriorate moldability. There is FA during the period when #humidity deteriorates etc.

In the present invention, the amount of the reaction product of the synthetic rubber and the thiol group-containing silane coupling agent used is preferably 0.1 to 5 thiol groups. If it is less than 1% by weight, the effect of reducing stress will be poor, and if it is more than 5% by weight, mechanical strength will decrease, etc. A decrease in the properties as a xylene resin is observed.

〔Effect of the invention〕

According to the method of the present invention, it is possible to create a low-resistivity mold that has excellent moldability, moisture resistance, and excellent crack resistance when subjected to thermal shock. A xy resin composition can be obtained. In particular, in semiconductor encapsulation applications, it is expected that plastic packaging will become more common in the future, and as a result, lower stress is required for plastics. big.

〔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, humidity, and scratch resistance, and have high added value that can be used industrially.

Example 1 A thiol group-containing silane coupling agent (A-1
89 Japan Nippon Unicar mixed in a ratio of 100:1, 100
C. and stirred for 5 minutes to obtain a reaction product of synthetic rubber and thiol group-containing silane coupling agent. 70 parts of fused silica (Tatsumori Ria) and 0 parts of surface treatment agent (Nippon Unicar A-186)
．． 4 parts were added and mixed using a mixer. More engineering? xy resin (Asahi Ciba: ECN-1273) 20 parts, phenol novolak (Gunei Chemical MP-120) 10 parts, curing accelerator (KAI Kasei PP-360/Shikoku Kasei 2MZ)
= 9/1) 0.2 parts, pigment (Mitsubishi Kasei) 0.5
1 part, 0.4 parts of a mold release agent (Hoechst OP/Hoechst S = 1/1), and 2 parts of a reaction product of synthetic rubber and a thiol group-containing silane coupling agent were added and mixed, and then kneaded in a co-kneader. An epoxy resin composition was obtained.

Comparative Example 1 An Ebixi resin composition was obtained in the same manner as in Example 1 except that 0.05 part of a reaction product of synthetic rubber and a thiol group-containing silane cassilling agent was used.

Comparative Example 2 Synthetic rubber and thiol group-containing silane coupling agent
An epoxy resin composition was obtained in the same manner as in Example 1, except that the following procedure was used.

Example 2 Solid acrylonitrile butadiene copolymer (CHEMIGLJM P83 Good Yeah) as synthetic rubber
r! 8, a thiol group-containing silane coupling agent (A
-189 (manufactured by Nippon Unicar)) was heated to 150° C. while mixing with a mixer at a ratio of iloo to 2 to obtain a reaction product. Using this, an Ebixi resin composition was obtained in the same manner as in Example 1 except for this.

Comparative Example 3 0.4 parts of a surface treatment agent was added to 70 parts of fused silica and mixed with a mixer. In addition, 20 parts of Ebiki side fat, 10 parts of phenol novolac, 0.2 parts of hardening accelerator, 05 parts of pigment,
After adding and mixing 0.4 parts of mold release agent (all the same raw materials as in Example 1) and 2 parts of synthetic rubber (R-45EPT, Idemitsu Petrochemicals), it was mixed in a co-kneader. 2 xy resin composition was obtained.

Comparative Example 4 0.4 part of a surface treatment agent was added to 70 parts of fused silica and mixed with a mixer. Further, 20 parts of niboxy resin, 10 parts of phenol novolac, 0.2 parts of curing accelerator, 0.5 parts of pigment, and 0.4 parts of mold release agent were added and mixed, and then kneaded in a co-kneader to obtain an edoxy resin composition.

As a result of measuring the moldability, crank resistance, moisture resistance, and bending strength of these molding materials, it was found that the examples were superior to the comparative examples. When the usage of synthetic rubber and thiol group-containing silane coupling agent was too large, the bending strength decreased, and when it was too low, the crank resistance was poor.

*1.16 pin DIP k Judgment based on the degree of occurrence of paris on the lead bin when forming ) D *2 TCT 14 wn
(30 minutes) 200 cycles of 5A thermal shock at room temperature (5 minutes) and -150°C (30 minutes) Judging by the number of crank occurrences/total number *3TST, sealing a simulated element with a size between 4 x 6 1 6 pin DIP - 165℃ (2 minutes) 150℃
(2 minutes) 200 cycles of thermal shock and judged by the number of cracks generated / total number * 1 Moisture resistance, 1 6 pi sealed with aluminum simulated element
nDIP i 1000 at 135℃, 100% condition
Determined by defective rate/a number due to aluminum corrosion after hr storage

Claims (1)

[Claims] (a) Epoxy resin (b) Curing agent (c) Silica filler (
d) Curing accelerator (e) Contains 0.1 to 5% by weight of a synthetic rubber having an unsaturated double bond in its skeleton and a reactant of a thiol group-containing silane coupling agent of 0.1% or more by weight of the synthetic rubber. An epoxy resin composition characterized by: