JPH01272623A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition forming little burr in molding and capable of giving a cured material having reduced residual stress without lowering the Tg of the cured material, by using a specific polycondensation product as a modifier to reduce the residual stress of a cured material. CONSTITUTION:The objective silicone resin composition contains preferably 0.5-5wt.% of a substance produced by the hydrolysis and polycondensation of alkoxysilanes [e.g., gamma-(2-aminoethyl)aminopropylmethoxysilane] as a modifier to reduce the residual stress of a cured material.

Description

[Detailed description of the invention] [Industrial application field] TECHNICAL FIELD This invention relates to epoxy resin compositions.

[Conventional technology]

Epoxy resin compositions have conventionally been used as adhesives, laminates, materials for semiconductor devices, and the like in order to construct electronic devices and parts. In particular, recently, there has been an increasing demand for sealing materials for ICs and even LSIs in the electronics field.

Semiconductor devices are becoming denser and have larger chip sizes. When a large chip is sealed with an epoxy resin composition, the stress of the cured product causes problems such as displacement of aluminum wiring and cranking of the passivation layer. For this reason, reducing stress in cured products of epoxy resin compositions has become one of the major challenges.

Therefore, it was considered that the elastic modulus of the cured product could be reduced by introducing an ordinary silicone elastic body into the epoxy resin composition.

[Problem to be solved by the invention]

However, a typical epoxy resin composition containing a silicone elastomer has problems in that it causes flaking during molding and that the Tg of the cured product decreases.

Therefore, an object of the present invention is to provide an epoxy resin composition that can reduce stress in a cured product without impairing moldability or lowering the Tg of the cured product.

[Means to solve the problem]

In order to solve the above problems, the epoxy resin composition according to the present invention uses a product obtained by hydrolyzing and condensing alkoxysilanes as a modifier to reduce stress in the cured product.
(hereinafter also referred to as "hydrolysis/condensation product of alkoxysilane").

[For production]

When the epoxy resin composition contains a product obtained by hydrolyzing and polycondensing alkoxysilanes as a modifier, it is possible to reduce the internal stress of the cured product, and also prevent the generation of flakes during molding. , it is possible to prevent the Tg of the cured product from decreasing.

〔Example〕

The epoxy resin composition of the present invention includes at least an epoxy resin, a curing agent, and a product obtained by hydrolyzing and condensing an alkoxysilane. , for example, is made as follows, but may be made by other methods.

Alkoxysilanes, 0.1 to 5.0 equivalents of oval ice,
Then, a water-soluble solvent for dissolving the alkoxysilanes is added in an amount sufficient to dissolve the alkoxysilanes, and the mixture is stirred at 15 to 80° C. for about 1 hour to about 2 days to react. In this case, it is better to lengthen the reaction time as the temperature is lower. It is then produced by removing the water-soluble solvent and water using an evaporator or the like.

(An example of the reaction of γ-glycyl[xypropyltrimethoxysilane) ↓+H10 (hydrolysis) ↓-H80 (condensation polymerization) 0-Si.

When the product obtained by the reaction as described above is analyzed by IC-NMR, the peak is broad, and
Since it can be seen that functional groups other than alkoxy bonded to St remain, it can be assumed that this is a result of hydrolysis/condensation polymerization of alkoxysilanes, and liquid chromatography analysis indicates that polymerization has occurred. It can be estimated.

The reason why alkoxysilanes are hydrolyzed and polycondensed is used because polymerization increases the length of the chain between the inorganic substance such as silica and the resin, lowering stress and relieving stress. This is because it is effective.

Examples of alkoxysilanes include ■γ-(2-
aminoethyl) aminopropyltrimethoxysilane, ■
γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, ■γ-methacryloxypropyltrimethoxysilane, ■T-glycidoxypropyltrimethoxysilane, ■γ-mercaptopropyltrimethoxysilane,
■Methyltrimethoxysilane, ■Methyltriethoxysilane, ■Vinyltriacetoxysilane, ■γ-anilinopropyltrimethoxysilane, [phase] vinyltrimethoxysilane, ■T-mercaptopropylmethyldimethoxysilane, etc., each individually. Or used in combination of two or more. As the alkoxysilane, it is preferable to use one that does not contain CI, in view of improving the moisture resistance of the cured product. The structural formulas of the compounds (1) to (2) above are shown below.

■NHxCHxCHzNHCIIxCH〜CHzSi
(OCHx) t■ N)IgCHtCHJHCHz
CH low CLSi (OCL) tHI ■ CHg=C-C00CH*CH*CHtSi (O
CHx) *Hs ■ H5CH=CHiCH*5i(OCRs) s■
CHsSi (OCH bulk).

■ CI=Si(OCHtCHs) s■ ◇)NHC
)IxCIzCHzSl (OCHri, [phase] CH
x=CI-5i (QC)I-) *■ H5CHz
CHsCHzSi (QC)Is)zC)Is As the water-soluble solvent, for example, methanol, ethanol, acetone, etc. are used.

The product obtained by hydrolyzing and condensing alkoxysilanes is 0.5 to 5% by weight of the entire epoxy resin composition.
It is preferable that If it is less than 0.5% by weight, the effect of low stress physical properties may not be obtained; on the other hand, if it is 5.0% by weight
If it exceeds , the Tg of the cured product may decrease or problems may arise in moldability.

Examples of the epoxy resin used in the present invention include bisphenol A-based epoxy resins, novolak-based epoxy resins, and alicyclic epoxy resins. When using an epoxy resin composition as a molding material for encapsulating semiconductor elements, etc., it is preferable to use novola-based or 7-based epoxy resins, considering physical properties such as Tg and moisture resistance of the cured product. It is not limited.

As the curing agent, for example, phenol novolak resin, acid anhydride, amines, etc. are used. For the same reason as in the case of epoxy resins, it is preferable to use phenol resins such as phenol novolac resins as the curing agent, but the invention is not limited thereto. As a curing agent, a phenol resin and another curing agent may be used together. The blending ratio of the curing agent is not particularly limited and may be set as appropriate.

The epoxy resin composition of the present invention may contain other substances as necessary in addition to the epoxy resin, the curing agent, and the product obtained by hydrolyzing and polycondensing alkoxysilanes. For example, one or more of a curing aid (or curing accelerator), a filler, an N reagent, a mold release agent, a coloring agent, etc. are blended.

As the curing aid, for example, tertiary amine is used.

As the filler, for example, silica powder, alumina powder, calcium carbonate powder, etc. are used. In addition, when using a filler, it is preferable to make it become 10-80 weight part with respect to 100 weight part of whole epoxy resin compositions. If the amount is more than 80 Jii parts, the cavity may not be completely filled, resulting in poor moldability.

Moreover, if it is less than 10 parts by weight, the coefficient of linear expansion (αl)
This may result in poor heat dissipation.

Examples of flame retardants used include brominated epoxy, antimony trioxide, and hydrated alumina.

As the coupling agent, for example, aminosilane, epoxysilane, mercaptosilane, etc. are used.

Examples of mold release agents include wax, stearic acid,
Stearates, etc. are used.

As the coloring agent, for example, pigments such as carbon black and metal oxides are used.

The above-mentioned essential materials and other additives are not limited to those mentioned above, and those other than those mentioned above can also be used as appropriate.

An epoxy resin composition can be obtained as a molding material by mixing the above-mentioned essential materials and other additives added as necessary, for example, in a mixer, etc., and kneading them using a kneader, rolls, etc. can. After kneading,
If necessary, it may be cooled and solidified, and then pulverized into granules. Note that the hydrolyzed/condensed product of alkoxysilanes may be mixed in advance with the hot-melted epoxy resin, and then mixed with other components. This is preferable from the standpoint of uniformly mixing the hydrolyzed/condensed product of alkoxysilanes and the resin.

Examples and comparative examples of the present invention are shown below, but the present invention is not limited to the following examples.

Examples 1 to 7 - 0-talesol novolac type epoxy resin (WPE=2
00. Average degree of polymerization 4), hydrolysis of alkoxysilane
The polycondensate, curing agent, curing aid, mold release agent, filler, and pigment were mixed in a mixer in the proportions shown in Table 1, and kneaded using a kneader to obtain a molding material.

This molding material was transfer molded at a pressure of 50 kg/mJ and a temperature of 170°C for 3 minutes according to a conventional method, and was cured by after-curing at 170°C for 5 hours. The polymer is the second
It was made as described above under the conditions shown in the table.

A phenol novolac resin was used as a curing agent, 2-ethylimidazole was used as a curing aid, natural carnauba wax was used as a mold release agent, silica powder was used as a filler, and carbon black was used as a pigment.

- Comparative Example 1 - Curing was carried out in the same manner as in Example 1, except that no modifier for reducing stress in the cured product was used.

Comparative Example 2 A product was cured in the same manner as in Example 1, except that alkoxysilane was used as a modifier to reduce stress in the cured product without being hydrolyzed or polycondensed. .

For each of the epoxy resin compositions of the above Examples and Comparative Examples, the occurrence of flakes during molding, wire tension coefficient (α1), glass transition temperature (Tg), and flexural modulus (E) were investigated.

The occurrence of paris during molding was indicated by whether seepage from between the mold slits of lO to 100n was observed (x) or not observed (0).

The coefficient of linear expansion (α1) and the glass transition temperature (Tg) are
It was determined by the TMA method. The flexural modulus (E) was determined using a flexural strength tester.

The results (physical properties) are shown in Table 1 along with the formulation.

As can be seen from Table 1, in the examples, there is no occurrence of paris, and there is no decrease in Tg (α, and E are decreased, that is, stress is reduced).

〔Effect of the invention〕

As described above, the epoxy resin composition according to the present invention is less likely to cause flaking during molding, and can provide a cured product with low stress without lowering the Tg of the cured product.

Agent: Patent Attorney Takehiko Matsumoto

Claims (1)

[Claims] 1. An epoxy resin composition containing a product obtained by hydrolyzing and condensing alkoxysilanes as a modifier for reducing stress in a cured product.